8.

4 Analyzers Operating on Electrochemical AIT To

Receiver

Principles
R. GILBERT (1982) J. N. HARMAN III (1995) B. G. LIPTÁK (2003) Flow Sheet Symbol

Design Variations: Amperometric, coulometric, galvanometric, polarographic, and potentiometric

principles

Sections Discussing 8.10—carbon monoxide, 8.11—chlorine, 8.17—conductivity, 8.24—fluoride,

Specific Applications: 8.26—hydrogen sulfide, 8.28—ion-selective electrodes, 8.33—moisture in gas,
8.41—ORP probes, 8.42—oxygen, 8.44 and 8.45—ozone, 8.48—pH, 8.56—sulfur
oxide, 8.59—toxic gases

Inaccuracy: Generally 1% of full scale with absolute error values down to under 1.0 parts per
billion (ppb)

Costs: Amperometric or polarographic residual chlorine transmitters cost about $8000, with
the yearly cost of chemicals for the amperometric units adding another $3000 (some-
what less for polarographic). An electrochemical gas diffusion detector for hydrogen
sulfide costs $2500. Potentiometric probes for pH, oxidation–reduction potential, and
ion-selective measurements cost about $500, with associated transmitter about $2500.
Electrochemical probes for nitrogen oxide detection in stacks cost $7000. The elec-
trolytic dissolved oxygen probe and transmitter cost $3500. Costs for amperometric
gas and dissolved ozone detector range from $4000 to $8000. An electrochemical
membrane diffusion system to automatically monitor toxic gas concentration in 16
locations costs from $12,000 to $20,000. For more detailed cost information, refer
to the sections in this chapter where the specific analyzers are discussed.

Partial List of Suppliers: ABB (www.abb.com)

Advanced Sensor Technologies Inc. (www.astisensor.com)
American Gas & Chemical Ltd. (www.amgas.com)
Analytical Technologies Inc. (www.analyticaltechnologies.com)
B&W Technologies Ltd. (www.gasmonitors.com)
Bacharach Inc. (www.bacharach-inc.com)
Bran & Luebbe Analyzing, Technicon Industrial Systems (www.branluebbe.com)
Brinkmann Instruments Inc. (www.brinkmann.com)
Broadley James (www.broadleyjames.com)
CEA Instruments Inc. (www.ceainstr.com)
Cole-Parmer Instrument Co. (www.coleparmer.com)
Control Instruments Corp. (www.controlinstruments.com)
Custom Sensors and Technology (www.customsensors.com)
Detector Electronics Corporation (www.detronics.com)
Draeger Safety Inc. (www.draeger.com)
EcoChem Analytics (www.ecochem.biz)
Electro-Chemical Devices (www.ecdi.com)
Emerson Process—Process Analytic Div. (www.processanalytic.com)
Endress + Hauser (www.endress.com)
Enmet Analytical Corp. (www.enmet.com)
Fisher Scientific (www.fishersci.com)
The Foxboro Company (www.foxboro.com)
+GF+ Signet (www.gfsignet.com)

1198
© 2003 by Béla Lipták
 8.4 Analyzers Operating on Electrochemical Principles 1199

GLI International (www.gliint.com)

Global FIA (www@globalfia.com)
Hamilton Co. (www.hamiltoncompany.com)
Honeywell (www.honeywell.com)
Horiba Instruments Inc. (www.horiba.com)
International Sensor Technology (www.intlsensor.com)
Ionics Inc. (www.ionics.com)
Knick (www.knick.de)
Mettler-Toledo (www.mt.com)
Milton Roy, Process Analytical Div. (www.miltonroy.com)
Mine Safety Appliances (www.msanet.com)
Osmonics Lakewood (www.osmonics.com)
Pfaudler Inc. (www.pfaudler.com)
Phoenix Electrode Co. (www.phoenixelectrode.com)
Rosemount Analytical Inc., Uniloc Div. (www.rauniloc.com)
Sargent-Welch Scientific (www.sargentwelch.com)
Scott Instruments (www.scottinstruments.com)
Sensidyne Inc. (www.sensidyne.com)
Sensorex (www.sensorex.com)
Sierra Monitor Corp. (www.sierramonitor.com)
Teledyne Analytical Instruments (www.teledyne-ai.com)
Thermo Environmental Instruments (www.thermoei.com)
Thermo Gas Tech (www.gastech.com)
Thermo Orion (www.thermo.com)
Thornton (www.thorntoninc.com)
Universal Sensors & Devices Inc. (www.universalsensors.com)
Van London Co. (www.vanlondon.com)
Yokogawa (www.yca.com)
Zellweger Analytics—MDA Scientific Inc. (www.zelana.com)

