1. POTENTIOMETRY
&
ION SELECTIVE ELECTRODE
DR.RUCHI GOKANI
Dept of biochemistry
s.b.k.s.m.i.r.c

2. Potentiometry
 In potentiometry, the potential of an electrochemical cell is
measured under static conditions because no current flows
while measuring a solution’s potential.
 Use of electrodes to measure voltage that provide chemical
information.
 Concentration of ions in solution is calculated from the
measured potential difference between the two electrodes
immersed in solution under condition of zero current.
 This type of system includes at least two electrodes,
identified as an indicator electrode (right half-cell) and a
reference electrode (left half-cell ) which act as the cathode
and anode respectively.

3.  Each electrode is in contact with either the
sample (in the case of the “indicator
electrode”) or a reference solution ( in the case
of the “reference electrode”).
 Electrodes + solution = electrochemical cell
Each electrode represent half cell reaction with
correspondance half cell potential.

5. Potentiometer
• A device for measuring the potential of an
electrochemical cell without drawing a current or
altering the cell’s composition.
• The potential 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.

6. • Two electrodes connected to Potentiometer to measure
potential difference
• Indicator electrode (Eind) – potential respond to change
according to conc. of ions
• Reference electrode (Eref) – half cell potential does not
change.
Ecell = Eind ─ Eref + Elj

7. Schematic diagram of an electrochemical cell of potentiometric measurement
Example 1

8.  System Components
 Liquid Junction
 Reference electrode
 Indicator or measuring electrode
 Readout device (Potentiometer)

9.  Liquid junction – also known as a salt bridge are
required to complete the circuit between the
electrodes.
Functions:
It allows electrical contact between the two solutions.
It prevents the mixing of the electrode solutions.
It maintains the electrical neutrality in each half cell as
ions flow into and out of the salt bridge.

10.  Reference Electrode- is an electrochemical half-cell
that is used as a fixed reference for the measurement
of cell potentials.
 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
 Always treated as the left-hand electrode
Examples:
Normal hydrogen electrode
Saturated calomel electrode
Ag-AgCl electrode

11. Reference Electrodes
Calomel electrode- composed of
mercury/mercurous chloride; It is dependable but
large, bulky, and affected by temperature.
Silver/silver chloride- Widely used because simple,
inexpensive, very stable and non-toxic.
o reference electrodes are more compact -- overall
better & faster
Normal Hydrogen Electrode- consists of a
platinized platinum electrode in HCl solution with
hydrogen at atmospheric pressure bubbled over the
platinum surface.
-determination of pH of the solution.

12. Saturated calomel electrode

13. Silver-silver chloride electrode
Standard hydrogen electrode (SHE)

14. Indicator or measuring electrode
• The potential of this electrode is proportional to the
concentration of analyte.
• Two classes of indicator electrodes are used in
potentiometry:
o metallic electrodes
• Electrodes of the first kind
• Electrode of the second kind
• Redox electrode
o membrane electrodes (ion-selective electrodes)
• glass pH electrode

15. Metallic electrodes
Electrodes of the first kind
• A metal in contact with a solution containing its cation.
• The potential is a function of concentration of Mn+ in a
Mn+ / M. The most common ones:
o Silver electrode (dipping in a solution of AgNO3)
• Ag+ + e ↔ Ag
o Copper electrode
• Cu+2 + 2e ↔ Cu
o Zn electrode
• Zn+2 + 2e ↔ Zn

16. 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.

17. Redox 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.

18.  Indicator Electrode- also called the measuring
electrode
It is immersed in a solution of the analyte,
develops a potential, Eind that depends on the
activity of the analyte.
Is selective in its response
It is the other electrochemical half-cell that
responds to changes in the activity of a
particular analyte species in a solution.
Example:
Ion-Selective Electrodes

19. Ion selective electrode
 An ion-selective electrode (ISE), also known as a
specific ion electrode (SIE), is a transducer (or sensor)
that converts the activity of a specific ion dissolved in a
solution into an electrical potential, which can be
measured by a voltmeter or pH meter.
 indicator electrode based on determination of cations
or anions by the selective absorption of these ions to a
membrane surface.

