ELECTRO-ANALYTICAL

METHODS

Dr. A. Waseem
Department of Chemistry
QaU, Islamabad
Classical Methods of Analysis
Early years of chemistry
• Separation of analytes by precipitation, extraction,
or distillation.
• Qualitative analysis by reaction of analytes with
reagents that yielded products that could be
recognized by their colors, boiling or melting points,
solubilities, optical activities, or refractive indexes.
• Quantitative analysis by gravimetric or by
titrimetric techniques.

Waseem
Instrumental Methods
• Measurement of physical properties of analytes
such as conductivity, electrode potential, light
absorption or emission, mass-to-charge ratio,
and fluorescence-began to be employed for
quantitative analysis of inorganic, organic, and
biochemical analytes
• Efficient chromatographic separation
techniques are used for the separation of
components of complex mixtures.
• Instrumental Methods of analysis (collective
name for newer methods for separation and
determination of chemical species.)
 ElectroChemistry
❖Electrochemistry is a branch of chemistry that
studies chemical reactions which take place in
a solution at the interface of an electron
conductor (a metal or a semiconductors) and
an ionic conductor (the electolyte), and which
involve electron transfer between the electrode
and the electrolyte or species in solution.
❖Alessandro Volta's discovery, in 1793, that
electricity could be produced by placing two
dissimilar metals on opposite sides of a
moistened paper.
❖In 1800, Nicholson and Carlisle, using Volta’s
primitive battery as a source, showed that an
electric current could decompose water into
oxygen and hydrogen.
❖By 1812, the Swedish chemist Berzelius could propose that
all atoms are electrified, hydrogen and the metals being
positive, the nonmetals negative.

❖Humphry Davy prepared the first elemental sodium by

electrolysis of a sodium hydroxide melt.

❖Michael Faraday, to show that there is a direct relation

between the amount of electric charge passed through
the solution and the quantity of electrolysis products.

❖Chemical reactions where electrons are transferred

between molecules are called oxidation/reduction
(redox) reactions. In general, electrochemistry deals with
situations where oxidation and reduction reactions are
separated in space or time, connected by an external
electric circuit to understand each process.
 Michael Faraday
(September 22, 1791 – August 25,
1867) was a British scientist (a
physicist and chemist) who
contributed significantly to the
fields of electromagnetism and
electrochemistry.
Alessandro Giuseppe Antonio Anastasio
André-Marie Ampère
Volta

VOLTA, AMPERE AND OTHER SCIENTISTS CONTRIBUTED A LOT TO THE

D E V E L O P M E N T O F E L E C T R O C H E M I S T R Y
 FARADAY’S LAWS OF ELECTROLYSIS
(REVIEW)
❖The laws, which govern the deposition of substances (In the form of ions)
on electrodes during the process of electrolysis, is called Faraday's laws
of electrolysis. These laws given by Michael Faraday in 1833.

❖Faraday's first law: It states that, the mass of any substance deposited or
liberated at any electrode is directly proportional to the quantity of
electricity passed.
WαQ
W = Mass of ions liberated in gm,
Q = Quantity of electricity passed in Coulombs
= Current in Amperes ( i ) × Time in second (t)

Wαit
W=Zit

Where, Z = constant, known as electrochemical equivalent (ECE) of the ion

deposited
❖Faraday's second law: It states that, when the same quantity of
electricity is passed through different electrolytes, the masses of different
ions liberated at the electrodes are directly proportional to their chemical
equivalents (E=Equivalent weights).

