Potentiometry

Introduction

• In potentiometry, the potential of an electrochemical

cell is measured under static conditions because no
current flows while measuring a solution’s potential,
its composition remains unchanged.

• Information on a composition of the sample is

obtained through the potential appearing between two
electrodes.
 Basic Principles

Potentiometer

• A device for measuring the potential of an electrochemical cell

without drawing a current or altering the cell’s composition.
• The potential of an electrochemical cell is measured under
static conditions. Because no current, or only a negligible
current flows while measuring a solution’s potential, its
composition remains unchanged.
• For this reason, potentiometry is a useful quantitative method.
 Potentiometry
Electrochemistry
Redox reactions
Spontaneous Reactions
Non-spontaneous reactions
Types of cells
Electrolytic cell
Galvanic cell
Nernest Eqution
Types of Reference and Indicator Electrode
Electrochemical cell
• Electrochemical cell consists of two solutions connected
by a salt bridge and electrodes to form electrical circuit.
Sample cell consists of solutions of ZnSO 4 and CuSO4.
• Metallic Zn and Cu electrodes are immersed in
respective solutions. Electrodes have contacts firstly
through wires connected to the voltmeter and secondly
through solutions and a salt bridge, forming an electric
circuit.
Electrochemical cell…
Salt bridge consists of a tube filled with
saturated salt solution (e.g. KCl solution). The
ends of the tube are capped with porous frits
that prevent solutions from mixing, but permit
movement of ions
Electrochemical cell…
Three distinct charge transfer processes are described
for the system in Fig are
• 1. Electrons move in electrodes and wires from zinc
electrode to copper electrode.
• 2. Ions move in solutions:(a). In solution on the left,
zinc ions move away from the electrode and sulfate
ions move towards it.
Electrochemical cell…
(b). In solution on the right, copper ions
move towards the electrode and negatively
charged ions (sulfate) away from it.
(c). In salt bridge positive ions move right
and negative ions left.
• 3. On the surfaces of electrodes electrons
are transferred to ions or vice versa:
a. Zinc electrode dissolves: Zn → Zn+2 +
2e
b. Metallic copper is deposited on the
electrode surface:
Cu +2e → Cu
2+
Electrochemical cell…
• Three processes mentioned above are important
parts of a closed electrical circuit making the flow
of electrical current possible.
• Potential on an electrode depends on the ions
present in the solution and their concentration.
So, electrochemical cells can be used to determine
ions and their concentration in solution. The
dependence of potential between electrodes from
concentration of ions is expressed by Nernst equation
 Electrochemical cell…
• The first quantitative potentiometric application appeared soon
after the formulation of Nernst equation.

• In 1889, the Nernst equation relating an electrochemical cell’s

potential to the concentration of electroactive species in the
cell.

• Potentiometric methods of analysis are based upon

measurements of the potential of electrochemical cells under
conditions of zero current, where the Nernst equation governs
the operation of potentiometry.
 Potentiometry…
Overall potential of cell can be measured by following equation
Ecell = Eindicator – Ereference
Nernst equation in practice
Due to the complex nature of overall potential, Nernst equation is often
used in form of equation 2 (compare to equation 1):

Ecell - overall potential,

c - concentration of analyte ions, which can be used instead of activity (a) only
in case of dilute solutions
K - includes all remaining potentials in the system (including junction potential
and potential of reference electrode).
Nernst equation:
Ecell = E0cell - (RT/nF) lnQ

Ecell = cell potential under nonstandard conditions

E0cell = 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
Potentiometric measurements
• Made by using a potentiometer to determine the difference in
potential between a indicator electrode and a reference
electrode.
 Cathode is the sensing electrode. (right half-cell)
 Anode is the reference electrode. (left half-cell)

Ecell = Ec ─ Ea

Where : Ec is the reduction potential at the cathode.

: Ea is the reduction potential at the anode.
• 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).
• This movement of ions in the salt bridge completes the
electrical circuit.
• Reference electrode : left electrode (anode) which
undergoes oxidation.
• Sensing electrode : right electrode (cathode) which
undergoes reduction.
• When the potential of an electrochemical cell is measured,
the contribution of the liquid junction potential must be
included;
Ecell = Ec ─ Ea  Elj
Example 2
+ 2 e–     Cu(s)
   Fe2+
 Potentiometry
• Potentiometry is a quantitaive method to measure the
voltage by the use of electrodes which provides the chemical
information.
• Potentiometry is based on the measurement of the potential
of an electrode system (e.g.electrochemical cell).
• Potentiometric measurement system consists of two
electrodes called reference and indicator electrode,
potentiometer and a solution of analyte.
 Potentiometry…
• Reference electrode is an electrode with potential which is
• (a) independent of concentration of analyte (or other) ions in
solution; b) independent of temperature.
• Potential of an indicator electrode depends mainly on the
concentration of the analyte ions
 Potentiometry…
• Potentiometric measurements enable selective detection of
ions in presence of multitude of other substances.
• In case of figure, the potential of the indicator electrode is
sensitive to hydrogen ions. In a system like this, the potential
is measured in reference to a calomel electrode, e.g. calomel
electrode functions as the reference electrode.
 Potentiometry…
Overall potential of cell can be measured by following equation
Ecell = Eindicator – Ereference
Nernst equation in practice
Due to the complex nature of overall potential, Nernst equation is often
used in form of equation 2 (compare to equation 1):

