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Potentiometry

Potentiometry is a field of electroanalytical chemistry that measures potential under conditions of no current flow. The measured potential can be used to determine the concentration of a component in a solution. Potentiometry includes measurements using ion-selective electrodes like pH electrodes that produce a potential proportional to the concentration of an analyte ion. Ion-selective electrodes consist of an ion-sensitive membrane, internal reference electrode, external reference electrode, and voltmeter. A pH meter measures pH using a pH electrode that produces a voltage proportional to hydrogen ion concentration.

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413 views

Potentiometry

Potentiometry is a field of electroanalytical chemistry that measures potential under conditions of no current flow. The measured potential can be used to determine the concentration of a component in a solution. Potentiometry includes measurements using ion-selective electrodes like pH electrodes that produce a potential proportional to the concentration of an analyte ion. Ion-selective electrodes consist of an ion-sensitive membrane, internal reference electrode, external reference electrode, and voltmeter. A pH meter measures pH using a pH electrode that produces a voltage proportional to hydrogen ion concentration.

Uploaded by

alexpharm
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Potentiometry

Introduction

Potentiometry is the field of electroanalytical chemistry in which potential is measured


under the conditions of no current flow. The measured potential may then be used to
determine the analytical quantity of interest, generally the concentration of some
component of the analyte solution. The potential that develops in the electrochemical cell
is the result of the free energy change that would occur if the chemical phenomena were
to proceed until the equilibrium condition has been satisfied.

This concept is typically introduced in quantitative analysis courses in relation to


electrochemical cells that contain an anode and a cathode. For these electrochemical
cells, the potential difference between the cathode electrode potential and the anode
electrode potential is the potential of the electrochemical cell.

If the reaction is conducted under standard state conditions, this equation allows the
calculation of the standard cell potential. When the reaction conditions are not standard
state, however, one must utilize the Nernst equation to determine the cell potential.

Physical phenomena which do not involve explicit redox reactions, but whose initial
conditions have a non-zero free energy, also will generate a potential. An example of this
would be ion concentration gradients across a semi-permeable membrane. This can also
be a potentiometric phenomena, and is the basis of measurements that use ion-selective
electrodes.
Instrumentation

See the documents on ion-selective electrodes and pH meters.

Ion-Selective Electrodes (ISE)


Introduction

An Ion-Selective Electrode (ISE) produces a potential that is proportional to the


concentration of an analyte. Making measurements with an ISE is therefore a form of
potentiometry. The most common ISE is the pH electrode, which contains a thin glass
membrane that responds to the H+ concentration in a solution.

Theory

The potential difference across an ion-sensitive membrane is:

E = K - (2.303RT/nF)log(a)

where K is a constant to account for all other potentials, R is the gas constant, T is
temperature, n is the number of electrons transferred, F is Faraday's constant, and a is the
activity of the analyte ion. A plot of measured potential versus log(a) will therefore give a
straight line.

ISEs are susceptible to several interferences. Samples and standards are therefore diluted
1:1 with total ionic strength adjuster and buffer (TISAB). The TISAB consists of 1 M
NaCl to adjust the ionic strength, acetic acid/acetate buffer to control pH, and a metal
complexing agent.

Instrumentation
ISEs consist of the ion-selective membrane, an internal reference electrode, an external
reference electrode, and a voltmeter. A typical meter is shown in the document on the pH
meter.

Schematic of an ISE measurement

Commercial ISEs often combine the two electrodes into one unit that are then attached to
a pH meter.

Picture of a commercial fluoride ISE

pH Meter
Introduction
The pH meter measures the pH of a solution using an ion-selective electrode (ISE) that
responds to the H+ concentration of the solution. The pH electrode produces a voltage
that is proportional to the concentration of the H+ concentration, and making
measurements with a pH meter is therefore a form of potentiometry. The pH electrode is
attached to control electronics which convert the voltage to a pH reading and displays it
on a meter.

Instrumentation

A pH meter consists of a H+-selective membrane, an internal reference electrode, an


external reference electrode, and a meter with control electronics and display.
Commercial pH electrodes usually combine all electrodes into one unit that are then
attached to the pH meter.

Picture of a pH meter

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