Che 437: Analytical Instrumentation

GROUP 03

ELECTROANALYTICAL
METHODS
Coulometry

ALILIO | ANDAL | ATIENZA | DELA RAMA |

ICE 3203
01 Introduction

02 Basic Concepts

03 Types of Coulometry

04 Advantage and Disadvantage

05 Real life applications

06 Current trends
 Introduction
Coulometry: An Overview

Charles-Augustin de Coulomb has been recognized

with the term coulometry.

Coulo: “Coulomb” unit of electric charge.

metry: means to measure

Charles-Augustin
de Coulomb
 COULOMETRY
Introduction

What is Coulometry?

Coulometry is an analytical method for Coulometry is based on an exhaustive

measuring an unknown concentration electrolysis of the analyte.
of an analyte in solution by completely
converting the analyte from one
oxidation state to another
 COULOMETRY
Introduction

Faraday’s law
Faraday’s Law- the amount of substance produced at
each electrode is directly proportional to the quantity of
charge flowing through the cell

Where
Q= total charge in coulombs
𝑛 = number of electrons per mole of analyte
𝐹 = Faraday’s constant (96485 C/ mol)
𝑁A = moles of analyte
𝑖 = current
𝑡e = electrolysis time
 COULOMETRY
Introduction

Faraday’s law
If the current varies with time, as it does in controlled
potential coulometry, then the total charge is

Current Efficiency- percentage of current that actually

leads to the analyte’s oxidation or reduction
 COULOMETRY
Basic Concepts

Definition of Concepts

01 02 03 04

Analyte Electrode Electrolysis Reagent

a substance whose solid electric conductor chemical substance or

chemical constituents that carries electric decomposition compound added to a
are being identified and current into non- produced by passing system to cause a
measured. metallic solids, or an electric current chemical reaction, or
liquids, or gases, or through a liquid or added to test if a
plasmas, or vacuums. solution containing reaction occurs.
ions

Coulometry
 COULOMETRY
Basic Concepts

Definition of Concepts

05 06 07 08

Oxidation Reduction Electrochemical Potentiostat

Cell
Electrochemical Cell
gain of oxygen and loss of oxygen and device capable of either device used to control
loss of hydrogen and gain of hydrogen and generating electrical the potential at the
electrons electrons energy from chemical working electrode.
reactions or using
electrical energy o cause
chemical reactions.

Coulometry
 TYPES OF COULOMETRY
Types of Coulometry

01
COULOMETRY 02

CONTROLLED- CONTROLLED-
POTENTIAL CURRENT
(POTENTIOSTATIC) (AMPEROSTATIC)
COULOMETRY COULOMETRY

In controlled-potential coulometry,
Controlled-current coulometry
the potential of the working
uses a constant current, which
electrode (the electrode at which
passes through a cell until an
the analytical reaction occurs) is
indicator signals the completion
maintained at a constant level
of the analytical reaction
such that quantitative oxidation or
reduction of the analyte occurs
without involvement of less-
reactive species in the sample or
solvent.
CONTROLLED-POTENTIAL
01 COULOMETRY
Types of Coulometry

(POTENTIOSTATIC) COULOMETRY
Principle of Operation

The working electrode is the electrode where the electrochemical

reaction of interest occurs.
The reference electrode is used to control the potential of the
working electrode.
The counter electrode is used to complete the electrical circuit
and balance the charges.
 COULOMETRY
Types of Coulometry

01
CONTROLLED-POTENTIAL
(POTENTIOSTATIC) COULOMETRY
Electroactive Analytes
Metal Ions Halide Ions

The specific analytes that

can be measured using
potentiostatic coulometry
depend on the
electrochemical properties
of the analyte and the
conditions of the
measurement, such as the
Redox-active species Oxygen Organic Molecules
applied potential and the
composition of the solution.
 COULOMETRY
Types of Coulometry

01
CONTROLLED-POTENTIAL (POTENTIOSTATIC) COULOMETRY
Instrumentation

Integrators are used to measure and

integrate the charge generated by
The electrochemical cell typically The potentiostat is used to apply a
the electrochemical reaction of the
consists of a working electrode, a constant potential to the working
analyte at the working electrode,
reference electrode, and a counter electrode and measure the
allowing for determination of the
electrode, which are immersed in resulting current over time.
quantity of the analyte being
the solution containing the analyte.
analyzed based on the integrated
charge.