Ecell - overall potential,

c - concentration of analyte ions, which can be used instead of activity (a) only
in case of dilute solutions
K - includes all remaining potentials in the system (including junction potential
and potential of reference electrode).
 Types of Electrodes
Reference Electrode
(i) Standard Hydrogen Electrode
(ii) Saturated Calomel Electrode
(iii) Silver-Silver Chloride Electrode
Indicator Electrode
(iv) Metallic Electrodes
(v) Membrane Electrode
Reference Electrode General Characteristics

 Known electrode Potential

 Half Cell Potential
 Insensitive to the composition of solution under
assay/analyte
 Acts as half cell anode or half cell cathode
Ideal Conditions
 Obeys Nernset Equation
 Constant Potential
 Little change with temperature
 SHE
• Standard Hydrogen Electrode (SHE)
• Normal Hydrogen Electrode (NHE)
• Gas-ion Electrode
 SHE
Acts as Cathode half cell

2H+ + 2e- H2

Acts as Anode half cell

H2 2H+ + 2e-
 Saturated Calomel Electrode
Oxidation(Anode)
2Hg 2 Hg+ + 2 e-
2 Hg + 2 cl- Hg2Cl2 + 2 e-
Reduction( Cathode)
2 Hg+ + 2 e- 2Hg
Hg2Cl2 + 2 e- 2 Hg + 2 cl-
 Ag-Agcl Electrode
• Oxidation(Anode)
Ag + Cl- AgCl + e-

• Reduction ( Cathode)

• AgCl + e- Ag + Cl-
 Reference electrode
• It has a standard potential on its own and its potential does
not change to whichever solution it is dipped.
• It is treated as the left-hand electrode (anode)

Example of reference electrode

 Standard hydrogen electrode (SHE)

 Saturated calomel electrode
 Silver-silver chloride electrode
 Standard hydrogen electrode (SHE)
• Defined as the potential that is developed between H2
gas adsorbed on the Pt metal and H+ of the solution .
• It is used for

 Determination of electrode potential of metal

electrode system
 Determination of pH of the solution
Pt,H2 (g, 1atm) | H+ (aq, a = 1.00) ||2 H+ (aq) + 2 e ─ ↔ H2 (g)
 Saturated calomel (Hg2Cl2) Electrode (SCE)
• Contains of an inner jacket and outer sleeve.
• Inner jacket has wire contact with Hg and plugged with a mixture of
calomel Hg2Cl2 & KCl.
• Outer sleeve has crystals of KCl & porous plug of asbestos
• Application: pH measurement, cyclic voltammetry and general
aqueous electrochemistry.
• Advantages: Ease of construction and stability of potential.

Hg(l) | Hg2Cl2 (sat’d), KCl (aq, sat’d) || Hg2Cl2(s) +2e– ↔2Hg(l ) + 2Cl-(aq)
 Silver-silver chloride electrode

• Widely used because simple, inexpensive, very stable

and non-toxic.
• Mainly used with saturated potassium chloride (KCl)
electrolyte.
• Advantages : Easy to use
• Disadvantage : Difficult to prepare

Ag(s) | AgCl (sat’d), KCl (x M) ||AgCl(s) + e– ↔ Ag(s) + Cl- (aq)

 Indicator Electrode & Their Types
• Used in conjugation with reference electrode
• Used to determine the conc. Of analyte in
sample solution
Types
 Metallic Electrode
 Membrane Electrode
Metallic Electrode

 First Kind of Electrodes

 2nd Kind of Electrodes
 Redox Electrode (Noble metal Electrode)
Membrane Electrode (Ion Selective Electrode)

 Glass Membrane Electrode (pH meter)

 Polymer Ion Electrode
 Crystalline Membrane Electrode
 Gas Sensio Probe
 Indicator Electrodes

Two classes of indicator electrodes are used in potentiometry:

 Metallic electrodes
• Electrodes of the first kind
• Electrode of the second kind
• Redox electrode

 Membrane electrodes (ion-selective electrodes)

• Glass pH electrode
 Metallic electrodes

Electrodes of the first kind

• A metal in contact with a solution containing its cation.
• The most common ones:
Silver electrode (dipping in a solution of AgNO3)
• Ag+ + e ↔ Ag
Copper electrode (dipping in a solution of Cu So4)
• Cu+2 + 2e ↔ Cu 
Zn electrode (dipping in a solution of Zn So4)
• Zn+2 + 2e ↔ Zn
Electrode of the second kind
• A metal wire that coated with one of its salts precipitate.
• Respond to changes in ion activity through formation of
complex.

