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Electro Analytical Methods
Electroanalytical methods are a class of techniques
in analytical chemistry which study an analyte by
measuring the potential (volts) and/or current (amperes) in
an electrochemical cell containing the analyte.
1. Voltammetry: Voltammetric system usually measures
current in an electrolytic cell (consumes power to cause
an electrochemical reaction to occur).
2. Potentiometry: Potentiometric system measure voltage
(i.e. potential) of a galvanic cell (produces electricity
spontaneously).
Difference Between Potentiometry and Voltammetry
Potentiometry Voltammetry
Two electrode system Three electrode system
(Reference electrode and (Reference electrode,
Indicator electrode) Indicator electrode and
counter electrode)
Follows the Nernst equation Deviated form the Nernst
equation; depends upon
concentration polarization
Potential is measured Current measured with
applied potential
POTENTIOMETRIC TITRATIONS
The process of determining the quantity of a sample by adding
measured increments of a titrant until the end-point, at which
essentially all of the sample has reacted, is reached. The titration is
followed by measuring the potential difference between indicator
and reference electrodes under conditions where the current
passed is sufficiently small to maintain thermodynamic equilibrium.
WHY POT ENTIOMETR IC TITR ATIONS?
• Provides more reliable data than titrations involving chemical
indicators
• Titrations that result in turbid solutions or precipitations
• Automation possible
POTENTIOMETR IC TITRAT IONS
Potentiometric titration set-up
1. Reference Electrode
2. Indicator Electrode
3. Potential Measuring Device
Reference electrode I Salt bridge I analyte solution I Indicator electrode
Eref Ej
Eind
Ecell = Eind – Eref + Ej
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CLAS SIFICATION OF POTENTIOMETRIC T ITR ATIONS
1. Acid- Base titrations (Strong acid vs. Strong base)
Acidic or basic titrant react with an analyte that is a base or acid
2. Redox titrations
Titrant is an oxidizing or reducing agent
3. Precipitation titrations (the one performed in the laboratory)
Analyte and titrant react to form precipitate
4. Complexometric titrations
Involves metal-ligand complexation reaction
EQ UIVALENCE P OINT IN POT ENTIOMETR IC TITR ATIONS
1. Acid- Base titrations curve
The point on the curve with the maximum slope
2. First derivative of titration curve
The maximum point
3. Second derivative of the titration curve
The point at which the second derivative crosses zero is the end point
POTENTIOMETRIC PRECIPITATION TITRATION
Working electrode: Pt electrode
Reference Electrode: Calomel electrode
Titration of AgNO3 with NaCl
Ag+ + NO3- + Na+ + Cl- → AgCl + Na+ + NO3-
White precipitate
𝑯𝒈 𝒍 | 𝑯𝒈𝟐 𝑪𝒍𝟐 𝒔 | 𝑲𝑪𝒍 𝒔𝒂𝒕. 𝒔𝒐𝒍𝒏 ∥ 𝑨𝒈+ | 𝑨𝒈𝑪𝒍 𝑷𝒕
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝑹 − 𝑬𝑳 = 𝑬𝟎𝒆𝒍 + 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈 [𝑨𝒈+ ] − 𝑬𝑪𝒂𝒍𝒐𝒎𝒆𝒍
𝑬𝒄𝒆𝒍𝒍 = 𝟎. 𝟖𝟎 𝑽 + 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈 [𝑨𝒈+ ] − 𝟎. 𝟐𝟒𝟐𝟐 V
𝑬𝒄𝒆𝒍𝒍 = 𝟎. 𝟓𝟓𝟕𝟖 + 𝟎. 𝟎𝟓𝟗𝟏 𝒍𝒐𝒈 [𝑨𝒈+ ]
As the Ag+ decreases Ecell value decreases
Voltammetry
• Volt • Ammeter
(Potential) (Current)
Types
1. Linear Sweep Voltammetry (LSV)
2. Cyclic Voltammetry (CV)
3. Differential Pulse Voltammetry (DPV)
4. Square Wave voltammetry (SWV)
5. Stripping Voltammetry (SV)
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Linear Sweep Voltammetry (LSV)
The potential is varied linearly from an initial potential
(Initial E) to a final potential (Final E) at a constant rate
(Scan Rate), and the current is monitored as a function of
the applied potential.
▪ Only a small amount of sample (analyt) is used.
Observed Current Changes
Apply Linear Potential with Time
with Applied Potential
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E 1/2 = Half wave potential
▪ Half-wave potential (E1/2) - The potential at which the
current is equal to one half the limiting current.
▪ Half-wave potential is closely related to the standard
potential for the half-reaction but is usually not identical to
it.
▪ Half- wave potentials are sometimes useful for
identification of the components of a solution.
Voltammograms for Mixtures of Reactants
Voltammograms for a pair of two component mixtures
➢ Two or more species are observed in voltammogram
➢ Difference in separate half-wave potentials are sufficient
0.1V 0.2V