❖ WαE

W1/W2 = E1/E2 or Z1it / Z2it or Z1/Z2 = E1/E2 (W = Zit)

Thus the electrochemical equivalent (Z) of an element is directly

proportional to its equivalent weight (E), i.e.,
E α Z or E = FZ or E = 96485 × Z

❖Faraday's law for gaseous electrolytic product for the gases, we use
V = It Ve/96500
Where, V = Volume of gas evolved at S.T.P. at an electrode
Ve = Equivalent volume = Volume of gas evolved at an electrode at S.T.P.
by 1 Faraday charge
Electrical charge is the basis of the other electrical quantities,
current, voltage, and power. The charge on an electron (and
proton) is defined as 1.6022x10-19 coulombs (C). A rate of charge
flow equal to one coulomb per second is the definition of one
ampere (A) of current. Thus, a coulomb can be considered as
that charge carried by a constant current of one ampere for one
second. The charge Q that results from a constant current of (I)
amperes operated for (t) seconds:

(The coulomb (C) is the amount of charge required to produce

0.00111800 g of silver metal from silver ions. 1 C=1amperex1s)
One faraday equals to F=96,485 C. Faraday’s law relates the
number of moles of the analyte nA to the charge Q.

∴ (grams)(n) / formula wt. = It / 96485

(moles of analyte nA=mass gm/fwt)

 Electroanalytical Chemistry
A group of quantitative analytical methods that
are based upon the electrical properties
(electrical response) of a solution of the analyte
(chemical system) when it is made part of an
electrochemical cell.
Chemical System: Electrolyte; measuring
electrical circuit; Electrodes
 USES OF ELECTROANALYTICAL CHEMISTRY

• Electroanalytical techniques are capable of

producing very low detection limits.
• Electroanalytical techniques can provide a lot
of characterization information about
electrochemically addressable systems.
• Stoichiometry and rate of charge transfer.
• Rate of mass transfer.
• Extent of adsorption or chemisorption.
• Rates and equilibrium constants for
chemical reactions.
ADVANTAGES COMPARED TO OTHER METHODS

• Inexpensive

• Used for ionic species not total concentration

• Responds to ionic activity rather than

concentration

• Ion selective electrodes and developing of the

measuring devices in voltammetry made wider
spread of the methods
• SELECTIVITY AND SPECIFICITY (From the
choice of electrode and potential)
• HIGH SENSITIVITY AND LOW DETECTION
LIMIT
• READY TO USE COMPACT INSTRUMENTS
• SPEED AND ACCURACY
• NO TECHNICAL SKILL REQUIRED
ALL THE FREE ENERGY FOR LIFE PROCESS COMES
FROM AN ELECTRON TRANSFER PROCESS
O2 + 4e + 4H+ → 2H2O
A RESTING HUMAN WILL USE ~ 0.2 L O2 /MIN ~
9mmol oF O2 ~ 36 mmol OF ELECTRONS/MIN ~
0.6 mmol OF ELECTRONS PER SECOND ~
60 AMPERES OF CURRENT.
THE MAIN CURRENT PANEL IN MANY HOUSES
HAVE ONLY A CAPACITY AROUND THIS.
 Types of Electroanalytical Procedures

• Based on relationship between analyte

concentration and electrical quantities such
as current, potential, resistance (or
conductance), capacitance, or charge.
• Electrical measurement serves to establish
end-point of titration of analyte.
• Electrical current converts analyte to form
that can be measured gravimetrically or
volumetrically.
 METHOD MEASUREMENT PRINCIPLE Det. limit COMMENTS
APPLICATIONS
Voltammetry Current as a Quantitative analysis of 10-1-10 –3 A large number of
(Polarography) function of voltage electrochemically ppm voltage programs may
(amperometric at a polarized reducible organic or be used. Pulse Polarg.
titrations) electrode inorganic material and DPP improve
chronoamperometry detection limits.
Potentiometry Potential at 0 Quantitative analysis of 10-2 -102 Measures activity
(potentiometric current ions in solutions, pH. ppm rather than
titration) concentration.
(chronopotentiometry
Conductimetry Resistance or Quantification of an Commonly used as a
(conductometric conductance at inert ionized species, detector for ion
titrations) electrodes titrations chromatography.
Coulometry Current and time as Exhaustive electrolysis 10-9 -1 g High precision
number of Faradays possible.

