POTENTIOMETRY  The two electrodes are named as reference electrode
and indicator electrode. The reference electrode is the
POTENTIOMETRY- the measurement of electrical potential as
a technique in chemical analysis
 Is an instrumental technique that involves the
measurement of a voltage (potential) difference
between two electrodes that comprise an
electrochemical cell under equilibrium conditions.
 Potential or voltage is the signal measured in
potentiometry
 The two electrodes are the indicator electrode
(redox, metal, membrane electrodes), one that
responds selectively to a certain analyte usually in
ionic form, and a reference electrode that provides
a constant and stable potential
 This voltage is directly related to the logarithm of
the activity (in more practical terms, concentration)
of the analyte through the Nernst equation
 The Nernst equation serves as the basis for
quantitation for this technique
POTENTIOMETRIC TITRATION
 is a technique similar to direct titration but in this no
indicator reagent is used instead an electrode is used as
an indicator.
 In potentiometric titrations, a cell is used with
reference electrode, salt bridge, analyte and an
indicator electrode.
INSTRUMENTATION IN POTENTIOMETRY
 The instrumentation involved in potentiometry is
inexpensive as the technique only requires a reference
electrode (anode) and an indicator electrode (cathode),
which is also the input transducer, a high impedance
meter (output transducer)
 The voltage developed in the indicator electrode is due
to either (1) the reduction of an analyte or (2) the
presence of a concentration difference (chemical
potential) associated with an analyte across a highly
sensitive membrane
 The voltage in the indictor electrode is compared to the
voltage provided by the reference electrode (anode)
POTENTIOMETRIC TITRATION PRINCIPLE:
 When the pair of electrodes are placed in the sample
solution or analyte it shows the potential difference
between two electrodes by addition of the titrant or by
the change in the concentration of ions.
electrode which maintains its potential and remains
stable when dipped into a sample solution. Indicator
electrode is the electrode which responds to variation in
the potential of analyte solution. A salt bridge is used to
prevent interference of analyte with reference
electrode.
 The electromotive force or over all potential difference
can be calculated by using following formula
Ecell = Eind – Eref + Ej
Where Ecell = electromotive force of the complete cell
Eind = electromotive force of the indicator electrode
Eref = electromotive force of the reference electrode
Ej = electromotive force at the junction across the salt bridge
POTENTIOMETRIC TITRATION PROCEDURE
 Potentiometric titration involves measurement of the
potential of an indicator electrode with respect to a
reference electrode as a function of titrant volume.
 In this titration we measure and record the cell
potential (in millivolts or pH) after adding titrant each
time.
 As we approach the end point, we start adding titrants
in very small quantities.
 The most straight forward and mostly used method of
end point detection in potentiometric titration is
plotting a graph between cell potential and volume of
titrant. The midpoint of the steeply rising portion of the
graph or curve is estimated visually and taken as an end
point.
TYPES OF POTENTIOMETRIC TITRATION
1. Acid - base titration – Titration of HCl with NaOH can be
done by potentiometric titration. In this concentration of a
given acid/base is determined by using a standard solution.
2. Redox Titration – Potentiometric titration was first used
for redox titration by Crotogino. He titrated halide ions with
KMnO4 using a platinum electrode and calomel electrode.
3. Complexometric titration – In this type of potentiometric
titration concentration of metal ions are determined in the
analyte. In this membrane electrodes are used.
4. Precipitation Titration – In this type of titration precipitate
is formed as the name suggests. When addition of the titrant
no longer forms a precipitate, that point is noted as the
endpoint.
APPLICATIONS OF POTENTIOMETRIC TITRATIONS
 It is used in clinical chemistry for analysis of metals.
 It is used for analysis of cyanide, ammonia etc. in water
or wastewater.
 It is used in agriculture for detection of different
elements in soils, fertilizers etc.
 It is used in detergent manufacturing, food processing
etc.
POTENTIOMETER
For any potentiometric measurement we must have:
1. Reference electrode
2. Indicator electrode.
3. Potentiometer
4. Salt bridge to connect the two electrode solutions and
complete the circuit.
REFERENCE ELECTRODE
Reference electrode must:
1. Have a constant potential
2. Its potential must be definite
To express any electrode we have to mention:
1. Redox reaction at the electrode surface.
2. Half cell and Nernst equation.
3. Sketch of its design.
4. Any necessary conditions for its preparation.
5. Any necessary precautions for its use.
NERNST EQUATION
 States that the electrochemical cell potential is directly
proportional to the concentration of the sample
solution.
 Discovered year 1889
Ag/AgCl
Disadvantage of silver-silver chloride electrode:
1. It is more difficult to prepare than SCE.
2. AgCI in the electrode has large solubility in saturated
KCl
Advantage of Ag-AgCI electrodes over SCE.
3. It has better thermal stability.
4. Less toxicity and environmental problems with
consequent cleanup and disposal difficulties.
INDICATOR ELECTRODE
Ecell=Eindicator-Ereference
It must be:
(a) give a rapid response and
(b) its response must be reproducible.