INTRODUCTION
The purpose of this section is to give an overall perspective
of the many electrochemical analyzers used in the processing
industries. These instruments will be discussed in more detail
in later sections of this chapter. Electrochemical analyzers
measure composition or concentration by detecting the
changes in voltage or current that occur between two elec-
trodes in a solution (electrolyte) over time, because of the
oxidation or reduction of that solution.
In galvanic and polarographic analyzers (such as CO, O2,
and toxic gas sensors discussed in Sections 8.10, 8.42, and
8.59), the electrolyte is usually a gel. The gel is separated
from the process stream by a membrane and the electrochem-
ical reaction in this electrolyte either occurs spontaneously
or is caused by a polarizing voltage.
In potentiometric analyzers (such as Cl, conductivity,
ion-selective, oxidation–reduction potential (ORP), and pH
probes discussed in Sections 8.11, 8.17, 8.28, 8.39, and 8.48),
an electrical potential is detected, which is generated in
response to the presence of dissolved ionized solids. The ORP
probe detects the ratio of oxidizing to reducing agent. Con-
ductivity sensors measure the solution’s ability to conduct
electricity, which depends on the concentration of dissolved
ionized solids.
In amperometric analyzers (such as Cl, Fl, HS, moisture
in gas, O3, and toxic gases covered in Sections 8.11, 8.24,
8.26, 8.33, 8.44, 8.45, and 8.59) if a strong oxidizing agent
is present, the polarization of the measuring electrode is
depolarized and a current flow is generated, which is propor-
tional to the concentration of the oxidizing agent.
In coulometric analyzers (such as CO, oxygen in gas, and
SO sensors discussed in Sections 8.10, 8.42, and 8.56), the
measured gas diffuses through the potassium hydroxide elec-
trolyte to the cathode of the electrochemical cell, where it is
reduced to hydroxyl ions. As an external voltage causes these
ions to migrate to the anode, the resulting cell current is a
measure of concentration.
VOLTAMETRIC ANALYSIS
Voltametric analyzers monitor the current, voltage, or charge
that results from a specific oxidation–reduction reaction of
the component of interest. During an oxidation–reduction
reaction, one or more electrons are transferred from one atom
or molecule to another.
This section presents a brief review of voltametry, includ-
ing a discussion of the concepts and properties of electro-
chemical probes, potentiometry, amperometry, polarography,
and coulometry. The distinctions among voltametric methods
are summarized in Table 8.4a. This table lists the common
voltametric methods of analysis and their usual applications.

© 2003 by Béla Lipták

1200 Analytical Instrumentation

TABLE 8.4a
Summary of Voltametric Methods
†
Measured On-Line
a
Method Variables Instrument Determinations
Potentiometry V Yes pH
− = –
Anions (F , S , Cl )
+ ++ ++
Cations (NH4 , Ca , Mg )
Polarography i, v Yes Pesticides
Mercaptans
Thiosulfates
Chlorinated organics
Toxic heavy metals
Stripping i, v No Heavy metals
Selenides
Halogens
Thioamides
Trace metals
Amperometry i, t, c Yes Sulfates
Halides
Phenols
Aromatic amines
Olefins
Controlled ∫ i(t) Yes Precious metals
potential Alloys
coulometry Dissolved oxygen
Differential i, v No Aromatic hydrocarbons
pulse Aromatic amines
polarography Phenol
Ammonium salts
Carboxylic anhydrides
N-nitrosamines

Note: i = current; v = applied potential; c = concentration; i(t) = current as function of time.

a
Partial list.

