POTENTIOMETRY

INTRODUCTION:
• It is one of the volumetric techniques of electro-analytical chemistry which is
used to measure electrochemical potential of charged particles.
• Potentiometry is a technique used to measure the concentration of an analyte in
a solution by determining the potential difference between two electrodes.
• PRINCIPLE: It relies on the principle that the potential of an electrode immersed
in a solution is related to the concentration of certain ions or molecules in that
solution.
• The potential measured depends on the activity or concentration of ions,
calculated using Nernst equation, making quantitative analysis possible, under
the conditions when no current or minimum current passed through the
potentiometer circuit.
COMPONENTS OF POTENTIOMETER APPARATUS:

• Electrodes:
1. Working electrode
2. Reference electrode
• Salt bridge:
• Voltmeter:
• Electrodes:
• An electrode is an electrical conductor used to make contact with a
nonmetallic part of a circuit (e.g. a semiconductor, an electrolyte, a
vacuum or air).
• Electrodes used for electrochemical measurement in potentiometer
include:
• Reference Electrodes: A half-cell with an accurately known electrode
potential, Eref, that is independent of the concentration of the
analyte or any other ions in the solution. It is always treated as the
left-hand electrode. Commonly used reference electrodes are:
• 1. Silver-silver electrode
• 2. Saturated calomel electrode (SCE)
• 3. Mercury (I) sulfate electrode
• 4. Standard Hydrogen electrode (SHE)
• Indicator Electrodes: It is immersed in a solution of the analyte,
develops a potential, E(ind) that depends on the activity of the
analyte. It is selective in its response.
• Indicator Electrodes are:
1. Glass electrode
2. Ion-selective electrodes
a) Solid state/ crystal membrane electrode
b) Coated wire electrode
c) Liquid liquid electrode
d) Plastic membrane ionophore electrodes
e) Potentiometric enzyme based electrodes to measure substrates &
many others.
• Salt Bridge:
• It is usually a U-shaped glass tube containing a neutral inert salt in an
agar medium, used to obtain electrical neutrality between the two
half cells of a voltaic cell or electrochemical cell.
• Preventing components from mixing with those of the reference
electrode.
• A potential develops across the liquid junctions at each end of the salt
bridge
• Potassium chloride is a nearly ideal electrolyte for the salt bridge
because the mobilities of the K+ ion and the Cl- ion are nearly equal.
 REFERENCE ELECTRODES:
• PRIMARY STANDARD ELECTRODE /
STANDARD HYDROGEN ELECTRODE (SHE):

• The standard hydrogen electrode is set up by passing pure hydrogen gas at

one atmospheric pressure in a solution of H+ ions of concentration
of 1mol/L in contact with a platinized platinum foil.
• Standard Hydrogen Electrode can work both as an anode and as a cathode.
• When a standard hydrogen electrode undergoes oxidation in a cell, it acts as
an anode. During this process, hydrogen gets changed into ions which go
into the solution.
• When a standard hydrogen electrode undergoes a reduction in a cell, it acts as a
cathode. During this process, H+ ions from the solution change into hydrogen gas.
• 2H+ + 2e– →H2
• Thus, the electrode is reversible concerning H+ ions.
• The electrode potential of the standard hydrogen electrode is zero at 298K.
• Measurement of Electrode Potential:
• To determine an electrode’s potential, a cell is set up using the electrode as one
of the electrodes and the second electrode as the standard hydrogen electrode.
The emf of the cell is then measured. The emf of the cell is the sum of the
oxidation potential and reduction potential of the cell.
• One of the electrodes involved in the standard hydrogen electrode has an
electrode potential that is zero; therefore, the emf of the cell will be directly
given the electrode potential of the electrode under investigation.
• Advantages of Standard Hydrogen Electrode
• It can be used for a range of pH values.
• The standard hydrogen electrode potential is zero. Therefore, the electrode
potential of another electrode can be easily calculated.

• Disadvantages of Standard Hydrogen Electrode

• Platinum is expensive, and platinized platinum is difficult to prepare.
• Maintaining the pressure of hydrogen and the concentration of acid is not easy.
• It isn’t easy to obtain pure hydrogen.
Secondary reference electrode / Standard calomel electrode (SCE):

• A saturated calomel electrode (SCE) consists of a glass vessel having a bent

side tube.
• At the bottom of the tube is pure mercury, which is covered with calomel
paste – mercury-mercurous chloride (Hg+Hg2Cl2).
• Mercury provides a stable and conductive medium for the electrode to
operate. This choice of mercury is crucial as it exhibits low reactivity and
remains liquid across a wide temperature range.
• Calomel paste serves as a salt bridge that allows ion exchange while
maintaining a constant chloride ion concentration. It also contributes to the
SCE’s stable potential.
• The SCE acts either as an anode or cathode. When functioning as an anode, the
reaction that occurs is an oxidation reaction, where mercury first oxidizes to
mercuric ions.

