ELECTROANALYTICAL

METHODS
or
ELECTROCHEMICAL
ANALYTICAL METHODS

by
O.C. Othman
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 The Analysis Concept

PROBE RESPONSE
Sample
Electrons, photons, atoms, For Heat, ions, molecules,
Atoms, photons, electrons
molecules, ions, heat Analysis
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 General Instrument for Analysis
Components of a typical instrument

Electrical
Meter
or
or
mechanical Scale
Analytical Input input
signal transducer signal Output
Signal Signal Recorder
/ signal
generator processor
detector
or sensor
12.301
Output transducers
Digital
unit
Readouts
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Applicable concentration range - linear

LOQ – Limit of Quantitation

LOL – Limit of Linearity
Cm – Minimum detectable concentration
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Electrochemical methods
• A group of quantitative analytical methods that are
based upon the electrical properties (response) of a
solution of the analyte (chemical system) when it is
made part of an electrochemical cell.

• Chemical System: electrolyte, electrodes, analyte,

buffer/additives

• Electrical responses (signals) include current (I),

potential (V), capacitance (C), resistance (R) and
charge (Q).
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Electroanalytical methods:
are: • fast
• inexpensive
• in situ
• very low detection limits
Provide information about:
• oxidation states
• stoichiometry
• rates
• charge transfer
• equilibrium constants
• activity / concentration
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Electrochemical methods
Methods in which the electrical response
of a chemical system (sample) is
measured as a function of analyte
concentration.

The basic part of all electrochemical

measurements is the Electrochemical
Cell.

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Electrochemical methods:
• can inform on specific forms of an analyte
(i.e. Fe2+, Fe3+ and total Fe).

• respond to the available (free) analyte

concentration (activity) e.g. free Ca 2+ as
compared to Ca tied to proteins which a
flame method would analyze.

• instrumentation is more electronic in nature

and mostly computerized and automated.
• wider scope and applicability in analysis
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 General Electroanalytical Instrument

Components:
Meter
Electrical or
input Scale
Analytical Input signal
signal transducer Output
Signal Signal signal Recorder
generator or processor
detector

12.301

Electrochemical Output transducers

Sensor (Input -Trans) Digital
unit
Readouts
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Electrochemical Cells:
• Oxidation and reduction (redox) reactions occur
• Usually separate species to prevent direct reaction

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Electrochemical Cells:

Most contain
• external wires (electrons carry current)
• ion solutions (ions carry current)
• interfaces or junctions

All contain
• complete electrical circuits
• conducting electrodes (metal, carbon)

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Electrochemical cells - Terminology

• Electrons transferred at electrode surface

and liquid/solid interface
• Potential difference (voltage) is measure
of tendency to move to equilibrium
• Galvanic cell - cell develops spontaneous
potential difference
• Electrolytic cell – requires power to
operate

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Electrochemical Cells - terminology
• 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.

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• Galvanic cells produce electrical
energy.
• Electrolytic cells consume energy.
– A chemically reversible cell 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.
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Galvanic Cells

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Galvanic cell

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Electrolytic cells

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Electrolytic cells

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Schematic Representation of Electrochemical Cells

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Use shorthand-notation to represent this cell

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Use shorthand-notation to represent this cell

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The hydrogen electrode

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If voltage is 0.337V, what is the electrode 26
here?
Standard Hydrogen Electrode (SHE)

• assigned 0.000 V
• can be anode or cathode
• Pt does not take part in reactions
• Pt electrode coated with fine particles of Pt
(Pt black) to provide larger surface area
• cumbersome to operate

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Others

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Standard electrode potentials

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Some understandings

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Equilibrium reactions

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Equilibriums

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Limitations

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Electrode boundaries

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Charging current Double
layer

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Double layer

Inner part of
double layer
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Faradaic Processes
• 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.

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 Ideally polarized electrode

Electrodes at which no charge transfer takes place. Only

nonfaradaic process takes place regardless of the applied
potential
e.g. A Hg electrode in contact with a NaCl solution at potential of
0.0 up to –2.0 V.
Capacitance of the electrode, C = q / V, where
q = charge in Coulombs
V = voltage across the capacitor
Current, i,  electrode capacity and resistance of solution

With constant electrode area, current (i) dies within a fraction of

second
With a Dropping Mercury Electrode, DME, i dies more slowly.