Anodic Stripping Weight Quantitative trace 10-3 -103 g Electrodeposition step

Voltammetry analysis of provides improved
(Electrodeposition) electrochemically detection limits over
reducible metals that normal voltammetry.
form amalgams with
mercury
 Summary of Common Electroanalytical Methods

Quantity measured in parentheses.

I = current, E = potential, R = resistance,
G = conductance, Q = quantity of
charge, t = time, vol = volume of a
standard solution, wt = weight
of an electrodeposited species
• Electrochemistry - study of redox processes at interfaces
Oxidant = oxidizing agent
• reactant which oxidizes another reactant and which is
itself reduced
Reductant = reducing agent
• reactant which reduces another reactant and which is
itself oxidized
TYPES OF CELLS
ELECTROCHEMICAL CELLS
CONSISTS OF TWO CONDUCTORS (CALLED ELECTRODES)
EACH IMMERSED IN A SUITABLE ELECTROLYTE SOLUTION.

FOR ELECTRICITY TO FLOW:

THE ELECTRODES MUST BE CONNECTED EXTERNALLY BY

MEANS OF A (METAL) CONDUCTOR.

THE TWO ELECTROLYTE SOLUTIONS ARE IN CONTACT TO

PERMIT
MOVEMENT OF IONS FROM ONE TO THE OTHER.
Electrochemical Cells

• Cathode is electrode at which reduction

occurs.
• Anode is electrode at which oxidation
occurs.
• Indicator and Reference electrodes
• Junction potential is small potential at the
interface between two electrolytic solutions
that differ in composition.
 GALVANIC AND ELECTROLYTIC CELLS

• Galvanic cells produce electrical energy.

• Electrolytic cells consume energy.
• If the cell is a chemically reversible cell,
then it can be made electrolytic by
connecting the negative terminal of a
DC power supply to the zinc electrode
and the positive terminal to the copper
electrode.
Galvanic Cells
ELECTROLYTIC CELLS
 STANDARD HYDROGEN ELECTRODE (SHE)
To develop a useful list of relative half-cell or electrode
potentials, we must have a carefully defined reference electrode
that is adopted by the entire chemical community. The standard
hydrogen electrode, or the normal hydrogen electrode, is such a
half-cell. Hydrogen gas electrodes were widely used in early
electrochemical studies not only as reference electrodes but
also as indicator electrodes for determining pH. The composition
of this type of electrode can be represented as
Pt, H2,(p atm) / H+(xM) //
The terms in parentheses suggest that the potential at the
platinum surface depends on the hydrogen ion activity of the
solution and on the partial pressure of the hydrogen used to
saturate the solution. The hydrogen electrode may act as the
positive or the negative electrode, depending on the half-cell
with which it is coupled with the salt bridge. When the cell is
short circuited, hydrogen is oxidized to hydrogen ions when the
electrode is an anode; the reverse reaction takes place when the
electrode is a cathode. Under proper conditions, then, the
hydrogen electrode is electrochemically reversible.
 SHE
The potential of a hydrogen electrode
depends on the temperature, the hydrogen
ion activity in the solution, and the pressure of
the hydrogen at the surface of the electrode.
Values for these experimental variables must
be defined carefully for the half-cell to serve
as a reference, Specifications for the standard
hydrogen electrode (SHE) call for a hydrogen
ion activity of unity and a partial pressure for
hydrogen of exactly one atmosphere. By
convention, the potential of this electrode is
assigned the value of exactly zero volt at all
temperatures.
SHE
Measurement of the electrode potential for an M electrode. If the Mn+ ion activity
in the right-hand compartment is 1.00, the cell potential is the standard electrode
potential of the half-reaction Mn+ (aq)+ ne- ⇌ M (s).
ELECTRODE POTENTIAL AND STANDARD ELECTRODE POTENTIAL
Electrode potentials are defined as cell potentials for a cell
consisting of the electrode in question behaving as the
cathode and the standard hydrogen electrode acting as the
anode. The cell in Figure above illustrates the definition of the
electrode potential for the half-reaction:
M+ + e- ⇌ M(s)
In the figure shown above, the half-cell on the right consists of
a strip of the metal M in contact with a solution of M+. The half-
cell on the left is a SHE. By definition, the potential E observed
on the voltmeter is the electrode potential for the M+/M
couple. In this general example. we assume that the junction
potentials across the salt bridge are zero. If we further assume
that the activity of M2+ in the solution is exactly 1.00, the
potential is called the standard electrode potential for the
system and is given the symbol EO That is, the standard
electrode potential for a half-reaction is the electrode
potential when the reactants and products are all at unit
activity.
STANDARD ELECTRODE POTENTIALS
If M is cadmium, and the solution has a cadmium ion
activity of 1.00, the potential is observed to be -0.403 V. In
this case, the cadmium electrode is negative, and the cell
potential has a negative sign. The spontaneous cell reaction
would be