• A common example is silver electrode and AgCl as its salt

precipitate.
• This kind of electrode can be used to measure the
activity of chloride ion in a solution.
REDOX ELECTRODE (Noble Metal
Electrode)
• An inert metal is in contact with a solution containing the
soluble oxidized and reduced forms of the redox half-
reaction.
• The inert metal is usually is platinum (Pt).
• The potential of such an inert electrode is determined
by the ratio of the reduced and oxidized species in the
half-reaction.
• A very important example of this type is the hydrogen
electrode.
REDOX ELECTRODE…

In the Nernst equation

E is the potential at the indicator electrode,
E° is the standard potential of the electrochemical reduction (a
value that changes as the chemical identity of the couple
changes),
R is the gas law constant, T is the absolute temperature of the
solution, n is the number of electrons transferred in the
reduction (the value in the half reaction)
F is the faraday constant, and the aOx and aRed terms are the
activities of the oxidized and reduced chemical species,
respectively, in the solution. The activities can be replaced by
concentrations of the ionic species if the solution is sufficiently
dilute.
 Membrane electrodes
Glass pH electrode
Advantages over other electrodes for pH measurements:

 Its potential is essentially not affected by the presence of

oxidizing or reducing agents.
 It operates over a wide pH range.
 It responds fast and functions well in physiological
systems.
Glass pH electrode
Principle:
• For measurement, only the bulb needs to be submerged.
• There is an internal reference electrode and electrolyte
(Ag| AgCl| Cl─) for making electrical contact with the glass
membrane, its potential is necessarily constant and is set by
the concentration of HCl.
• A complete cell, then, can be represented by:

 
Theory of the glass membrane potential

• Both the inside and outside surfaces of the glass

membrane in the GE bulb have SiOH groups.
• The interior surface of the glass membrane is in contact
with a constant concentration of HCl, and so the number
of SiO– groups on the interior surface remains constant.
• By contrast, the number of SiO– groups on the exterior
of the glass membrane will change when the pH of the
solution the glass membrane is immersed in changes.
• The difference in charge on the inside and outside of the
glass membrane results in a membrane potential.
• If we can set up an experiment to measure the membrane
potential, then this corresponds to measuring the pH of
the solution in which the glass electrode is immersed.
 Alkaline Error
• Systematic error occurs when using glass pH electrode to
measure pH of extremely alkaline solution

• Glass pH electrode responds very selectively to H+ ions, but,

sensitive to alkali metal ions too

• Caused by interference of high concentration of alkaline metal

ions, e.g: Li+, Na+, K+
 Alkaline Error…

Figure 2: Cross-section of glass pH membrane.

Alkaline metal cations will compete with H+for free spaces
in solvated layer.
 Application of Potentiometric
Measurement
• Clinical Chemistry
– Ion-selective electrodes are important sensors for clinical samples
because of their selectivity for analytes in complex matricies.
– The most common analytes are electrolytes, such as Na+, K+, Ca2+,H+, and Cl-, and
dissolved gases such as CO2.

• Environmental Chemistry
– For the analysis of of CN-, F-, NH3, and NO3- in water and wastewater.
– One potential advantage of an ion-selective electrode is the ability to
incorporate it into a flow cell for the continuous monitoring of
wastewater streams.

• Potentiometric Titrations
– Use a pH electrode to monitor the change in pH during the titration.
– For determining the equivalence point of an acid–base titration.
– Possible for acid–base, complexation, redox, and precipitation titrations,
as well as for titrations in aqueous and nonaqueous solvents.
Agriculture

NO3, NH4, Cl, K, Ca, I, CN in soils, plant material, fertilizers and feedstuffs

Detergent Manufacture

Ca, Ba, F for studying effects on water quality

Food Processing

 NO3, NO2 in meat preservatives

 Salt content of meat, fish, dairy products, fruit juices, brewing solutions.
 F in drinking water and other drinks.
 Ca in dairy products and beer.
 K in fruit juices and wine making.
 Corrosive effect of NO3 in canned foods
Thank you