Current, Voltage, and Time
Successful application of voltametry for monitoring and con-
trolling process streams requires an understanding of the
significant voltametric variables. The fundamental require-
ments for voltametry instrumentation are two electrodes, pro-
visions for a current and voltage supply, and monitors for the
ing electrode is the usual transport mechanism required if
the analytical expressions for the curves of Figure 8.4b are
to be obtained. The control of diffusional mass transport is
important for chronopotentiometry, amperometry, and
polarography.
The electrochemical surface presented in Figure 8.4b is
generated from the following equation:
1

respective voltage and current responses as a function of time.

The characteristic response curves indicate the nature of the
electrochemical analysis occurring in the solution between
the electrodes. Figure 8.4b illustrates a surface that relates
the three variables (current, voltage, and time), which are of
interest in an electrochemical analysis.
The exact shape of a particular response curve in Figure
8.4b depends on the mass transport phenomena associated
with the movement of the component of interest (analyte)
to the working electrode. (The working electrode is the
electrode in which the electrochemical process of interest
occurs, while the reference electrode is passive. The usual
working electrode is made from a metal, such as mercury,
platinum, palladium, or gold.) Analyte diffusion to the work-
1/2
E = (E° + (RT/nF) ln(fo/fr(Dr/Do) )
1/2 1/2
+ (RT/nF) ln[K − it )/it )] 8.4(1)
Equation 8.4(1) expresses the potential (E) of the working
electrode in terms of E°, the standard thermodynamic potential;
R, the gas constant; T, the absolute temperature; F, Faraday’s
constant; n, the number of electrons transferred for the spec-
ified oxidation–reduction reaction; f, the activities of oxi-
dized and reduced analyte forms; i, the current; and K, a
constant dependent upon particular analysis parameters other
than voltage, current, or time.

© 2003 by Béla Lipták

 8.4 Analyzers Operating on Electrochemical Principles 1201

B Screened Cable
(V = Const.) Cable

Cap Cap

C
Current (I)

Inner
Reference Salt
Element Bridge
Solution
Insulating
Glass
Stem E9
(I = Const.)
Inner Ag-AgCl
Ti A Reference Reference
m e Buffer Element

E1 E5 E8
pH Liquid
Membrane Junction
E2
E3
E4 E6 E7
Volts (V)
E1 To E9 Represents Potentials Developed
Between Glass Solution and Reference Electrode
FIG. 8.4b
Response surface for voltametry, showing curve A, the process of Typical Glass Typical Reference
chronopotentiometry; curve B, amperometry; and curve C, the Electrode Electrode
polarographic process.
FIG. 8.4c
pH electrodes.
Potentiometry