And we may write

The standard electrode potentials for the four half-cells just

described can be arranged in the following order:
SIGN CONVENTION FOR ELECTRODE
POTENTIALS
It is perhaps not surprising that the choice of sign
for electrode potential has led to much
controversy and confusion in the course of the
development of electrochemistry. In 1953, The
IUPAC meeting in Stockholm, attempted to
resolve this controversy. The sign convention
adopted at this meeting is called IUPAC
convention.
Any sign convention must be based upon half-cell
processes written in a single way, i.e, entirely as
oxidation or reductions. According to IUPAC
convention the term electrode potential (or more
exactly, relative electrode potential) is reserved
exclusively for half-reaction written as reductions.
THE STANDARD ELECTRODE POTENTIAL, E˚
If the reactants and products are in their standard states, the resulting cell
potential is called the standard cell potential. This latter quantity is related
to the standard free energy change for the reaction and thus to the
equilibrium constant by

The standard electrode potential is an important physical constant that

provides quantitative information regarding the driving force for a half-
cell reaction. The important characteristics of these constants are the
following:
1. The standard electrode potential is a relative quantity in the sense that it
is the potential of an electrochemical cell in which the reference
electrode (left-hand electrode) is the standard hydrogen electrode,
whose potential has been assigned a value of 0.000 V.
2. The standard electrode potential for a half-reaction refers exclusively to
a reduction reaction; that is, it is a relative reduction potential.
3. The standard electrode potential measures the relative force tending to
drive the half-reaction from a state in which the reactants and products
are at unit activity to a state in which the reactants and products are at
their equilibrium activities relative to the standard hydrogen electrode.
4. The standard electrode potential is independent of the number of
moles of reactant and product shown in the balanced half-reaction.
Thus, the standard electrode potential for the half-reaction.

5. A positive electrode potential indicates that the half-reaction in

question is spontaneous with respect to the standard hydrogen
electrode half-reaction. That is, the oxidant in the half-reaction is a
stronger oxidant than is hydrogen ion. A negative sign indicates just
the opposite.
6. The standard electrode potential for a half-reaction is temperature
dependent.
Standard electrode potential data are available for an
enormous number of half- reactions. Many have been determined
directly from electrochemical measurements. Others have been
computed from equilibrium studies of oxidation/reduction systems and
from thermochemical data associated with such reactions.
Schematic Representation of Electrochemical Cells
NERNST EQUATION
OR For a system