Metallic electrodes: where the redox reaction takes place at

the electrode surface.
Membrane (specific or ion selective) electrodes:

INDICATOR ELECTRODES FOR NEUTRALIZATION REACTION

GLASS MEMBRANE ELECTRODE

INDICATOR AND REFERENCE ELECTRODES

Types of Indicator electrodes
1. Metal (inert or response to the analyte according to a
redox reaction)
2. Membrane (sparingly-soluble solids, PVC-based
membranes)
3. Ion-Sensitive Field Effect Transistors (ISFETS)

Types of Reference electrodes

1. Standard hydrogen electrode (SHE)
2. Saturated calomel electrode (SCE)
3. Silver | silver chloride electrode
MEASUREMENT OF PH
 pH meters use electrochemical reactions.
 Ion selective probes: respond to the presence of a
specific ion. pH probes are sensitive to pH+3O.
Glass Membrane Electrode
E = K + 0.059 (pH1-pH2)
K = constant known by the asymmetry potential.
PH1 = pH of the internal solution 1.
PH2 = pH of the external solution 2.
The final equation is: E = K-0.059 pH

Advantages of glass electrode:

 It can be used in presence of oxidizing, reducing,
complexing
Disadvantage:
 Delicate, it can’t be used in presence of dehydrating
agent e.g. conc. H2SO4, ethyl alcohol….
 Interference from Na+ occurs above pH 12 i.e Na+
exchange together with H+above pH 12 and higher
results are obtained.
 It takes certain time to come to equilibrium due to
resistance of glass to electricity.
QUINHYDRONE ELECTRODE
Advantages:
1. It is not affected by catalytic poisons.
2. Easy to prepare and use.
3. It comes to equilibrium rapidly.
Disadvantages:
4. It cannot be used in presence of oxidising agents and
reducing agents
5. The upper limit of the electrode use is pH 8
6. It needs to be used freshly.
Potentiometric titration
 It is used for all types of volumetric analysis: acid base,
precipitimetry, complexometry and redox
 It is used when it is not easy or impossible to detect the
end point by ordinary visual methods i.e:
1. For highly coloured or turbid solutions.
2. For very dilute solutions 10-3, 10-6 M.
3. When there is no available indicator
APPLICATION OF POTENTIOMETRIC TITRATION IN:
a) Neutralization reactions: glass /calomel electrode for
determination of pH
b) Precipitation reactions: Membrane electrodes for the
determination of the halogens using silver nitrate reagent
c) Complex formation titration: metal and membrane
electrodes for determination of many cations (mixture of
Bi3+, Cd2+ and Ca2+ using EDTA)
d) Redox titration: platinum electrode For example for
reaction of Fe3+/ Fe2+ with Ce4+/Ce3+
SUMMARY
 Potentiometry is an instrumental technique that relies
on the measurement of potential (voltage) across an
indicator and reference electrodes under equilibrium
conditions (zero current flowing)
 Common reference electrodes used in potentiometry
are SHE, SCE and Ag/AgCl
 There are different types of indicator electrodes (metal,
membrane, liquid-exchanger, PVC-based, solid-state,
gas-sensing)
 Quantitation in potentiometry is based on the Nernst
equation that provides a linear relationship between the
cell potential and the log activity or concentration of the
ion of interest
 External calibration and standard addition techniques
are approaches used in quantitative analysis in
potentiometry