Potentiometry

 It is technique used to measure potential (voltage) at an electrode (relative to some

reference) in the absence of current flow.
 Potentiometry is one of volumetric technique of electro-analytical chemistry
 Potentiometrey is the method used in electroanalytical chemistry usually to find the
concentration of solute in solution in potentiometric measurement the potential
between two electrode is measured using the high impedance voltmeter
Potentiometer
 It is instrument used to determine the potential differences between a reference
electrode and an indicator electrode. These two electrodes form electro chemical
cell that are dipped in solution to be analyzed.
 Measured potential can be used to determine the quantity of analyte in terms of
concentration
Electrode Potential
 Tendency of electrode to lose or gain electrons
Standard Potential
 Potential of pure metal when it is dipped in 1Molar solution of its own ions at 25°C
(298K) is known as standard Electrode potential.
Principle
 When a metal strip is placed in a solution of its own ions there are two possibilities
or tendencies:
 Metal atoms may dissolve in the solution as positive ions leaving electrons on the
electrode.
 Metal ions may take up electrons from electrode and get deposited as neutral atoms
 In this way A POTENTIAL DIFFERENCE is setup b/w electrode and solution
Oxidation Potential
 The potential of substance to get oxidized is called oxidation potential.
Reduction Potential
 The potential of substance to get reduced is called reduction potential.
Construction
Potentiometric cell has following parts :
 Electrodes

 Salt bridge

 Analytical solution
 Galvanometer
Working Principle
 At its most basic, a potentiometer consists of two electrodes, whose reduction
potentials differ, inserted in a test solution.
 The voltmeter is attached to the electrodes to measure the potential difference
between them.
 One of the electrodes is a reference electrode, whose electrode potential is known.
 The other electrode is the test electrode.The test electrode is usually either a metal
immersed in a solution of its own ions, whose concentration you wish to discover,
or a carbon rod electrode sitting a solution which contains the ions of interest in two
different oxidation states.
 Oxidation take place at anode.
For example on zinc electrode
Zn → Zn2+ + 2e-
 Reduction take place at cathode.
For example on copper electrode
Cu2+ + 2e-→ Cu
When redox reaction take place than potential is develop which is measured by
galvanometer
 when the known potential electrode immersed in the sample solution then the
potential is given by Nernst equation:
 Nernst equation: Ecell = E0 cell - (RT/nF) lnQ
 Ecell = cell potential under nonstandard conditions (V)
 E 0 cell = cell potential under standard conditions
 R = gas constant, which is 8.31 (volt-coulomb)/(mol-K) T = temperature (K)
 n = number of moles of electrons exchanged in the electrochemical reaction (mol)
 F = Faraday's constant, 96500 coulombs/mol
 Q = reaction quotient
 Salt bridge contain inert electrolyte such as KCl connects the two half-cells.
 The ends of the salt bridge are fixed with porous frits (to allow the ions of electrolyte to
move freely between the half-cells and the salt bridge).
 Salt should be inert does not react with cathode or anode solution if it will react then
precipitation produce at bottom of cell
 Application of salt bridge
 To complete the circuit of cell, To maintain electrical neutrality by making ionic balance
in both cell
 Electrode Potential is the potential of electrochemical cell and can be
represented as :
E cell = E indicator – E reference +E j
Ej= potential develops across the liquid junction at each end of salt bridge it is negligible
Electrodes
Reference Electrode
1. Standard Hydrogen electrode
2. Calomel electrode
3. Silver-Silver Chloride electrode
Indicator Electrode
1. Metal Electrode
2. Hydrogen electrode
3. Quinhydrone electrode
4. Glass Membrane Electrode
 The standard H2 electrode potential is defined as the potential that is developed
between the H2 gas adsorbed on the pt metal and H+ of the solution when the H2
gas at a pressure of 760 mm of Hg is in equilibrium with H+ of unit concentration
Working:
 Pt foil : coated with black pt use to increase the surface area of foil
 1 molar HCl solution
 Pure H2 gas bubbled continuously at 1 atm.
 Pt act as conductor, inert and facilitate in attaining equilibrium, Pt wire cannot be
affected by acidic solution that’s why Pt is used
 Electrode Potential is 0.00 volts
H2 (gas) ↔ 2H+ (ions) + 2e- (electrons)
Limitations :
1. Can’t be used in solution containing strong oxidizing agents.
2. Difficult and expensive to maintain.
3. Excess of H2 bubbling out carries little HCl with it and hence the H+ concentration
decreases. In such a system, it is difficult to maintain the concentration of HCl at 1M.