aOx + ne ⇋ bRed
𝑜2.302RT [Red]b
E=𝐸 − 𝑙𝑜𝑔
nF [Ox]a

OR

𝑜
0.059 a Red b
𝐸=𝐸 − 𝑙𝑜𝑔
n 𝑎 𝑂𝑥𝑎
Ox=oxidant
Red=reductant
a= activities
 CALCULATING HALF-CELL
POTENTIALS FROM EO VALUES
We illustrate typical applications of the Nernst equation to
calculate half-cell potentials with the following examples.
What is the electrode potential for a half cell consisting of
Cd electrode immersed in 0.015M Cd2+ solution?
Cd +2e ⇋ Cd(s) Eº = -0.403V
Solution:
we assume the aCd2+ ion = [Cd2+ ]
0.059 a Red b
𝑬 = 𝑬𝒐 − 𝒍𝒐𝒈
n 𝒂 𝑶𝒙𝒂
0.059 1
E𝑪𝒅𝟐+ = −0.403 − 𝑙𝑜𝑔
2 0.015
= − 0.457V
The sign for the potential calculated in above Example indicates the direction of
the reaction when this half cell is coupled with the SHE. The fact that it is
negative shows that the reaction: Cd(s) + 2H+ ⇋ H2(g) + Cd2+
occurs spontaneously. Note that the calculated potential is a larger negative
number than the standard electrode potential itself. This follows from mass-law
considerations because the half-reaction, as written, has less tendency to occur
with the lower cadmium ion concentration.

Example: Calculate the potential for a platinum electrode immersed in a

solution prepared by saturation a 0.015M solution of KBr with Br2.

Br2(l) + 2e ⇋ 2Br- Eº = 1.065V

Notice that the (l) indicates that the aqueous solution is saturated with liquid
Br2, so the overall process would be the sum of two processes.

Br2(l) ⇋ Br2(aqsatd)
Br2(aqsatd) + 2e ⇋ 2Br- Assuming that the activity Br- = [Br-]

0.059 (0.015)2
E𝑩𝒓𝟐 = −1.065 − 𝑙𝑜𝑔 = 1.173V
2 1.00
 CALCULATION OF CELL POTENTIALS
FROM ELECTRODE POTENTIALS
An important use of standard electrode potentials is the
calculation of the potential of a galvanic cell or the
potential required to operate an electrolytic cell. These
calculated potentials (sometimes called thermodynamic
potentials) are theoretical in the sense that they refer to cells
in which there is no current. Additional factors must be taken
into account when there is a current in the cell. Furthermore,
these potentials do not take into account junction potentials
within the cell. Normally, junction potentials can be made
small enough to be neglected without serious error.

Ecell = Ecathode – Eanode or Ecell = Eright – Eleft

where Eright & Eleft are the electrode potentials for the two
half-reactions constituting the cell.
Consider the hypothetical cell:
Zn/ZnSO4(a=1.00) IICuSO4 (a= 1.00)/Cu
Because the activities of the two ions are both 1.00,
the standard potentials are also the electrode
potentials. Thus, using the data from Table, Ecell can
be calculated as:
Ecell = ECu – EZn
= +0.337 - (-0.763) = + 1.100V

The positive sign for the cell potential indicates that

the reaction
Zn(s) + Cu2+ ⇋ Zn2+ + Cu(s)
occurs spontaneously under standard conditions,
and elemental zinc is oxidized to zinc(Il) and
copper(II) is reduced to metallic copper.
What happens to Ecell when we reverse the position?
 CURRENTS IN ELECTROCHEMICAL CELLS
Only one general type of electroanalytical method is based on
measurements made in the absence of appreciable current:
potentiometric methods. which were discussed later. The remaining
electroanalytical methods, all involve electrical currents and current
measurements. Thus. we must discuss the behavior of cells with
significant currents. As noted earlier. electricity is carried within a cell by
the movement of ions. With small currents, Ohms law is usually obeyed
and we may write E = IR, where E is the potential difference in volts
responsible for movement of the ions, I is the current in amperes, and R
is the resistance in ohms of the electrolyte to the current. The resistance
depends upon the nature and concentrations of ions in the solution.
When there is a direct current in an electrochemical cell, the measured
cell potential is usually differs from the thermodynamic potential
calculated. This difference can be attributed to a number of phenomena,
including ohm resistance and several polarization effects, such as
charge transfer overvoltage, reaction overvoltage, diffusion overvoltage,
and crystallization overvoltage. Generally, these phenomena reduce the
voltage of a galvanic cell or increase the voltage required to produce
current in an electrolytic cell.
Faradaic and Non-Faradaic Processes

