Electrodes and

Potentiometry
Presented by:
Emmanuel Alexis C. Banga
MS Chemistry
 Potentiometric Methods
Measuring the potential of electrochemical cells without
drawing appreciable current.
Have been used to locate end points in titration.
Also used in fundamental studies to determine
thermodynamic constants such as Ka, Kb, and Kw.
Simple and inexpensive
It includes a reference electrode, an indicator electrode,
and a potential-measuring device.
 General Principles

Reference electrode 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 under study.
Examples: Standard hydrogen electrode
 General Principles

Indicator electrode - which is immersed in a

solution of the analyte, develops a potential, Eind,
that depends on the activity of the analyte.
Most indicator electrodes used in potentiometry
are selective in their responses.
 General Principles

Salt bridge prevents the components of the

analyte solution from mixing with those of the
reference electrodes.
Potassium chloride is nearly ideal electrolyte for
the salt bridge because the mobilities of K+ ion
and the Cl- ion are nearly equal.
 Preparing a salt bridge
Fill a U-tube with a conducting gel.
Prepare the conduction gel by heating 5 g of
agar in 100 mL aqueous solution containing
about 35 g of potassium chloride.
When the liquid cools, it sets up into a gel that is
a good conductor, but prevents the two
solutions at the ends of the tube from mixing.
A cell for potentiometric determination
 Sample Exercise

1. Write the electrode potentials of each. (Hint: Nernst

equation)
2. Write the equation in determining the potential
difference.
 Sample Exercise
Answers
1.

2.
 Reference Electrodes
The ideal reference electrode:
Has a potential that is accurately known
Constant
Completely insensitive to the composition of the
analyte solution
Rugged
Easy to assemble
Should maintain a constant potential while passing
minimal currents
Some of the reference electrodes
1. Calomel Electrode

2. Silver-Silver Chloride Electrode

Calomel Electrode
Calomel reference electrodes consist
of mercury in contact with a solution
that is saturated with mercury(I)
chloride (calomel) and that also
contains a known concentration
of potassium chloride.

Half-cell representation:

Half-cell reaction:
Silver-Silver Chloride Electrode
The most widely marketed reference
electrode system consists of a silver
electrode immersed in a solution of
potassium chloride that has been
saturated with silver chloride.

Half-cell representation:

Half-cell reaction:

At 25C, the potential of the saturated Ag/AgCl electrode vs.

SHE is 0.199 V.
 Calomel Electrode vs. Silver-silver
chloride electrode

They can be used at mercury(II) ions react with

temperatures greater than fewer sample components
60C than do silver ions (which can
react with proteins, for
example)
 Indicator Electrodes
An ideal indicator electrode responds rapidly and
reproducibly to changes in the concentration of an analyte
ion (or group of analyte ions).

Three types:
Metallic
Membrane
Ion-sensitive field effect transistors
 Metal Indicator Electrodes
Metal indicator electrodes are classified as:

Electrodes of the first kind

Electrodes of the second kind
Inert redox electrodes
 Electrodes of the first kind

An electrode of the first kind is a pure metal electrode that
is in direct equilibrium with its cation in the solution. A
single reaction is involved.

For example, the equilibrium between a copper and its

cation Cu2+.

Electrode potential of the half-cell reaction:

 Electrodes of the first kind

Electrode systems of the first kind are not widely used for
potentiometric determinations for several reasons.
1. Metallic electrodes are not very selective and respond not
only to their own cations but also to other more
easily reduced cations.
2. Many metal electrodes, such as zinc and cadmium, can
only be used in neutral or basic solutions because they
dissolve in the presence of acids.
3. Other metals are so easily oxidized that they can be used
only when analyte solutions are deaerated to remove
oxygen.
 Electrodes of the second kind

Metals not only serve as indicator electrodes for their own

cations but also respond to the activities of anions that
form sparingly soluble precipitates or stable complexes
with such cations.
The potential of a silver electrode, for example, correlates
reproducibly with the activity of chloride ion in a solution
saturated with silver chloride.
Electrode potential of the half-cell reaction:
 Membrane Electrodes
The most convenient method for determining pH has
involved measurement of the potential that appears
across a thin glass membrane that separates two
solutions with different hydrogen ion concentrations.
Membrane electrodes are sometimes called p-ion
electrodes because the data obtained from them are
usually presented as p-functions, such as pH, pCa, or
pNO3.
Potentiometric
Titration
Potentiometric Titration
o The potential of a suitable indicator
electrode is measured as a function of
titrant volume.
o Potentiometric titrations provide data
that are more reliable than data from
titrations that use chemical indicators
o The operator measures and records the
cell potential (in units of millivolts or pH,
as appropriate) after each addition of
reagent.
Detecting the endpoint
o A direct plot or other
recording is made of cell
potential as a function of
reagent volume.
Detecting the endpoint
o A second approach to end-
point detection is to
calculate the change in
potential per unit volume
of titrant (DE/DV ), that is,
we estimate the numerical
first derivative of the
titration curve.
Detecting the endpoint
o The point at which the
second derivative crosses
zero is the inflection point,
which is taken as the end
point of the titration, and
this point can be located
quite precisely.
 Titration Curves

Titration curve First-derivative curve Second-derivative curve

Potentiometric determination of
equilibrium constants
The potential of a silver
electrode in a solution
containing silver ion,
cyanide ion, and the It is possible to measure
complex formed between this potential with
them depends on the negligible current.
activities of the three
species.
Potentiometric determination of
equilibrium constants
Potentiometric determination of
equilibrium constants
Amperometry
 Amperometry
When current proportional to analyte concentration
is monitored at a fixed potential, the technique is
called amperometry
The electric current is measured between a pair of
electrodes that are driving an electrolysis reaction.
One reactant is the intended analyte and the
measured current is proportional to the
concentration of analyte.
 Typical Amperometric
Titration Curves

Analyte is Reagent is Both reagent and

reduced; reagent reduced; analyte analyte are
is not is not. reduced.
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Blood Glucose Monitor

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