Ideal Characteristics of Reference Electrode

 Obeys the Nernst equation

 Exhibit constant potential

 Exhibit little change with temperature

 Constant output response

 Always treated as left hand electrode

 Most commonly used electrode in potentiometry
 Tube 5-15cm long, 0.5-1 cm in diameter.
 Slurry of mercury & mercurous chloride with saturated soln of KCl
 Connected by a small opening with saturated solution of KCl.
 Pt metal is placed inside the slurry
 Ceramic fiber act as salt bridge
 Mercurous chloride is also called calomel
2Hg +2Cl¯ → Hg2Cl2 + 2e¯
E = 0.2444 at 25°C
Advantages:
 Concentration of chloride ions don’t change even
some of the solvent get evaporated.
 Generates small junction potential so more accurate

Limitations :
 Mostly saturated solution of KCl is used and that is
temperature dependent.
 It consist of silver wire coated with AgCl
 Coating may be electroplating or Physical.
 This coated wire is placed in 1M solution of AgCl.
Ag + Cl¯ ↔ AgCl + 1e¯
E= 0.199V
 The electrode body contains potassium chloride to stabilize the silver chloride
concentration
Advantages:
 Easy handling, and inexpensive to manufacture
 Stable potential
 Non toxic components
Limitation:
 sometimes show reactivity.
 Indicator electrode use in conjugation with reference electrode to determine the concentration
of analyte in sample solution
Metal Indicator Electrode
 Metal electrode develops electric potential as a result of redox reaction at its surface.
1. First Order Electrode
A first order electrode involves the metal in contact with its own ions, such as silver metal
electrode dipping in solution of silver nitrate.
Ag⁺ + e¯ ↔ Ag (s) E= 0.800
 The potential becomes increasingly positive with increasing Ag+(cation activity). This is the
case for any electrode measuring cation
Limitation:
 Metallic indicator electrodes are not very selective and respond not only to their
own cations but also to other more easily reduced cations.
 Many metal electrodes can be used only in neutral or basic solutions because they
dissolve in the presence of acids
 Easily oxidized can be used only when analyte solutions are de aerated to remove
oxygen

2. Second Order Electrode

 Second order electrode is consist of silver wire coated with silver chloride
precipitate, actually as silver is dipped in chloride solution it adopts a thin layer of
silver chloride
 A second-order electrode is one that respond to the activities of anions that form
sparingly soluble precipitates or stable complex ions
 For example, silver wire could serve as the indicator electrode for detection of
chloride ions.
 It means this electrode is used to measure the activity of chloride ion in solution
 As the activity of chloride increases, the potential decreases, this is true for any
electrode measuring anion
Inert Electrode
 The most commonly used indicator electrodes are known as inert.
 In this type of electrode an inert metal is in contact with solution containing soluble
oxidized and reduced forms of the redox half reaction
 Inert electrode is made up of material that conducts electric current but can not
oxidized or reduced
 Typical inert electrodes are platinum, gold, and carbon.Inert electrodes are
responsive to any reversible redox system; these are widely used in potentiometric
work.
 Its most commonly used indicator electrode
 It involves Ion Exchange reaction, Potential is not affected by the presence of
oxidizing or reducing agent
 Membrane is made up of chemically bonded Na2O, SiO2 and Al2O3
 The Glass bulb is filled with solution of HCl, silver acetate coated with AgCl is
inserted as Electrode.
 The internal reference electrode and electrolyte used for making electrical contact
with glass membrane
 The glass membrane should be hydrated for all time, If membrane is dry for
sometime then pH electrode is calibrated
Working
 First glass absorb water
 Then H ions can move in the direction of lesser concentration and replace Na ions
and others in the glass membrane.
SiO2-Na⁺ + H⁺ SiO- H⁺ + Na⁺
 As a result of diffusion and exchange process a potential develops on each side of
glass membrane
Boundary Potential
 When electrode is dipped in aqueous solution a boundary potential is built up at the
surface of glass membrane, which is determined by activity of hydrogen ions in
external solution and activity of hydrogen ions on the surface of gel
 The ions will tend to migrate in direction of lesser activity. In result microscopic
layer of charge built up on the surface of membrane which represents the potential
 If solution is more acidic then protons migrate to the surface of gel building up
positive charge and potential of electrode increases
Diffusion Potential
 The tendency of protons in the inner part of gel layer to diffuse toward the dry
membrane which contains SiO-Na+
 And tendency of sodium ions in dry membrane to diffuse to hydrated layer. The ions
migrate at different rate creating type of liquid junction potential and similar
phenomena occurs on other side of membrane only in opposite direction. These
effect cancel each other and potential of membrane is determined largely by
boundary potential
 Quinhydrone is bronze coloured needle shaped crystals
 Quinhydrone is slightly soluble in water, dissolving to form a mixture of two
substances, quinone and hydroquinone, with the two substances present at equal
concentration. Each one of the two substances can easily be oxidised or reduced to
the other.
2QH → Q+H2Q
 Q(s) + 2H+ + 2e- H2Q
 K=aH2Q/ aQxa2H+
 The electrode consists of an inert metal electrode (usually a platinum wire) in
contact with quinhydrone crystals and a water-based solution.
 The potential at the inert electrode depends on the ratio of the activity of two
substances (quinonehydroquinone), and also the hydrogen ion concentration.
 For practical pH measurement, a second pH independent reference electrode (such
as a silver chloride electrode) is also used. This reference electrode does not respond
to the pH.
 The difference between the potential of the two electrodes depends (primarily) on
the activity of H+ in the solution. It is this potential difference which is measured
and converted to a pH value.
Advantages
 It attains equilibrium very quickly

 It is less expensive than glass electrode

 It has low internal resistance

 It is very simple

 It is highly accurate in measurement

Disadvantages
 Quinhydrone electrode cannot be applied to solutions more basic than pH 9
because hydroquinone being weak acid is neutralized by base.
 Strongly oxidizing and reducing agents affect on its performance

 It is not stable for long time particularly above 300C

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