Electrochemical Cells Potentiostats Integrators

 potentiostatic
COULOMETRY
Instrumentation

Working Electrode

Reference Electrode

ELECTROCHEMICAL
CELLS Counter Electrode
 TWO TYPES OF
potentiostatic
COULOMETRY
Instrumentation

ELECTROCHEMICAL CELLS
Platinum-Gauze Mercury Pool
Type Type
 potentiostatic
COULOMETRY
Instrumentation

PLATINUM GAUZE
Type of cells that are used for potentiostatic
coulometry

The first consists of a platinum-gauze working

electrode and a platinum-wire counter electrode,
which is separated from the test solution by a porous
tube containing the same supporting electrolyte as the
test solution.
potentiostatic
COULOMETRY
Instrumentation

MERCURY POOL
Type of cells that are used for potentiostatic
coulometry

A mercury cathode is particularly useful for separating

easily reduced elements as a preliminary step in an
analysis. These are specialized setups used in
electrochemical measurements, notably in potentiostatic
coulometry. These cells use a pool of liquid mercury as the
working electrode
 potentiostatic
COULOMETRY
Instrumentation

ELECTROCHEMICAL CELLS

Platinum-Gauze Mercury Pool

Type Type
In the presence of a mercury electrode or
a platinum gauze, the analyte can
undergo electrochemical reactions, such
as oxidation or reduction.
 potentiostatic
COULOMETRY
Instrumentation

POTENTIOSTAT
The potentiostat is used to apply a constant potential
to the working electrode and measure the resulting
current over time.

The potential applied is typically controlled by a

feedback loop that adjusts the voltage between the
working and reference electrodes to maintain a
constant potential at the working electrode.
 potentiostatic
COULOMETRY
Instrumentation

When an analyte is introduced into the

electrochemical cell, the potentiostat
applies a potential to the working
HOW DO electrode that is sufficient to cause an
oxidation or reduction reaction to occur.
ANALYTES As the reaction progresses, the
REACT? potentiostat adjusts the potential
maintain a constant current flow through
to

the cell, which is proportional to the

amount of analyte being oxidized or
reduced.

The reaction can be monitored by

measuring the current flowing through the
cell, which is directly related to the amount
of analyte being oxidized or reduced.
 potentiostatic
COULOMETRY
Instrumentation

INTEGRATOR
Integrators play a crucial role in potentiostatic
coulometry, which is a type of electrochemical
analysis used to determine the quantity of a
substance undergoing an electrochemical
reaction.

Potentiostatic coulometry involves applying a

constant potential to an electrode and measuring
the total charge (coulombs) passed during the
electrolysis.

Integrators are used to integrate the current (i.e.,

measure the charge) over time, allowing for
accurate determination of the quantity of
substance being analyzed.
 potentiostatic
COULOMETRY
Instrumentation

ROLE OF INTEGRATORS

Charge Data Acquisition Accuracy & Control of

Calibration
Measurement & Processing Precision Electrolysis
Integrators measure Integrators acquire Integrators are Integrators may Integrators may also
the current flowing the current data from designed to provide require calibration to be used to control the
through the working the potentiostat and accurate and precise ensure accurate duration of the
electrode and process it to calculate measurements of the measurement of the electrolysis by setting
integrate it over time the integrated charge. charge passed during charge. the time or the total
to obtain the total the electrolysis. charge to be passed
charge passed during during the
the electrochemical experiment.
reaction.
 potentiostatic
COULOMETRY
Instrumentation

HOW DO ANALYTES REACT?

In potentiostatic coulometry, analytes do not directly react
with integrators. The analyte reacts electrochemically at
the working electrode, and the integrator measures and
integrates the resulting current over time to calculate the
total charge.

The role of integrators in potentiostatic coulometry is to

measure the current flowing through the working
electrode and integrate it over time to obtain the total
charge passed during the electrolysis.

Integrators are typically connected to the potentiostat,

which is the instrument used to apply and control the
potential (voltage) at the working electrode during the
electrochemical reaction.
 potentiostatic
COULOMETRY

PRACTICAL CIRCUIT
 ELECTROCHEMICAL CELLS, POTENTIOSTAT, & INTEGRATORS
READOUT ORGANIZATION & PRESENTATION

Total Charged Endpoint Current-time Potential-time Electrochemical

Passed Detection profile profile Properties
potentiostatic
COULOMETRY

APPLICATIONS
Controlled-potential coulometry has numerous
applications in various fields, including chemistry,
materials science, and biology.

