Chapter V-Potentiometry

In potentiometry we measure the potential of an electrochemical cell under static

conditions. Because no current—or only a negligible current—flows through the electrochemical
cell, its composition remains unchanged. For this reason, potentiometry is a useful quantitative
method. The first quantitative potentiometric applications appeared soon after the formulation,
in 1889, of the Nernst equation, which relates an electrochemical cell’s potential to the
concentration of electroactive species in the cell.
Potentiometry initially was restricted to redox equilibria at metallic electrodes, limiting its
application to a few ions. In 1906, Cremer discovered that the potential difference across a thin
glass membrane is a function of pH when opposite sides of the membrane are in contact with
solutions containing different concentrations of H 3O+. This discovery led to the development of
the glass pH electrode in 1909. Other types of membranes also yield useful potentials. For
example, in 1937 Kolthoff and Sanders showed that a pellet of AgCl can be used to determine
the concentration of Ag+. Electrodes based on membrane potentials are called ion-selective
electrodes, and their continued development extends potentiometry to a diverse array of
analytes.

Potentiometric Measurements
We use a potentiometer to determine the difference between the potential of two
electrodes. The potential of one electrode—the working or indicator electrode—responds to the
analyte’s activity, and the other electrode—the counter or reference electrode—has a known,
fixed potential. In this section we introduce the conventions for describing potentiometric
electrochemical cells, and the relationship between the measured potential and the analyte’s
activity.

Potentiometric Electrochemical Cells

A schematic diagram of a typical potentiometric electrochemical cell is shown in Figure 11.7.
The electrochemical cell consists of two half-cells, each containing an electrode immersed in a
solution of ions whose activities determine the electrode’s potential. A salt bridge containing
an inert electrolyte, such as KCl, connects the two half-cells. The ends of the salt bridge are
fixed with porous frits, allowing the electrolyte’s ions to move freely between the half-cells and
the salt bridge. This movement of ions in the salt bridge completes the electrical circuit.
History Of Potentiometry
Shown below are major milestones in the development of potentiometry.

The origin of the measured potential at an indicator electrode is most generally the
separation of charge across an interface between solutions of differing ionic strengths (an inner
solution at fixed analyte activity and an outer solution with variable analyte activity).
The mechanism leading to this charge separation varies with electrode type. After defining
what is meant by a junction potential, we will consider two types of indicator electrodes
1. the metallic direct indicator electrode, whose response involves a surface or solution
redox reaction, and
2. the membrane electrode, or ion-selective electrode (ISE).
Direct Indicator Electrodes
The simplest type of direct indicator electrode
is a metal, M, in contact with a solution
containing its own cation, M +. At the metal-
solution interface, a potential develops that is
proportional to the activity of the metal ion in
solution.
Ion-Selective Electrodes
So far you have learned that during the technique of potentiometry, the potential, or voltage, of
an electrochemical cell is
measured. The cell consists of
both an indicator and reference
electrode. Since the potential of
the reference electrode is
constant, it is the potential
developed at the indicator
electrode that contains
information about the amount of
analyte in a sample. During the
measurement, there is little to no
current flow. An electrochemical
cell for making a potentiometric
measurement with a membrane
electrode (also known as an ion-
selective electrode, ISE) is shown
in Figure 1. As you can see the
main difference between an ISE
and the direct indicator electrode
is in the ISE's composition.
Figure 2. Electrochemical cell for making a
potentiometric measurement with an ISE.

As indicated by their name, ion-selective electrodes possess a high degree of selectivity. The
selectivity of the ISE is determined by the composition of the membrane. Ideally the membrane
allows the uptake of only one specific ion into it. The analyte ion may be a cation or an anion.
The three main components of making a measurement at an ISE are an inner reference, or
standard, solution and an outer analyte, or sample, solution separated by a thin membrane.
These components are shown in Figure 2. Redox processes do not occur at ISEs. The potential
developed at the membrane is the result of either an ion exchange process or an ion transport
process occurring at each interface between the membrane and solution. The basics of ion
exchange and ion transport are reviewed in the next sections.

Types of Potentiometry

Potentiometric Titration
It is the procedure through which the quantity of the given test substance is determined
by the measured addition of titrant until the entire test substance undergoes reaction. After
the titration process, the potential difference between the two electrodes (namely the reference
and indicator electrode) is measured in conditions where a thermodynamic equilibrium is
maintained and the current passing through the electrodes does not disturb this equilibrium.

Potentiometric Titration Principle

 Potentiometric titration is a laboratory method to determine the concentration of a given
analyte. It is used in the characterization of acids. In this method, there is no use of a chemical
indicator. Instead, the electric potential across the substance is measured.