During a potentiometric analysis, such as in ORP, pH, or ion-
selective measurements, no current is passing between elec-
trodes. The potential difference (at zero current) is monitored
between the measuring and reference electrodes. At the mea-
suring electrode, an oxidation or reduction of a solution spe-
cies is taking place. Such an analysis is called chronopoten-
tiometry when the potential difference between a metallic
measuring electrode and a reference electrode is monitored
as a function of time.
Potentiometry may be done with a bare metal electron-
conducting electrode and a reference electrode, in which case
the technique responds to the oxidation–reduction couples
present in the test solution. If a potentiometric determination
is conducted using an ion-selective electrode and a reference
electrode, one may determine solution species over a wide
dynamic concentration range with good selectivity, and there
is no need for oxidation–reduction couples in the solution.
Examples of ion-selective electrodes are glass electrodes for
pH (Figure 8.4c) and sodium ion determination; solid-state
electrodes for fluoride, chloride, and sulfide determination;
and liquid ion exchange electrodes for the determination of
calcium, magnesium, and nitrate ions.
If a constant current is supplied to the electrodes, the
progress of the electrochemical reaction is observed by mon-
itoring the change in potential as a function of reaction time.
This procedure is labeled chronopotentiometry, and a
response curve would be similar to curve A in Figure 8.4b.
If the electrochemical process occurs at a constant poten-
tial, the reaction response is monitored as a changing current
as a function of time. This type of analysis is called constant
potential voltametry, or amperometry. A typical response
curve is labeled B in Figure 8.4b.
Finally, monitoring reaction current as a function of
applied potential is called polarography, and a typical polaro-
graphic curve is represented by C, which is a diagonal cut
through the response surface, in Figure 8.4b.
Galvanic and Electrolytic Probes
A probe is galvanic when no external voltage is applied across
the electrodes. In that case, the current flows as the cell is
depolarized as diffusion of the analyte occurs. Electrodes are
consumed during this operation and require periodic replace-
ment. An electrolytic probe is similar to a galvanic one,
except that a potential is applied across the electrodes and
the electrodes are not consumed. Dissolved oxygen detection
is a primary application of this type of probe.
Electrochemical probes are electrochemical cells that
have been designed to respond to the presence of a particular
analyte. Similar to electrochemical cells, electrochemical
probes can be classified as either galvanic or electrolytic.
Electrolytic probes require an external potential to be applied
across the electrodes; galvanic probes do not. Both types of
probes require a pair of electrodes, usually metallic, which
are immersed in an electrolyte so that current passes through
the electrodes as the desired oxidation or reduction occurs at
the surface of the working electrode.
The difference between an electrolytic and a galvanic
probe is whether or not a potential from an external source is

© 2003 by Béla Lipták

1202 Analytical Instrumentation

Port to
Add
Cap
Water/ Plug
Electrolyte
Purge Gas Out Purge Gas In

Thermistor Red
Black
O-Ring
Mounting White
Plate Coupling Nut
Tab-Lug
Ring Terminal Connector

Sample Electrode Nut

Electrolyte
Out Fill Plug
Reservoir Thermistor
Seal Screw
Sample Anode O-Ring
In
Counter Electrode

Assembly
Electrode
O-Rings
Cathode
Electrode Chamber
Insulator
FRIT Electrolyte
Ammeter O-Ring Solution

Membrane Assembly
FIG. 8.4d
Galvanic oxygen detector cell. (Courtesy of Teledyne Analytical
Instruments.) Measuring Oxygen Permeable
Electrode Membrane

applied across the electrodes. Galvanic probes are constructed
in such a manner that the presence of the analyte depolarizes
the cell and allows a flow of electrons in the cell (Figure 8.4d).
Because the electrochemical reaction occurs spontaneously,
no external potential need be applied across the electrodes.
However, galvanic probes have a major disadvantage in that
the electrodes are consumed as the reaction continues. This
limitation restricts their usefulness to monitoring situations in
which periodic replacement of spent probes is acceptable.
Electrolytic probes are principally used as monitoring
devices for dissolved oxygen in aqueous and nonaqueous
media. Unlike with the galvanic probe, here a potential is
applied from an external source across the electrodes. The
choice of potentials is controlled by the analyte to be deter-
mined. The current from the probe is obtained at constant
potential as a function of time, location of the probe within
the process, or the process state.
Membrane-Covered Probes To reduce the chemical inter-
ference from the process, a diffusion-limiting membrane can
be placed over both electrodes. These membranes are perme-
able to the component of interest and are filled with the
appropriate electrolyte. The thin analyte-permeable mem-
brane separates the cell components and the electrolyte from
the solution to be analyzed (Figure 8.4e).
A deficiency of this technique is the dependence of the
membrane permeability on the process temperature. This is
usually corrected by measuring the process temperature and
adjusting the gain of the analyzer unit to compensate for the
permeability effects. Another problem is the interferences
FIG. 8.4e
An oxygen-permeable membrane protects the working components
of a galvanic dissolved oxygen probe. (Courtesy of ABB Inc., for-
merly Fischer & Porter.)
caused by dissolved gases other than oxygen, which permeate
the membrane and cause interferences as they are oxidized
or reduced at the working electrode. Fouling or coating of
the probe necessitates frequent cleaning, although the equi-
librium-dissolved oxygen sensor greatly reduces the fouling
problems and also allows use in almost stagnant flows with
very small face velocity at the probe.
Figure 8.4f shows a nominal configuration for an elec-
trolytic probe. The probe consists of an inner and outer ele-
ment. The inner element contains the cathode and anode with
wires leading to the power supply and current-monitoring
circuit. The anode is positioned in a way that isolates the
cathode from the anode. The outer element fits over the inner
element and provides a space for the electrolyte. The mem-
brane is mounted on the outside of this outer element and
secured with an O-ring.
Sensors are available in disposable, nonrechargeable con-
figurations, as well as in rechargeable configurations, in
which access is provided to allow electrolyte change, elec-
trode cleaning, and membrane replacement.
Amperometry
Amperometric titration is when the end point is determined
by measuring the current (amperage) that passes through the
solution at a constant voltage. Amperometry is the process

