Electrochemical sensors

Electrochemical sensors

Electrochemical sensors are the gas detectors that measure the

concentration of a target gas by oxidizing or reducing the target gas at
an electrode and measuring the resulting current

Electrochemical sensors can be like a micro-fuel cell composed of

metal electrodes in an electrolyte

The electrolyte is usually an aqueous solution of strong inorganic acids

When a gas is detected, the cell generates a small current proportional

to the concentration of gas

Electrochemical sensors are used primarily to detect oxygen and toxic

gases

Each sensor is designed to be specific to the gas it is intended to

detect

related to the rate of the electrolytic process at the sensing ele

known as working electrode) whose potential commonly is kep
using another electrode (the so-called reference electrode).

Working principle

Electrochemical sensors operate by reacting with the gas of

Working
interest and producing electrical signal proportional
to the gas Principle
concentration

A typical electrochemical sensor consists of a sensing electrode

(or working electrode), and a counter electrode separated by a
thin layer of electrolyte

Target gas molecules that come in contact with the sensor first
pass an anti-condensation membrane which serves also as a
protection against dust

Then the gas molecules diffuse through a capillary, potentially

through a subsequent filter, and then through a hydrophobic
membrane to reach the surface structure of the sensing electrode

When the gas diffuses through the membrane and into the working
electrode, an electrochemical reaction occurs, either an oxidation
or reduction depending upon the type of gas molecules
A MEMBRAPOR

Hydrophobicgas
electrochemical
sensor works
as follows:
membrane
(semipermeable
membrane)
is used
to an an
For example, CO can be oxidised to CO2 or O2 can
be reduced
to come in
molecules
that
contact with
the sensor
first pass
control the amount of gas reaching
H2O
condensation membrane which serves also as a protection aga
the electrode surface
An oxidation reaction results in the flow of electrons
fromthe
thegas molecules
Then
diffuse
a capillary,
potentially
These
arethrough
usually teflon
membranes
working electrode to the counter electrode through the external
porosity
subsequent filter, andwith
thenlow
through
a hydrophobic membrane
circuit
surface structure of the sensing electrode. There the molecules
Conversely, a reduction reaction results in the flow of electrons
from counter electrode to the working electrode immediately oxidized or reduced on active catalytic sites, cons

This flow of electrons constitutes an electric current which is

http://www.membrapor.ch/electrochemical-gas-sensors/
proportional to the gas concentration

cell where equilibrium is not established. The current is quanti

related to the rate of the electrolytic process at the sensing elec
known as working electrode) whose potential commonly is kep
using another electrode (the so-called reference electrode).

Working principle

Working
Principle
By optimizing the pathway, in accordance with
the desired
measurement range, an adequate electrical signal is obtained

The electrochemical cell is completed by the so called counter

electrode, which balances the reaction at sensing electrode

The ionic current between the counter and sensing electrode

is transported by the electrolyte, whereas current path is
provided through wires terminated with pin connectors

A third electrode is also included in the sensor known as

reference electrode

Its function is to maintain the potential of sensing electrode at

a fixed value

A MEMBRAPOR electrochemical gas sensor works as follows:

For this purpose and generally for the operation of an
molecules
electrochemical sensor a potentiostatic circuit
( external that come in contact with the sensor first pass an an
driving voltage) is needed
condensation membrane which serves also as a protection agai
Then the gas molecules diffuse through a capillary, potentially
The circuit that controls the potential of the working electrode
subsequent
filter, and then through a hydrophobic membrane
and converts the signal current to a voltage is
called a
potentiostat
surface structure of the sensing electrode. There the molecules
immediately oxidized or reduced on active catalytic sites, conse

s both in industry and

ncreased demand for
ents. The application of
the measurement of the
or containing a
ing of the oxygen
stion streams in giant
to insure safe and

energy is stored externally; the rate at which the

chemicals are fed into the fuel cell determines the
amount of energy or power that is obtained.