Faradaic Process
• Charge is transferred across the electrode
solution interface. Redox process takes place
Non-Faradaic Process
• A transitory changes in current or potential as a
result of changes in the structure of the
electrode-solution interface e.g adsorption
• The electrode may be in a potential region
that does not facilitate occurrence of a
charge transfer reaction. The process is
thermodynamically or kinetically unfavorable
• Faradaic Process
When a substance is added to the electrolyte and it is
oxidized or reduced at a particular potential the
current flows and the electrode is depolarized, (Non-
polarizable electrode). The substance is called
“Depolarizer”
• Reversible Process
When the Faradaic process is rapid, oxidized and
reduced species will be in equilibrium and the Nernst
equation is applicable. The process is then reversible.
The electrode is called reversible electrode.
• Reversibility and irreversibility depends upon
* Rate of electrode process
* Rapidity of the electrochemical measurement
 Charging Current

When a dc potential is
applied across the
electrochemical cell, a
momentary surge of
currents is observed,
which rapidly decays to
zero. This current is called
the charging current that
creates an excess of
deficiency of negative
charge at the surface of
the two electrodes.
 ELECTRICAL DOUBLE LAYER

As a consequence of ionic
mobility, however, the layer of
the solution immediately
adjacent to the electrode
acquire an opposing charge
(figure). This assemblage of
charge at the electrode surface
and in the solution adjacent to
the surface is termed as an
electrical double layer.
 EFFECTS OF CURRENT ON CELL
POTENTIALS
When a direct current develops in an
electrochemical cell, the measured cell
potential normally departs from that derived
from thermodynamic calculations. This
departure can be traced to a number of
phenomena including ohmic resistance and
several other polarization effects such as
charge-transfer, reaction, diffusion and
crystallization overvoltage. Generally, these
phenomena reduce the voltage of a galvanic
cell or increase the voltage required to
produce current in an electrolytic cell.
 OHMIC POTENTIAL; IR DROP
To develop a current in either a galvanic or an
electrolytic cell. a driving force in the form of a
voltage is required to overcome the resistance of
the ions to movement toward the anode and the
cathode. Just as in metallic conduction, this force
follows Ohm's law and is equal to the product of
the current in amperes and the resistance of the
cell in ohms. This voltage is generally referred to as
the ohmic potential, or the IR drop. The net effect
of IR drop is to increase the potential required to
operate an electrolytic cell and to decrease the
measured potential of a galvanic cell. Therefore.
the IR drop is always subtracted from the
theoretical cell potential. That is:
Ecell = Ecathode – Eanode – IR
 POLARIZATION
“Departure of cell behavior from
thermodynamic calculations”
Ideally polarized electrode
Electrodes at which no charge transfer
takes place. Only nonfaradaic process
takes place regardless of the applied
potential.
• E.g. Hg electrode in contact of NaCl
solution at pot. 0 to –2 V.
•Or the one in which current remains
constant and independent of potential
over a considerable range.
 POLARIZATION
Figure (a) is a current-voltage curve for an electrode that
is ideally polarized in the region between A and B. Figure
(b) shows the current-voltage relationship for a
nonpolarized electrode that behaves ideally in the region
between A and B. For this electrode, the potential is
independent of the current.
 POLARIZATION
Figure below is 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 current-voltage curve has a finite slope
equal to R rather than the infinite slope for the ideal nonpolarized
electrode shown in Figure b above, and it obeys Ohm's law. Beyond
points A and B, polarization occurs at one or both electrodes, resulting in
deviations from the ideal straight line.
The upper half of the curve gives
the current-voltage relationship
when the cell is operating as an
electrolytic cell; the lower half
describes its behavior as a
galvanic cell.“ Note that when
polarization occurs in an
electrolytic cell, a higher
potential than that predicted
from the ideal line is required to
achieve a given current. Similarly,
polarization of a galvanic cell
produces a potential that is lower
than expected.
 AN INTERFACIAL PROCESS