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In Faradaic processes

• 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 a “Depolarizer”

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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 a reversible electrode?

Reversibility and irreversibility depends upon

* Rate of electrode process
* Rapidity of the electrochemical
measurement
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Overvoltage
• When the electrode potential changes from its
equilibrium value, the extra potential required to
cause / restore equilibrium 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 a 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 46
An Interfacial Process (at electrode surface)
For: O + ne- = R
5 separate events must occur:
 O must be successfully transported from bulk
solution (mass transport)
 O must be adsorbed transiently onto electrode
surface (non-faradaic)
 Charge transfer must occur between electrode
and O (faradaic)
 R must desorb from electrode surface (non-
faradaic)
 R must be transported away from electrode
surface back into bulk solution (mass transport)
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Modes of Electrochemical Mass Transport

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Migration

• Movement of a charged species due to a potential

gradient (difference in potential)
• 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 the species move
under diffusion only)

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Convection

• Movement of mass due to a natural or

mechanical force e.g. stirring
• At long times ( > 10 s), diffusing ions set up a
natural eddy of matter

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Diffusion
• Movement of mass (analyte) due to a concentration
gradient
• Occurs whenever there is chemical change at a
surface of the electrode, e.g. O  R
• Diffusion is described by the Cottrell Equation

it = (nFAD1/2C)/1/2t1/2
it = current at time t;
n = # electrons involved
A = surface area of the electrode
C = concentration of electro-active species
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D = diffusion coefficient
 Types of Electroanalytical Procedures

1. Based on relationship between analyte

concentration and electrical quantities such as
current, potential, resistance (or conductance),
capacitance, or charge.

2. Electrical measurement serves to establish end-

point of titration of analyte.

3. Electrical current converts analyte to a form that

can be measured gravimetrically or
volumetrically.
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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

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METHOD MEASUREMENT PRINCIPLE QUALIT- DESIRED DETECTION COMMENTS
APPLICATIONS ATIVE MINIMUM LIMIT
INFORM- SAMPLE
ATION SIZE

Voltammetry Current as a function Quantitative analysis Reversibility 100 g 10-1-10 –3 ppm A large number of
(Polarography) of voltage at a of electrochemically of reaction 10 g voltage programs may be
(amperometric polarized electrode reducible organic or used. Pulse Polarography
titrations) inorganic material and Differential Pulse
(chronoamperometr Polarography improve
y) detection limits.

Potentiometry Potential at zero Quantitative analysis Defined by 100 g 10-2 -102 ppm Measures activity rather
(potentiometric current of ions in solutions, electrode (e.g., than concentration.
titration) pH. F-, Cl-, Ca2+)
(chronopotentiomet
ry)

Conductimetry Resistance or Quantification of an Little 100 g Commonly used as a

(conductometric conductance at inert ionized species, qualitative detector for ion
titrations) electrodes titrations identification chromatography.
information

Coulometry Current and time as Exhaustive electrolysis Little 100 g 10-9 -1 g High precision possible.
number of Faradays qualitative
identification
information

Anodic Stripping Weight Quantitative trace Oxidation 100 g 10-3 -103 g Electrodeposition step
Voltammetry analysis of potential 10 ng provides improved
(Electrodeposition) electrochemically permits detection limits over
reducible metals that identification normal voltammetry.
form amalgams with of metal. 54
mercury
 Potentiometry
• Technique: measuring potentials in
electrochemical cells with respect to
the concentration of analyte in the
electrolyte solution

• Minimum two half cells are required

• An indicator half cell and a reference

half cell
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 Example: The pH Meter
• The first transducer is a pair of electrodes; one at a fixed
pH (reference) and the other sampling the unknown
solution (indicator). Together they produce a voltage
difference (ΔV).
• This is amplified and turned into a current to drive the
pen displacement motor on a chart recorder,
permanently recording the changes in pH with time.

Recorder
I
Amplifier
V–I
ΔV Converter

pH
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Reference half cells

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Choosing a reference

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Measurements

Nernst equation applies

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