Potentiometry and potentiometric measurements

potentiometer
A device for measuring the potential of an electrochemical cell
without drawing a current or altering the cells composition.
In potentiometry the potential of an electrochemical cell is measured
under static conditions. Because no current, or only a negligible current,
flows while measuring a solutions potential, 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 relating an
electrochemical cells potential to the concentration of electroactive
species in the cell.
When first developed, potentiometry was restricted to redox
equilibria at metallic electrodes, limiting its application to a few ions. In
1906, Cremer discovered that a potential difference exists between the
two sides of a thin glass membrane when opposite sides of the membrane
are in contact with solutions containing different concentrations of H3O+.
This discovery led to the development of the glass pH electrode in 1909.
Other types of membranes also yield useful potentials.
Potentiometric measurements:
Potentiometric measurements are made using a potentiometer to
determine the difference in potential between a working (an indicator)
electrode and a counter (a reference) electrode.
- Cathode is the working/indicator electrode. (right half-cell)
- Anode is the counter/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.
The role of the counter electrode is reduced to that supplying a reference
potential thus the counter electrode is called the reference electrode.
Potentiometric electrochemical cells:
The separation of the two electrodes is necessary to prevent the
redox from occurring spontaneously on the surface of one of the
electrodes.
The salt bridge containing an inert electrolyte such as KCl. The
movement of ions in the salt bridge will complete the electric
circuit.
When the potential of an electrochemical cell is measured, the
contribution of the liquid junction potential must be included;

Ecell = Ec Ea Elj
(lj is liquid junction : it develops at the interface between any two ionic
solutions that differ in composition and for which the mobility of the ions
differs)
Potentiometric electrochemical cells are constructed that one of the
half cells provides a known reference potential and the potential of
the other half cell indicates the analytes concentration.
Limitations and factors affecting the Nernst equation:
It is temperature dependent, should be maintained at 25C.
Matrix effects i.e. the solution of the interested analytes.
Presence of additional potentials in the electrochemical cells, this
called liquid junction potential. It could be minimized by a salt
such as KCl.
Shorthand Notation for Electrochemical Cells
A more useful representation is a shorthand, or schematic, notation that
uses symbols to indicate the different phases present in the
electrochemical cell, as well as the composition of each phase. A vertical
slash ( | ) indicates a phase boundary where a potential develops, and a
comma (,) separates species in the same phase, or two phases where no
potential develops. Shorthand cell notations begin with the anode and
continue to the cathode. For example
Zn(s) | ZnCl2 (aq, 0.0167 M) || AgNO3 (aq, 0.100 M) | Ag(s)
The double vertical slash ( || ) indicates the salt bridge, the contents of
which are normally not indicated. Note that the double vertical slash
implies that there is a potential difference between the salt bridge and
each half-cell.
Reference electrodes:
1- A standard hydrogen electrode (SHE)
Pt,H2 (g, 1atm) | H+ (aq, a = 1.00) ||
2H+ (aq) + 2 e H2 (g)
2-Saturated calomel (Hg2Cl2) Electrode (SCE), the term saturated refers
to the concentration of KCl
Hg(l ) | Hg2Cl2 (satd), KCl (aq, satd) ||
Hg2Cl2(s) +2e 2Hg(l ) + 2Cl(aq)
3- silver/silver chloride electrode:
Ag(s) | AgCl (satd), KCl (x M) ||

AgCl(s) + e Ag(s) + Cl(aq)

Indicator Electrodes:
The potential of the indicator electrode in a potentiometric
electrochemical cell is proportional to the concentration of analyte. Two
classes of indicator electrodes are used in potentiometry: metallic
electrodes, which are the subject of this section, and membrane electrodes
which also known as ion-selective electrodes, the glass pH electrode will
be the example of this kind.
Metallic indicator electrodes:
The potential of a metallic electrode is determined by the position of a
redox reaction at the electrodesolution interface. Three types of metallic
electrodes are commonly used in potentiometry, each of which is
considered in the following discussion.
1- Electrodes of the first kind:
An electrode of this type is 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:
a- Silver electrode (dipping in a solution of AgNO3)
Ag+ + e Ag
b- Copper electrode: Cu+2 + 2e Cu
c- Zn electrode: Zn+2 + 2e Zn
2- Electrode of the second kind:
Electrode of this kind is a metal wire that coated with one of its
salts precipitate. Its potential is a function of the concentration of X in an
MXn / M redox half reaction.
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. Another widely used electrode of this type is the Calomel
electrode.
3- Redox electrode:
An inert electrode that serves as a source of sink for electrons for
redox half reaction, or in another words; 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.

Cells with / without liquid junction:

There are two basic ways a cell may be set up, either without or with a
salt bridge. The first is called a cell without liquid junction. An example
of this type would be:
Pt | H2 (g), HCl (soln) | AgCl (s) | Ag
An electrical cell such as this is a Galvanic cell, and the cell is set up for
the spontaneous cell reaction. A cell without lj is always used for the most
accurate measurement because there are no uncertain potentials to
account for. However, there are a few examples of cells of this type and
these are inconvenient to use.
Cells with liquid junction: an example of this type of cell is:
Hg (l ) | Hg2Cl2 (s) | KCl (aq, satd) || HCl (soln), H2(g) | Pt
The double line represents the liquid junction between two dissimilar
solutions and is usually in the form of a salt bridge. The purpose of this is
to prevent mixing of the tow solutions. The electrode on the left side of
the cell is SCE which is a commonly used reference electrode.
The disadvantage of this type of cell is that there is a potential associated
with the liquid junction, which results from the unequal diffusion of the
ions on each side of the boundary.
Measurement of potential:
There are tow commonly used instrument for making potential
measurements. One is the potentiometer and the other is the pH meter. pH
measurements with a glass electrode involve the measurement of
potentials.
The potentiometer can be used for measurements of low resistance
circuits. The pH meter is a voltage measuring device designed for use
high-resistance glass electrodes and can be used with both low and highresistance circuits.
The 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.
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:
Reference electrode (external)| H+(unknown)| glass membrane |H+| reference electrode (internal)

Theory of the glass membrane potential:

The pH electrode functions as a result of ion exchange on the surface of a
hydrated layer. The membrane of a pH glass electrode consists of
chemically bonded Na2O and SiO2. For the electrode to become
operative, it must be soaked in water. During this process, the outer
surface of the membrane becomes hydrated. When it is so, the sodium
ions are exchanged for protons in the solution:
SiO Na+ (solid) + H+ (solution) SiOH+ (solid) + Na+ (solution)
The protons are free to move and exchange with other ions;
K Ecell
pH (unknown) =

2.303RT/F

Where k is a constant includes the potentials of the tow electrodes.

Measurements with the pH meter:
It has been mentioned earlier that because of the high resistance of the
glass electrode, an electrometer or pH meter must be used to make the
potential measurements.
The potential scale is calibrated in pH units, with each pH equal to
59.16(milli volt) at 25C. the pH meter is adjusted with the calibrated
knob to indicate the pH of the standard buffer then, the std buffer is
replaced by the unknown solution, and the pH is read from the scale. pH
meter contains a temperature adjusted dial, which changes the sensitivity
response mv /pH so that it will be equal to 2.303 RT/F .