• For: Ox + ne-⇋ Red

• 5 separate events must occur:
• Ox must be successfully transported from bulk
solution (mass transport).
• Ox must be adsorbed transiently onto electrode
surface (non-faradaic).
• Charge transfer must occur between electrode and
Ox (faradaic).
• Red must desorb from electrode surface (non-
faradaic).
• Red must be transported away from electrode
surface back into bulk solution (mass transport).
 SOURCES OF POLARIZATION
Figure shows three regions of a half-cell in an electrolytic cell where polarization
can occur. These regions include the electrode itself, a surface film of solution
immediately adjacent to the electrode, and the bulk of the solution. For this half-
cell, the overall electrode reaction is Ox + ne- ⇋ Red
Anyone of the several intermediate steps shown in the figure may, however, limit
the rate of this overall reaction. which thus limits the magnitude of the current.
One of these steps in the reaction, called mass transfer,
involves movement of Ox from the bulk of the solution to the
surface film. When this step (or the reverse mass transfer of
Red to the bulk) limits the rate of the overall reaction (and thus
the current), we have concentration polarization. Some half-cell
reactions proceed by an intermediate chemical reaction in
which species such as Ox' or Red' form; this intermediate is
then the actual participant in the electron-transfer process. If
the rate of formation or decomposition of the intermediate limits
the current, reaction polarization occurs. In some instances,
the rate of a physical process such as adsorption, desorption,
or crystallization limits the current. In these cases, adsorption,
desorption, or crystallization polarization occurs. Finally, when
the current is limited by a slow rate of electron transfer from the
electrode to the oxidized species in the surface film or from the
reduced species to the electrode, we have charge-transfer
polarization. It is not unusual to find several types of
polarization occurring simultaneously.
 Overpotential or overvoltage

The degree of polarization of an electrode in

an electrolytic cell is measured by the
overvoltage, or overpotential,П, which is the
difference between the actual electrode
potential E and the thermodynamic, or
equilibrium, potential Eeq. That is,
П = E – Eeq (П p or pi or η eta)
Where E<Eeq. It is important to realize that the
polarization always reduces the electrode
potential for a system. Thus, as we have
indicated, E is always smaller than Eeq and П is
always negative.
 OVERPOTENTIAL OR OVERVOLTAGE
•When the electorde potential changes from its
equilibrium value, the extra potential required to
cause equilibrium reestablished is called
overpotential
• If the electrode process is very fast overpotential is
zero (Fast charge transfer, mass transport, and
possibly adsorption or chemical reactions should be
achieved).
The electrode is then nonpolarizable electrode.
• When the system shows overpotential it is polarized
* Activation polarization: Charge transfer is slow
* Concentration polarization: movement of
depolarizer or product is slow
 Concentration Polarization

• Rate of transport of reactive species to

electrode surface is insufficient to maintain
current.
• Arises because of differing analyte
concentrations in solution when a reaction is
initiated.
• An electrical layer is created at the electrode
surface, This layer resists the flow of electrical
charge unless fresh ions are brought to the
electrode.
CHARGE-TRANSFER (KINETIC)
POLARIZATION
Magnitude of current is limited by the rate of the
electrode reaction(s) (the rate of electron transfer
between the reactants and the electrodes)
Charge-transfer polarization occurs when the rate of the
oxidation or reduction reaction at one or both electrodes is
not sufficiently rapid to yield currents of the size suggested
by theory. Overvoltage caused by charge-transfer
polarization has the following characteristics:

1. Overvoltages increase with current density (current

density is defined as the current per unit area [A/cm2] of
electrode surface).
2. Overvoltages usually decrease with increases in
temperature.
3. Overvoltages vary with the chemical composition of
the electrode, often being most pronounced with
softer metals such as tin, lead, zinc, and particularly
mercury.