Electrodeposition
Corrosion Studies
Battery research
Pharmaceutical Analysis
Electroplating
Polymer Analysis
COULOMETRY
Types of Coulometry

CONTROLLED-CURRENT
(AMPEROSTATIC)
COULOMETRY
 COULOMETRY
Types of Coulometry

CONTROLLED-CURRENT
(AMPEROSTATIC) COULOMETRY

Also known as amperostatic coulometry and coulometric titrations

It is an electroanalytical technique in which the current is held constant

while the potential between the working electrode and reference electrode
is allowed to vary.

The analyte is typically oxidized or reduced at the working electrode to

produce a measurable current. By holding the current constant, the
amount of charge that is passed through the electrochemical cell is
proportional to the amount of analyte present.
 COULOMETRY
Types of Coulometry

CONTROLLED-CURRENT
(AMPEROSTATIC) COULOMETRY

The instrumentation used is similar to that used in Controlled-

Potential Coulometry, with the exception that the current is held
constant instead of the potential. The data obtained includes
the current-time profile, the total charge passed, and the
endpoint detection.
 COULOMETRY

Conceptual Diagram
Types of Coulometry

coulometric titrations

Schematic of a manual Coulometric titration apparatus Image

Source: Principles of Instrumental Analysis, Seventh Edition (2018)
 COULOMETRY
Types of Coulometry

Principle of Operation of
Amperostatic Coulometry

It is based on Faraday's laws of electrolysis, which states that the amount

of a substance produced or consumed during an electrochemical
reaction is directly proportional to the amount of charge passed through
the cell.

The current is controlled by an amperostat, which maintains a

constant current by adjusting the voltage applied to the cell.

it can be used to measure both organic and inorganic analytes and is

particularly useful for measuring analytes that are difficult to detect by
other methods, such as low-concentration species, highly reactive
species, and unstable species.
 AMPEROstatic
COULOMETRY
Analytes

Electroactive Analytes in
Amperostatic Coulometry

can be used to analyze a wide range of analytes,

including organic and inorganic compounds,
metals, and biological samples (Skoog et al., 2018, Pharmaceutical
Compounds
668).
measure the concentration
of pharmaceutical
compounds, such as aspirin
and paracetamol.

Biological Molecules
measure the concentration
of biological molecules,
such as glucose, dopamine,
and serotonin.
Organic Compounds
measure the concentration
Metals of organic compounds, such
determine the as phenols, amines, and The endpoint of the analysis is typically determined
concentration of metals in alcohols by observing a change in the current or potential,
aqueous solutions. which corresponds to the completion of the reaction
(Bard & Faulkner, 2018)
 AMPEROstatic
COULOMETRY
Instrumentation

02
CONTROLLED-CURRENT (AMPEROSTATIC) COULOMETRY
Instrumentation

Galvanostat Potentiostat Electrochemical

Cells
a device that allows for the a device that allows for the the vessel in which the reaction
precise control of the current precise control of the potential at takes place and contains the
passing through the working the working electrode. working and counter electrodes
electrode.
 AMPEROstatic
COULOMETRY
Instrumentation

GALVANOSTAT
The galvanostat is connected to the
working electrode and provides a
constant current through the
electrode.

The current is controlled to remain

constant throughout the experiment,
which allows for the determination of
the amount of charge required to
react with the chemical species in
the solution.

The galvanostat also measures

the current passing through the
working electrode and converts
this measurement into a digital
signal that can be recorded.
GALVANOSTAT
How do analytes react with a galvanostat?
Analytes are introduced to a galvanostat that consists of a working electrode and a counter
electrode. The analytes undergo an oxidation or reduction reaction at the surface of the working
electrode, which is controlled by the galvanostat.

The analyte is introduced to the

electrochemical cell, and the
current is applied to the working It provides a constant current to the
When a current is applied to the working electrode, which ensures
electrode.
working electrode, it causes a The current causes the analyte that the rate of the electrochemical
reaction in the analyte. to undergo an electrochemical reaction is constant.
The counter electrode serves to reaction, which results in the This allows for accurate and precise
complete the electrical circuit, transfer of electrons between the measurements of the analyte
and it provides a path for the flow analyte and the electrode concentration.
of electrons. surface. The instrument can also be used to
The reaction that takes place at The amount of charge that is perform various electrochemical
experiments, such as cyclic
the working electrode is typically transferred is measured, and this
voltammetry, which allows for the
a reduction or oxidation reaction, provides information about the
determination of the
which depends on the nature of concentration of the analyte in
electrochemical properties of the
the analyte being measured. the solution.
analyte
 AMPEROstatic
COULOMETRY
Instrumentation

POTENTIOSTAT
In amperostatic coulometry, a potentiostat is
typically used to apply a constant current to the
working electrode during an electrochemical
reaction.

