Some Basics

There are two different types of Electrical Conductivity:

1) In Metals the electric current is carried by Electrons.

2) In Liquids the electric current is carried by Ions

Every Electrochemical Process (Galvanic Cell, Electrolysis, Electro-Analysis) involves both these types of
conductivity. The junctions where they meet and transfer the electrical charge are referred to as Metal-
Liquid Interfaces. These interfaces are originally called Electrodes, but now this term is also used for
various other devices such as welding electrodes or electro-cardiogram electrodes

The Electrochemical Circuit for an Ion Selective Electrode measurement.

An ISE is immersed in an aqueous solution containing the ions to be measured, together with a separate,
external reference electrode. The electrochemical circuit is completed by connecting the electrodes to a
sensitive milli-volt meter using special low-noise cables and connectors. A potential difference is
developed across the ISE membrane when the target ions diffuse through from the high concentration
side to the lower concentration side.

At equilibrium, the membrane potential is mainly dependent on the concentration of the target ion outside
the membrane Briefly, the measured voltage is proportional to the Logarithm of the concentration, and the
sensitivity of the electrode is expressed as the electrode Slope - in millivolts

Ion selective electrode

In the diagnosis and treatment of various diseases as well as in preventative health checkups, it is
becoming increasingly important to monitor the concentrations of certain ions in a patient's body.
The use of ion-sensitive electrodes (ISEs) for determination of the concentration or the activity of ions in
aqueous media has been known for a long time. An ion-selective electrode (ISE) is an electrode which
exhibits an electrical response which is a function of concentration of a specific ion contained in a solution
which is in contact with the ISE and a reference electrode. Ion selective electrodes operate on the basis
of the Nernst principle which defines a logarithmic relationship between the potential of a solution and its
ionic concentration. An ion selective electrode responds selectively to an ion for which the electrode is
designed to analyze and is used to measure ion concentrations, ion activities, etc.

The determination of a given ion's concentration in a solution is based on the fact that within
certain limits the potential of the electrode is directly proportional to the logarithm of the
ion's activity.

Ion selective electrode sensors that can measure the activity or concentration of analyte ions and
metabolites are useful in the analysis of biological fluids including blood, urine, plasma, saliva, spinal
fluid, and serum. An ion selective electrode apparatus usually comprises an ion selective electrode and a
reference electrode. The ion selective electrode includes an ion selective membrane on the surface of it.

An ion selective electrode is defined as an electrochemical sensor with a membrane whose potential
indicates the activity of the ion to be determined in a solution. The membranes of ISE consist of liquid
electrolyte solution that has negligible electrons conductivity under condition of measurement. It has
some advantages such as:

 Portability.
 Cheaper
 Do not effect the test sample.

The Function of the Reference Electrode

The membrane potential cannot be measured directly. It needs a Metal-Liquid interface on both sides of
the membrane thus the need for a so-called reference system on both sides of the ISE membrane, with a
particular metal-liquid interface which is known to have a stable potential.

The reference electrode is a half-cell that provides a constant potential which is dependent only on the
concentration of chloride ions in the filling solution.

Ionic Strength is a measure of the total effect of all the ions in a solution. It is the sum of the
molar concentration multiplied by the square of the valency of all the ions. The effective
concentration measured at the electrode head is known as the activity of the ion. In general
chemical terms it is the number of ions taking place in any chemical reaction – measured in
concentration units.

The activity coefficient is the ratio of the activity divided by the concentration. This is a variable
factor and depends on the valency of ions and the total ionic strength of the solution.

The activity coefficient is always less than one and becomes smaller as the ionic strength increases; thus
the difference between the measured activity and the actual concentration becomes higher at higher
concentrations.

Membrane potential (or transmembrane potential) is the difference in voltage (or electrical potential
difference) between the interior and exterior of a cell (Vinterior − Vexterior)
The membrane potential has two basic functions. First, it allows a cell to function as a battery, providing
power to operate a variety of "molecular devices" embedded in the membrane. Second, in electrically
excitable cells such as neurons, it is used for transmitting signals between different parts of a cell.
Opening or closing of ion channels at one point in the membrane produces a local change in the
membrane potential, which causes electric current to flow rapidly to other points in the membrane
Nernst equation
The Nernst equation was named after the German chemist Walther Nernst who established very useful
relations between the energy or potential of a cell to the concentrations of participating ions. This
equation can be derived from the equation linking free energy changes to the reaction quotient (Q reaction)