• Then, the chloride ions supplied by the KCl solution combine with the
mercuric ions to form insoluble mercurous chloride.

• On the other hand, if the SCE serves as a cathode in the galvanic cell,
a reduction reaction occurs.

• The measured potential, E, of the SCE is +0.241 V (SHE) for a saturated chloride
ion solution at 298 K.
• Advantages:
• The SCE is known for its stability over a wide range of experimental conditions.
• It maintains a relatively constant potential, making it suitable for long-term
measurements.
• SCEs are relatively low maintenance compared to some other reference
electrodes. They don't require constant recalibration or replenishment of
electrolyte solution

• Disadvantages:
• Calomel (mercury(I) chloride) is toxic, posing environmental and health risks.
• the potential of the SCE is temperature-dependent. Changes in temperature can
affect the performance and accuracy of measurements.
• Silver / silver chloride electrode:
• The silver/silver chloride reference electrode is composed of a silver wire,
sometimes coated with a layer of solid silver chloride, immersed in a solution that
is saturated with potassium chloride and silver chloride. The pertinent half
reaction is:
• AgCl(s)+e−⇔Ag(s)+ Cl−
• The silver-silver chloride reference electrode develops a potential
proportional to the chloride concentration.
• E0 value of silver/silver chloride electrode +0.222 V but its vary with
chloride concentration.
Nernst equation:
• The equation was given by Walther H. Nernst, he was awarded Nobel
Prize in 1920. The NERNST equation enables us to determine the:
1. Electromotive force EMF of many processes .
2. Cell potential of a system called Galvanic cell
3. Energy of a chemical reaction
• STANDARD CONDITIONS refers to a cell which is operated at 25⁰C and
concentrations of electrolytes are Unimolar, i.e. 1M.
• Eo(Cell) = Eo(Cathode) − Eo(Anode)
• Nernst Equation for Single Electrode Potential
• Ecell = E0 – [RT/nF] ln Q
• Nernst equation is a general equation that relates the Gibbs free energy and cell
potential in electrochemistry. It is very helpful in determining cell
potential, equilibrium constant etc.
• Gibbs free energy is used to measure the maximum amount of work done in a
thermodynamic system.
1) The Gibbs free energy change (Δ𝐺) of an electrochemical reaction is related to
the cell potential:
• ΔG=−nF ​Ecell

Where:
• 𝑛 is the number of moles of electrons transferred in the reaction.
• 𝐹 is the Faraday constant (approximately 96,485 C/mol).
• Using the Relationship between Δ𝐺 and Equilibrium Constant (𝐾):
• ΔG=−RT ln(K)
• Where:
• 𝑅 is the gas constant 8.314 J/(mol⋅K).
• 𝑇 is the temperature in Kelvin.
• Combining Equations: Equating the expressions for Δ𝐺, we get:
• −nFEcell​=−RT ln(K)
• For Nernst equation:

• Where:
• 𝐸 is the cell potential under non-standard conditions.
• 𝐸∘ is the standard cell potential.
• 𝑄 is the reaction quotient, which is the ratio of the activities of
products to reactants.
• The relationship between natural logarithm (ln) and logarithm to base
10 (log10) can be expressed as:
• E = Eo − (2.303RT/nF) log10 Q

• At standard temperature T = 298 K, the 2.303RTF, term equals:

• E = Eo − (0.0592/n) log10 Q
 Potentiometric titration:
• Potentiometric titration is a laboratory method to determine the
concentration of a given analyte. It is used in the characterization of acids.
In this method, there is no use of a chemical indicator. Instead, the electric
potential across the substance is measured.
• Principle:
• The principle of potentiometric titration is based on the concept of
measuring the electrical potential (voltage) between a reference electrode
and a measuring electrode (indicator electrode) as a function of the
amount of titrant (solution of known concentration) added to the analyte
solution. The potential difference between the electrodes changes as the
titration progresses, reaching a maximum (or minimum) at the endpoint
where the analyte has reacted completely with the titrant.
End Point Determination:
• Several methods can be used for the
determination of end point. The most straight
forward method involves a direct plot of
potential with respect to reagent volume.
• As fig, the midpoint is the steep rising position of
the curve is the estimated visually and taken as
the end point.
• Various graphical methods have been proposed
to aid in the establishment of the midpoint but is
doubtful that these procedures significantly
improves its determination (equivalence point).
End point determination:
Types:
• Various titrations can be performed by this method;
• Acid base titrations
• Redox titrations
• Precipitation reaction titrations
• Complex formation titrations
• Differential titrations
Advantages:

• Titrations that use chemical indicators the potentiometric end points

provides more reliable data.
• These are particularly useful for the titration of colored and turbid
solution.
• Useful for detecting the presence of unsuspected species in a
solution.
• Main disadvantage is that, more time consuming than those titrations
using indicators, on the other hand they are readily automated.