20. TYPES OF ION SELECTIVE
ELECTRODE
•Glass Membrane Electrode
•Solid State Electrode
•Liquid Membrane Electrode
•Gas Sensing Electrode

21. GLASS MEMBRANE ELECTRODE
• Responsive to univalent cations ( H+ , Na+)
• Glass electrodes available for Na+, K+, NH4+, Li+,
Ag+(cations only) by varying glass composition
• The selectivity for this cation by varying the
composition of a thin ion sensitive glass membrane.
• Glass membrane manufactured from SiO2 with
negatively charged oxygen atom.
• Inside the glass bulb, a dilute HCl solution and silver
wire coated with a layer of silver chloride.
• The electrode is immersed in the solution and pH is
measured
• Example: pH electrode

22. Glass pH electrode
• Advantages over other electrodes for pH
measurements:
o Its potential is essentially not affected by the
presence of oxidizing or reducing agents.
o It operates over a wide pH range.
o It responds fast and functions well in physiological
systems.
o Selective for monovalent cations only because
polyvalent ions can not penetrate the surface of
membrane.

23. pH electrode
 Selective for the
detection of hydrogen
ions.
 The measuring or
indicator electrode has
a “glass membrane”
 pH is then determined
from potential between
the pH electrode and a
standard reference
electrode.

24. SOLID STATE ELECTRODE
• Solid state electrode are selective primarily to anions.
• It may be a
- homogenous membrane electrode
- heterogeneous membrane electrode.
• Homogenous membrane electrode: ion-selective
electrodes in which the membrane is a crystalline
material (AgI/Ag2S).

25. • Heterogeneous membrane electrode: ion-selective
electrodes prepared of an active substance, or mixture
of active substances (silicone rubber or PVC)
• Example: Fluoride ion selective electrode

26. LIQUID MEMBRANE ELECTRODE
• Liquid membrane is a type of ISE based on water-
immiscible liquid substances produced in a polymeric
membrane used for direct potentiometric
measurement.
• Used for direct measurement of several polyvalent
cations (Ca ion) as well as a certain anions.
• Inner compartment of electrode contains reference
electrode & aqueous reference solution.
• Outer compartment – organic liquid ion exchanger

27. •The polymeric membrane made of PVC to separate the
test solution from its inner compartment which contains
standard solution of the target ion.
•The filling solution contains a chloride salt for
establishing the potential of the internal Ag/AgCl wire
electrode.

28. GAS SENSING ELECTRODE
• Available for the measurement of ammonia, carbon
dioxide and nitrogen oxide.
• This type of electrode consist of permeable membrane
and an internal buffer solution.
• The pH of the buffer changes as the gas react with it.
• The change is detected by a combination pH sensor.
• This type of electrode does not require an external
reference electrode.

29.  Measurement of PCO2 in
routine blood gases
 A modified pH electrode
with a CO2 permeable
membrane covering the
glass membrane surface
 A bicarbonate buffer
separates the
membranes
 Change in pH is
proportional to the
concentration of
dissolved CO2 in the
blood
pco2 electrode

30. Application of Potentiometric
Measurement
• Clinical Chemistry
o Ion-selective electrodes are important sensors
for clinical samples because of their selectivity
for analytes.
o The most common analytes are electrolytes,
such as Na+, K+, Ca2+,H+, and Cl-, and dissolved
gases such as CO2.
• Environmental Chemistry
o For the analysis of of CN-, F-, NH3, and NO3
- in
water and wastewater.

31. • Potentiometric Titrations
o pH electrode used to monitor the change in pH
during the titration.
o For determining the equivalence point of an
acid–base titration.
o Possible for acid–base, redox, and precipitation
titrations, as well as for titrations in aqueous
and nonaqueous solvents.
• Agriculture
o NO3, NH4, Cl, K, Ca, I, CN in soils, plant
material, fertilizers.
• Detergent Manufacture
o Ca, Ba, F for studying effects on water quality

32. • Food Processing
o NO3, NO2 in meat preservatives
o Salt content of meat, fish, dairy products, fruit
juices, brewing solutions.
o F in drinking water and other drinks.
o Ca in dairy products and beer.
o K in fruit juices and wine making.
o Corrosive effect of NO3 in canned foods.

33. advantages
• Relatively inexpensive and simple to use and have an
extremely wide range of applications and wide
concentration range.
• Under the most favourable conditions, when measuring
ions in relatively dilute aqueous solutions and where
interfering ions are not a problem, they can be used
very rapidly and easily.
• ISEs can measure both positive and negative ions.
• They are unaffected by sample colour or turbidity.

34. • Non-destructive: no consumption of analyte.
• Non-contaminating.
• Short response time: in sec. or min. useful in industrial
applications.

35. LIMITATION
• Precision is rarely better than 1%.
• Electrodes can be affected by proteins or other organic
solutes.
• Interference by other ions.
• Electrodes are fragile and have limited shelf life.