Potentiometric Titration Method

Potentiometric Titration is done via the usage of two electrodes – an indicator electrode
and a reference electrode (generally a hydrogen electrode or a silver chloride electrode). One
half-cell is formed with the indicator electrode and the ions of the analyte, which is generally an
electrolyte solution. The other half-cell is formed by the reference electrode.
 1. Acid-Base Titration: This type of potentiometric titration is used to determine the
concentration of a given acid/base by neutralizing it exactly using a standard solution of
base/acid whose concentration is known.
2. Redox Titration: This type of potentiometric titration involves an analyte and titrant
that undergo a redox reaction. An example of this type of titration would be the
treatment of an iodine solution with a reducing agent which produces iodide ion (a
starch indicator is used to get the endpoint).
3. Complexometric Titration: This type of titration can also be referred to as
chelatometry. In this method, a colored complex is formed, indicating the end point of
the titration. This method is used to determine a mixture of metal ions in a given
solution.
4. Precipitation Titration: This type of titration involves a reaction between the given
analyte and the titrant wherein an insoluble precipitate is formed. The end-point of this
titration is noted when the addition of the titrant no longer forms a precipitate

Voltaic Cell
In redox reactions, electrons are transferred from one species to another. If the reaction
is spontaneous, energy is released, which can then be used to do useful work. To harness this
energy, the reaction must be split into two separate half reactions: the oxidation and reduction
reactions. The reactions are put into two different containers and a wire is used to drive the
electrons from one side to the other. In doing so, a Voltaic/ Galvanic Cell is created.
When a redox reaction takes place, electrons are transferred from one species to the
other. If the reaction is spontaneous, energy is released, which can be used to do work.
Consider the reaction of a solid copper (Cu(s)) in a silver nitrate solution (AgNO3(s)).

The AgNO3(s) dissoci
-
ates in water to produce Ag+(aq)+ ions and NO−3(aq) ions. The NO  ions can be ignored
3 (aq)
since they are spectator ions and do not participate in the reaction. In this reaction, a copper
electrode is placed into a solution containing silver ions. The Ag +(aq) will readily oxidize
Cu(s) resulting in Cu2+(aq), while reducing itself to Ag(s).
This reaction releases energy. When the copper electrode solid is placed directly into a
silver nitrate solution, however, the energy is lost as heat and cannot be used to do work. In
order to harness this energy and use it do useful work, we must split the reaction into two
separate half reactions; The oxidation and reduction reactions. A wire connects the two
reactions and allows electrons to flow from one side to the other. In doing so, we have created
a Voltaic/ Galvanic Cell.
 Figure 
7:  Voltaic Cell

A Voltaic Cell (also known as a Galvanic Cell) is an electrochemical cell that uses spontaneous
redox reactions to generate electricity. It consists of two separate half-cells. A half-cell is
composed of an electrode (a strip of metal, M) within a solution containing M n+ ions in which M
is any arbitrary metal. The two half cells are linked together by a wire running from one
electrode to the other. A salt bridge also connects to the half cells. The functions of these parts
are discussed below.

Half Cells
Half of the redox reaction occurs at each half cell. Therefore, we can say that in each half-cell a
half-reaction is taking place. When the two halves are linked together with a wire and a salt
bridge, an electrochemical cell is created.

Electrodes
An electrode is strip of metal on which the reaction takes place. In a voltaic cell, the
oxidation and reduction of metals occurs at the electrodes. There are two electrodes in a voltaic
cell, one in each half-cell. The cathode is where reduction takes place and oxidation takes
place at the anode.
Through electrochemistry, these reactions are reacting upon metal surfaces,
or electrodes. An oxidation-reduction equilibrium is established between the metal and the
substances in solution. When electrodes are immersed in a solution containing ions of the same
metal, it is called a half-cell. Electrolytes are ions in solution, usually fluid, that conducts
electricity through ionic conduction. Two possible interactions can occur between the metal
atoms on the electrode and the ion solutions.
 1. Metal ion Mn+ from the solution may collide with the electrode, gaining "n"
electrons from it, and convert to metal atoms. This means that the ions are
reduced.
2. Metal atom on the surface may lose "n" electrons to the electrode and enter the
solution as the ion Mn+ meaning that the metal atoms are oxidized.

When an electrode is oxidized in a solution, it is called an anode and when an electrode is

reduced in solution. it is called a cathode.
 Anode: The anode is where the oxidation reaction takes place. In other words, this is
where the metal loses electrons. In the reaction above, the anode is the Cu(s) since it
increases in oxidation state from 0 to +2.
 Cathode: The cathode is where the reduction reaction takes place. This is where the
metal electrode gains electrons. Referring back to the equation above, the cathode is
the Ag(s) as it decreases in oxidation state from +1 to 0.

Parts of Voltaic Cell

 1. The anode is an electrode where oxidation occurs.
2. The cathode is an electrode where reduction occurs.
3. A salt bridge is a chamber of electrolytes necessary to complete the circuit in a voltaic
cell.
4. The oxidation and reduction reactions are separated into compartments called half-
cells.
5. The external circuit is used to conduct the flow of electrons between the electrodes of
the voltaic cell and usually includes a load.
6. The load is the part of the circuit which utilizes the flow of electrons to perform some
function.

Application

1. Direct Potentiometry
A rapid and convenient method of detecting the activity of cations and anions.
The technique used in this method is a comparison of the developed by the indicator
electrode when it is immersed in the solution with that when it is immersed in standard
solution of the analyte.
2. The Calibration Curve Method
It is applied for the determination of substance by direct potentiometry.
3. Environmental chemistry
 Pollution monitoring
4. Agriculture
 Plant materials
 Fertilizers
5. Food processing
6. Fluorine in drinking water
7. Salt content in meat, fish, dairy products, juices
8. Potentiometric Titrations