It ensures that the current remains constant,

allowing for precise control of the electrolysis
process and accurate measurement of the charge
passed during the reaction
 AMPEROstatic
COULOMETRY

HOW DO ANALYTES RESPOND TO THE

Instrumentation

POTENTIOSTAT??

analytes undergo a redox reaction at a working

electrode that is controlled by a potentiostat.

The potentiostat applies a The analytes react with On the other hand, if the
constant current to the the working electrode analyte is a reducible
working electrode, surface by either species, it will donate
causing the analytes to accepting or donating electrons and undergo
be oxidized or reduced. electrons. reduction, also resulting in
the generation of a current.
 AMPEROstatic
COULOMETRY
Instrumentation

An electrochemical cell is a crucial

component in the field of
electrochemistry. It comprises the
working and counter electrodes, as
well as the solution that is to be
analyzed
- Additionally, the electrochemical
cell includes a reference electrode

COULOMETRIC TITRATION
CELLS
AMPEROstatic

HOW DO ANALYTES REACT TO

COULOMETRY

COULOMETRIC TITRATION CELLS?

Electrode Electrolyte Concentration of Potential

Temperature Stirring
Material Composition Analytes Applied
At high
Different materials can The composition of At higher
concentrations, the The potential can Stirring the
affect reaction kinetics the electrolyte in temperatures,
diffusion of the control the rate of electrolyte solution
and rate due to their the reaction rates
analyte to the electron transfer can enhance the
distinct potentials and electrochemical normally rise due to
electrode surface and the extent of rate of mass
surface areas. cell might also the molecules'
might restrict the the redox reaction. transfer and
affect analyte greater kinetic
reaction rate. improve the
reactions. energy, but at lower
At low reaction kinetics.
temperatures,
concentrations, the
reaction rates drop.
availability of
analyte molecules
may restrict the
reaction rate.
 What type of Data does Amperostatic
Coulometry provide:

READOUT ORGANIZATION & PRESENTATION

Total Charged Endpoint Current-time Potential-time Electrochemical

Passed Detection profile profile Properties
AMPEROstatic
COULOMETRY

APPLICATIONS
Controlled-Current Coulometry has several
applications in various fields, including:
Quantitative analysis of electroactive
species
Electrodeposition and electroplating
Corrosion studies
Pharmaceutical research
Electrochemical sensing
AMPEROstatic
COULOMETRY

Limitations of controlled-current
coulometry:

1. Limited Range of Currents:

Controlled-current coulometry is effective within a specific
range of current values.
2. Limited to Homogeneous Systems:
Controlled-current coulometry assumes homogeneity within
the electrochemical system. In heterogeneous systems
3. Lack of Selectivity:
Unlike some other techniques, controlled-current
coulometry lacks selectivity.
 COULOMETRY

DIFFERENCE BETWEEN CONTROLLED-CURRENT (AMPEROSTATIC) COULOMETRY Basic Concepts

AND CONTROLLED-POTENTIAL (POTENTIOSTATIC) COULOMETRY

01 02

CONTROLLED-CURRENT CONTROLLED-POTENTIAL
(AMPEROSTATIC) (POTENTIOSTATIC)
COULOMETRY COULOMETRY

this method involves applying this method, a constant

a constant current to the potential is applied to the
electrochemical cell and electrochemical cell. The
measuring the amount of amount of charge required
charge required to complete to complete the reaction is
the reaction. However, then measured..
Amperostatic Coulometry is
more suited for determining
metals in solutions.
Coulometry
 COULOMETRY
Basic Concepts

Advantage of Coulometry

01 02 03 04
Accuracy Measurement Ease Cost-Effective Versatility

Coulometry is a highly Both time and current are Coulometry has lower Coulometry can be used
accurate technique as the easy to measure to a high reagent costs and reduced for precipitation, complex
amount of electricity degree of accuracy. downtime and maintenance formation,
required to complete the costs. oxidation/reduction, or
reaction is directly
neutralization reactions.
proportional to the
amount of analyte present.