Oxygen electrochemical sensor

Principle of Operation

The Micro-fuel Cell then is a fuel cell (strictly speaking,

a hybrid fuel cell) where part of the chemical energy is
Of all gases, oxygen
playsand
a unique
in human
stored within
the otherpart
chemical
reactantexistence
(oxygen)
comes from outside the device. Most fuel cells are
n detail TAI's Micro-fuel
power devices,
i.e. theboth
hydrogen-oxygen
that
Modern technological
advances
in industryfuel
andcells
medicine
have resulted in an increased
n transducer around
are used to power the manned space vehicles used by
demand for accuracy
in oxygen measurements
rs has been developed
NASA in the space program. The oxygen sensing cell
the end of this
under discussion here provides power normally in the
eration of other
oxygen
The
application1 of
oxygen
analyzers
ranges
measurement of the atmosphere inside an
to 200
microwatt
range, hence
thefrom
namethe
Micro-fuel
comparisons of each
Cell.
incubator containing
a premature baby to the monitoring of the oxygen content of process and
that of the Micro-fuel

combustion streams in giant chemical plants and refineries to insure safe and economical
All types of electrochemical transducers have three
operation
major component parts; an anode, a cathode, and an

In O2 sensor,

trochemical transducer.
onverts one form of
e, a loudspeaker is a
ical energy into
In basic
microphone is a
PbO)
al of this; mechanical
al energy.

The

electrolyte. In the Micro-fuel Cell, the cathode is the

cathode
would be
thesite
sensing
electrode,
where
sensing electrode
or the
where oxygen
is reduced.

reduction of O2 would take place

4e- + O2 + 2H2O -------> 4OH- (1)

The rear of the cell (inside the contact plate) is fitted

cathodic half-reaction occurs simultaneously with the
In theanodic
above
reaction,
four
electrons combine
with
with a flexible
designed to to
following
half
reaction:
electrolyte,
at the
counter
electrode,
anodic
halfone
reaction
willofmembrane
occur
( that
Pb isis
The rear
the cell (inside
theoxidised
contact plate) is fitted
cathodic
half-reaction
occurs
simultaneously
with the
oxygen molecule (in the presence of water from the accommodate internal volume changes that occur
with a flexible membrane that is designed to
following anodic half reaction:
throughout
the life of
the cell.
If it were
not for
electrolyte)
produce
four
hydroxyl
Pb + 2OH-to ------->
PbO
+ H2O
+ 2e-ions.
(2) This
accommodate
internal
volume
changes
thatthis
occur
volume
compensating
membrane,
the
membrane
throughout the life of the cell. If it were not for this
Pb + 2OH- -------> PbO + H2O + 2e- (2)
covering
thecompensating
cathode wouldmembrane,
move to accommodate
volume
the membranethe
The anode (lead) is oxidized (in a basic media) to lead
internal
volume
in changes
in output the
covering
thechanges
cathode resulting
would move
to accommodate
oxide The
and anode
in the process
electrons
transferred
(lead) is two
oxidized
(in a are
basic
media) to lead not related
oxygenchanges
concentration.
internaltovolume
resulting in changes in output
for each
atom
ofinlead
that
is oxidized.
oxide
and
the
process
two
electrons
are
transferred
overall reaction would be
not related to oxygen concentration.
for each atom of lead that is oxidized.
The
sensing membrane (covering the cathode) is
The sum of half-reactions (1) and (2),
made
of Teflon
thickness
is very
accurately
The
sensingwhose
membrane
(covering
the
cathode) is
The sum of half-reactions (1) and (2),
controlled.
The
entire
space
betweenisthese
two
made of
Teflon
whose
thickness
very accurately
O2 + 2Pb -------> 2PbO (3)
membranes
is filled
with electrolyte
(an aqueous
controlled.
The entire
space between
these two
O2 + 2Pb -------> 2PbO (3)
solution
typically is
offilled
potassium
hydroxide).
results
membranes
with electrolyte
(anThis
aqueous
results in the overall reaction (3). From this reaction it
in allsolution
surfaces
of the anode
and cathode
beingThis results
typically
of potassium
hydroxide).
thethe
overall
reaction
Frombe
thisvery
reaction it
can beresults
seen in
that
Micro-fuel
Cell(3).
should
in all in
surfaces
of the
anode
and cathode being
"bathed"
a common
pool
of electrolyte.

