Potentiometry 1

This document discusses the principles and applications of potentiometry. It begins by defining potentiometry as a method that measures potential under conditions of no current flow, where the measured potential is proportional to analyte concentration. It then provides details on the basic components and principles of potentiometric cells, including reference electrodes, indicator electrodes, and how cell potential relates to analyte concentration. Applications mentioned include pH measurement, environmental monitoring, and clinical analysis. Specific electrode types and the use of potentiometry for pH measurement are also outlined.

Uploaded by

Abdullah Bin Tariq

We take content rights seriously. If you suspect this is your content, claim it here.

Available Formats

Download as PPTX, PDF, TXT or read online on Scribd

0% found this document useful (0 votes)

24 views

Potentiometry 1

Uploaded by

Abdullah Bin Tariq

We take content rights seriously. If you suspect this is your content, claim it here.

Available Formats

Download as PPTX, PDF, TXT or read online on Scribd

You are on page 1/ 15

Potentiometry

References
• Modern Analytical Chemistry by David T. Harvey
• Fundamentals of Analytical Chemistry by Skoog and West
• https://youtu.be/P1wRXTl2L3I
Potentiometry
Potential is measured under the conditions of no current flow
The measured potential is proportional to the concentration of some component of the analyte
Introduction
 Potentiometric methods of analysis are based on measuring the potential of
electrochemical cells without drawing appreciable current.
 For nearly a century, potentiometric techniques have been used for locating end
points in titrations.
 Ion concentrations are measured directly from the potential of ion-selective
membrane electrodes. These electrodes are relatively free from interferences and
provide a rapid, convenient, and nondestructive means for quantitatively
determining numerous important anions and cations.
Applications

The number of potentiometric measurements

made on a daily basis is staggering.
Manufacturers measure the pH of many
consumer products, clinical laboratories
determine blood gases as important indicators
of disease states, industrial and municipal
effluents are monitored continuously to
determine pH and concentrations of
pollutants, and oceanographers determine
carbon dioxide and other related variables in
seawater.
Potentiometric measurements are also used in
fundamental studies to determine
thermodynamic equilibrium constants.
Equipment
The equipment for potentiometric methods is simple and inexpensive and includes
• a reference electrode,
• an indicator electrode, and
• a potential-measuring device

A reference electrode is a half-cell having a known electrode potential that remains constant at constant
temperature and is independent of the composition of the analyte solution.

An indicator electrode has a potential that varies in a known way with variations in the concentration of an
analyte.
Basic Principles of Potentiometry

• Combining two half-cells

(two half-redox
reactions) and measuring
the potential difference
between them that gives
Ecell

• If the potential of one

haf-cell (one- half
reaction) is held constant
then the potential of the
other half (half cell or
half reaction) will be
known and consequently
the concentration of the
species on this side can
be measured.
Equipment
Absolute values for individual half-cell potentials cannot be
determined in the laboratory, that is, only relative cell potentials
can be measured experimentally.
Figure shows a typical cell for potentiometric analysis.
This cell can be represented as

By convention the reference electrode is on the left hand side

The reference electrode in this diagram is 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. It can be a
standard hydrogen electrode but seldom is because a standard hydrogen
electrode is somewhat troublesome to maintain and use. By convention, the
reference electrode is always treated as the left hand electrode in
potentiometric measurements. The 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. The third component of a potentiometric cell is
a salt bridge that prevents the components of the analyte solution from
mixing with those of the reference electrode.

Potential develops across the liquid junctions at each end of the salt bridge.
These two potentials tend to cancel one another if the mobilities of the
cation and the anion in the bridge solution are approximately the same.
Potassium chloride is a nearly ideal electrolyte for the salt bridge because
the mobilities of the K1 ion and the Cl2 ion are nearly equal. The net
potential across the salt bridge, Ej, is thereby reduced to a few millivolts or
less. For most electroanalytical methods, the junction potential is small
enough to be neglected. However, the junction potential and its uncertainty
can be factors that limit the measurement accuracy and precision.
The potential of the cell we have just considered is given by the equation

The first term in this equation, Eind, contains the information that we are looking for—the concentration of the analyte.
To make a potentiometric determination of an analyte then, we must measure a cell potential, correct this potential for
the reference and junction potentials, and compute the analyte concentration from the indicator electrode potential. To
determine the concentration of the analyte, the electrode system must be calibrated with solutions of known
concentrations.
Reference Electrodes

The ideal reference electrode has a potential that is accurately known, constant, and completely insensitive
to the composition of the analyte solution. In addition, this electrode should be rugged, easy to assemble,
and should maintain a constant potential while passing minimal currents.
Some commonly used reference electrodes are

• Calomel Reference Electrodes

• Silver/Silver Chloride Reference Electrodes
Indicator Electrodes
An ideal indicator electrode responds rapidly and reproducibly to changes in the concentration of an
analyte ion (or group of analyte ions). Although no indicator electrode is absolutely specific in its
response, a few are now available that are remarkably selective. Indicator electrodes are of three types:
• metallic,
• membrane, and
• ion-sensitive field effect transistors.
pH meter
Measuring pH is about measuring the acidity (pH 0-7) or
alkalinity (pH 7-14) of an aqueous sample. The instrument used
to perform this function in the laboratory is the pH meter. The
main components of a typical meter are:

• Electrode (two electrodes can be used but one is more usual)

• Temperature probe
• Electronic control unit

pH meter is a potentiometer that measures the voltage between

two electrodes dipped in a solution. One of these electrodes is a
calomel electrode and the other a glass electrode. The calomel
electrode has a constant electrical potential and is the external
reference electrode. However, the glass electrode is the standard
test electrode and its electrical potential depends on the pH of
the test solution.
pH measurement with a glass electrode

The glass electrode used to measure pH is the most common ion-selective

electrode. A typical pH combination electrode, incorporating both glass and
reference electrodes in one body.

Potentiometry 1

Uploaded by

Potentiometry 1

Uploaded by

Potentiometry

The number of potentiometric measurements

• Combining two half-cells

• If the potential of one

By convention the reference electrode is on the left hand side

• Calomel Reference Electrodes

• Electrode (two electrodes can be used but one is more usual)

pH meter is a potentiometer that measures the voltage between

The glass electrode used to measure pH is the most common ion-selective

Further reading on pH meter is an assignment.

You might also like