Coulometry
 COULOMETRY
Basic Concepts

Disadvantage of Coulometry
03
01 02 04
Time-Consuming Requirement for 100% Measurement Errors: Titrations
Current Efficiency:

In controlled-potential All the current must be Errors in measuring current

coulometry, the current used to oxidize or reduce There may be
and time can impact the
decreases over time the analyte. discrepancies
precision of coulometric
analysis.

Coulometry
 COULOMETRY

Real Life Applications

Applications

Analysis of
radioactive materials

2 Inorganic
Analysis
Microanalysis 4

3
Electrolytic Determination of
Organic Compounds
 CURRENT TRENDS IN COULOMETRIC COULOMETRY

INSTRUMENTATION
917 COULOMETER FOR
The primary purpose of the 917 Coulometer COULOMETRIC WATER
is to accurately measure the water content DETERMINATION
in various samples using coulometric Karl
Fischer titration. This technique involves the
electrolysis of water and the measurement
of the consumed charge.
-The instrument is designed with a compact
and space-saving design, making it
suitable for laboratory use.
 COULOMETRY

CURRENT TRENDS IN COULOMETRIC

INSTRUMENTATION
ADVANCED ELECTROCHEMICAL
SENSORS & ELECTRODES New sensor technologies are being
-These advanced sensor and electrode materials allow for more developed and utilized to enhance
accurate and precise analysis of analytes in complex samples. the performance of Coulometric
measurements. These include:
-Scientists are currently exploring the use of advanced electrode
materials to enhance the efficiency and sensitivity of coulometric
techniques Screen-Printed Electrode
These materials include: Carbon Nanotube Electrode
Nanomaterials Nanostructured Electrode
2D materials
Composite materials
 COULOMETRY

THANK YOU!
References

Bard, A. J., & Faulkner, L. R. (2018). Electrochemical methods: fundamentals and

applications (Third ed.). Wiley.
Li, J., Zhu, L., & Chen, G. (2021). Recent advances in analytical
techniques for the detection of antibiotics in food and environmental
Bohari, N. R., Siddiquee, S., Saallah, S., Misson, M., & Arshad, S. E. (2020, samples. TrAC Trends in Analytical Chemistry.
November 14). (PDF) Optimization and Analytical Behavior of Electrochemical
Sensors Metrohm. (2018). 917 Coulometer with generator electrode with
Based on the Modification of Indium Tin Oxide (ITO) Using diaphragm. Metrohm. Retrieved March 25, 2023, from
PANI/MWCNTs/AuNPs for Mercury Detection. ResearchGate. Retrieved February https://www.metrohm.com/en/products/2/9170/29170010.html
25, 2023, from
https://www.researchgate.net/publication/346051252_Optimization_and_An Skoog, D. A., Holler, F. J., & Crouch, S. R. (2018). Principles of Instrumental
al Analysis. Cengage Learning.
ytical_Behavior_of_Electrochemical_Sensors_Based_on_the_Modification_
of ST Instruments. (n.d.). Potentiostat | Galvanostat | EIS. ST Instruments.
_Indium_Tin_Oxide_ITO_Using_PANIMWCNTsAuNPs_for_Mercury_Detection Retrieved February 18, 2023, from
https://www.stinstruments.com/electrochemistry/potentiostat-
CS300M Potentiostat/Galvanostat. (n.d.). CS300M Potentiostat/Galvanostat- galvanostat- eis/
Corrtest Instruments. Retrieved March 14, 2023, from
https://www.corrtest.com.cn/en/service1/1231.html
Wang, L., Kang, Z., & Zhang, J. (2020). Electrolysis for production of high-
value chemicals.
Cui, X., Zhao, J., & Zhang, H. (2018). Metal-organic frameworks for energy
storage: batteries and supercapacitors. Coordination Chemistry Reviews, 55-
Wyss Institute. (2021, September 9). eRapid: developing a multiplexed
81.
electrochemical diagnostic platform from the ground up. Wyss Institute.
Karl Fischer Titration | Learn Important Terms and Concepts. (2023, April 5). Retrieved March 25, 2023, from https://wyss.harvard.edu/news/erapid-
Vedantu. Retrieved February 18, 2023, from developing-a-multiplexed-electrochemical-diagnostic-platform-
https://www.vedantu.com/chemistry/karl-fischer-titration from-the- ground-up/

Langer, R. (2018). Electrocatalytic oxidation: a green and sustainable

alternative to chemical oxidation. Green Chemistry, (20(10)), 2225-2241.
Thank you for Listening