4. Overvoltages are especially significant for electrode

processes that yield gaseous products such as
hydrogen or oxygen, but they are frequently
negligible when a metal is being deposited or when
an ion is undergoing a change of oxidation state.

5. The magnitude of overvoltage in any given situation

cannot be exactly predicted because it is determined
by a number of uncontrollable variables.
How do you overcome or compensate for these issues?

Overpotential – choose an electrode material that

minimizes the overpotential (like the evolution of H2 at Pt
has a smaller overpotential compared to evolution of H2 at
Hg).
Ohmic potential – add an electrolyte to increase the ionic
strength of the solution which improves the conductivity of
the solution (decreases the resistance). Higher
conductivity means the ions are more mobile.
Concentration polarization – use methods to minimize the
depletion of analyte concentration at the electrode surface
(convection, flow cells, etc.).
Modes of Electrochemical Mass Transport

• Three Modes:
– Migration
– Convection
– Diffusion
 Migration

• Movement of a charged species (ions) due to a

potential gradient (or electrostatic field).
• Opposites attract.
• Mechanism by which charge passes through
electrolyte.
• Base or Supporting electrolyte (KCl or HNO3) is
used to minimize (make it negligible) migration of
electroactive species (makes it move under
diffusion only).
 Convection
Movement of mass due to a natural or
mechanical force.
Mass transfer due to stirring. Achieved by
some form of mechanical movement of the
solution or the electrode i.e., stir solution,
rotate or vibrate electrode. Difficult to get
perfect reproducibility with stirring, better to
move the electrode. Convection is
considerably more efficient than diffusion or
migration = higher currents for a given
concentration = greater analytical sensitivity
 Diffusion
• Movement of mass due to a concentration
gradient.
• Occurs whenever there is chemical change at a
surface, e.g., O → R
• Movement due to a concentration gradient. If
electrochemical reaction depletes (or
produces) some species at the electrode
surface, then a concentration gradient develops
and the electroactive species will tend to diffuse
from the bulk solution to the electrode (or from
the electrode out into the bulk solution)
OVERVOLTAGE AND THE LEAD/ACID BATTERY

If it were not for the high overvoltage of hydrogen on lead

and lead oxide electrodes, the lead/acid storage batteries
found in automobiles and trucks would not operate because
of hydrogen formation at the cathode both during charging
and use. Certain trace metals in the system lower this
overvoltage and eventually lead to gassing, or hydrogen
formation, therefore limiting the lifetime of the battery.
The basic difference between a battery with a 48-month
warranty and a 72-month warranty is the concentration of
these trace metals in the system. The overall cell reaction
when the cell is discharging is
Pb(s) + PbO2(s) + 2HSO4- + 2H+ → 2PbSO4(s) + 2H2O
The lead/acid storage battery behaves as a galvanic cell
during discharge and as an electrolytic cell when it is being
charged. Such batteries acting as galvanic cells were once
used as voltage sources for electrolysis.
Discharging
Negative plate reaction (Pb plate)

Pb(s) + HSO4−(aq) → PbSO4(s) + H+(aq) + 2e−

Release of two conducting electrons gives lead electrode a net negative
charge.
As electrons accumulate they create an electric field which attracts hydrogen
ions and repels sulfate ions, leading to a double-layer near the surface. The
hydrogen ions screen the charged electrode from the solution which limits
further reactions unless charge is allowed to flow out of electrode.

Positive plate reaction (PbO2)

PbO2(s) + HSO4−(aq) + 3H+(aq) + 2e− → PbSO4(s) + 2H2O(l)

The total reaction can be written as

Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)