CO electrochemical
sensor
Figaro Electrochemical-type gas sensor
are amperometric fuel cells with

two electrodes. The basic components of two electrode gas sensors are a
in
them. When
toxic gas
such and
as carbon
monoxide
The three electrodes are thebetween
working electrode,
the reference
electrode,
the counter
electrode (CO) comes in
contact
with
the working
electrode, oxidation of CO gas will occur on the
Operating
-Electrochemical-type
sensor
7/11/16
The working electrode is made
ofprinciple
platinum,
which is agas
catalytic
metal to CO (it catalyzes the oxidation of CO
working but
electrode
through
chemical
reaction with water molecules in the
to CO2), backed by a gas-permeable
hydrophobic
(water-proof)
membrane
shortEquation
circuit will
protons (H+) generated on the working electrode to
airthe(see
1).allow
The CO gas diffuses through
porous membrane
and is electrochemically oxidized
Operating principle
-Electrochemical-type
gas counter
sensor
7/11/16, 8(57 a
flow
toward the
electrode through the ion conductor. In addition,
+ + 2e- 1
CO generated
+ H2O electrons
CO2 2Hmove
to the counter electrode through the external
short circuit will allow protons (H+) generated on the working electrode to
wiring. A reaction
oxygen
in the air
will occur
onthe
the
counter electrod
The electrons involved in the electrochemical
reactionwith
flow from
the working
electrode
through
external
flow
toward
electrode
through
the
ion conductor.
Inthrough
addition,a
circuit, producing the output
signal
of thethe
sensor
Connecting
thecounter
working
electrode
and the
counter
electrode
(see Equation
2).
generated electrons move to the counter electrode through the external
A counter-electrode (CE) is provided to complete the circuit of the electrochemical cell. The counter electrode
+electrons
wiring.
A reaction
with
in2Othe
on the counter electrode Pa
functions solely as thehttp://www.figaro.co.jp/en/technicalinfo/principle/electrochemical-type.html
second
half-cell,
and
orair
leave
theoccur
electrolyte
1/2
O2 allows
+ 2H
+oxygen
2e- toHenter

2will
(see Equation 2).
The reaction with O2 in the air would occur at the counter electrode (other half cell reaction)
The overall reaction is shown in Equation 3. Figaro Electrochemical-type
+ + 2e- H O 2
1/2
gas O
sensor
operate
like a2 battery with gas being the active material for this
2 + 2H
overall battery reaction.
The overall cell reaction would be
The overall reaction is shown in Equation 3. Figaro Electrochemical-type
gas sensor
battery
with gas being the active material for this
CO + operate
1/2 Olike
2 aCO
2 3
overallwith
battery
reaction.
The CO sensor is also equipped
a chemically
selective filter
By measuring the current between the working electrode and the counter
This filter removes potentially interfering gases before they reach the working electrode. With the filter
CO +electrode,
1/2 Othis
CO2 3
electrochemical
cell
can be utilized as a gas sensor.
2
operating properly the sensor will
have minimal
response
to interfering
gases
The carbon monoxide sensor consists of three electrodes immersed in a liquid electrolyte (a non-metallic
liquid that conducts electricity,
usually(sensing)
through acids
or dissolved
salts)
working
electrode,
a counter
electrode, and an ion conductor

By measuring
the current
between
theCO
working
electrode and the counter
Theoretical
equation
for
detection

By measuring the current between the working electrode and the counter
electrode, this electrochemical cell can be utilized as a gas sensor.

In order
to measure
the sensors
Theoretical
equation
for CO detection
output current, it must be
In order
measure
the sensors
output
connected
totoan
external
circuit

current, it must be connected to an

external circuit. By controlling gas flowing
By controlling gas flowing toward
toward the working electrode with
the working electrode with diffusion
diffusion film, output current flowing
film, output
current flowing across
across the external circuit will be
the external
circuit will be
proportional to gas concentration (see
proportional
gastheconcentration
Equationto
4 and
chart at the right). The
linear relationship of gas concentration to
The linear
of gas
sensorrelationship
output makes this
technology ideal for gas sensing applications.

concentration to sensor output

F technology
(A/) D C ideal
n 4for gas
makesI =this
sensing
applications
where:
I: Sensor output
F: Faraday constant
http://www.figaro.co.jp/en/technicalinfo/principle/electrochemical-type.html

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