© 2003 by Béla Lipták

 8.4 Analyzers Operating on Electrochemical Principles 1203

O-Ring (a)
for Membrane

End

Current
Point
Electrolyte
Grooves for
Cavity
O-Ring Seals

Time
End
(b)
Point

Current
Outer Element

Time
Gold Cathode
(c) End
Silver Anode Point

Current

Time

FIG. 8.4g
Anode Connector Cathode Connector Response curves for polarographic cell system, showing curve A,
when analyte reacts at electrode; curve B, when reagent reacts at
Inner Element electrode; and curve C, when analyte and reagent react at electrode.

FIG. 8.4f
Configuration of an electrolytic probe. The inner element contains
the anode and cathode, while the outer element isolates the elec-
trolyte from the sample.
of performing an amperometric titration. During such titra-
tion, the current flow is monitored as a function of time
between working and auxiliary electrodes while the voltage
difference between them is held constant. Alternatively, the
current can also be monitored as a function of the amount of
reagent added to bring the titration of an analyte to the (sto-
ichiometrically defined) end point. This is also called con-
stant potential voltametry.
In amperometry, the titrating reagent is coulometrically
generated and the current that passes through a polarographic
cell (containing either a solid or dropping mercury electrode
at the appropriate oxidation or reduction potential) is mea-
sured as a function of reagent volume or time. Three types
of response curves can be expected (Figure 8.4g).
Curve (a) is the result of the analyte reacting at the
electrode, while the reagent does not. This curve indicates
that the diffusion current is detected as long as the analyte
remains. Once the reagent removes all the analyte, the current
stops. This dead-stop end-point technique is often used for
amperometric determinations of dissolved oxygen.
In curve (b), the analyte is not reduced at the working
electrode, but the reagent is. In this situation, there is no
current flow until the analyte is completely destroyed and the
reagent is allowed to react at the electrode surface.
Finally, curve (c) indicates the response when both ana-
lyte and reagent are electroactive. The increase after the
equivalence point indicates that the current is the result of
excess reagent reacting at the electrode surface.
Solid Electrodes If the polarographic cell is replaced by a
two-solid electrode system with a small applied potential (0.1
to 0.2 V), the response curves of interest are determined by
a number of reversible reactions occurring in the cell at the
voltage level impressed across the cell.
The set of reversible half-reactions of interest are sym-
bolized as
−
Rr f Ro + e 8.4(2)
and
−
Ao + e f Ar 8.4(3)
where Ao and Ro are the oxidized forms, and Ar and Rr are
the reduced forms of the analyte and reagent, respectively.
The fundamental concept of interest is the fact that the
applied potential will support current flow only when both
forms represented in Equation 8.4(2) or Equation 8.4(3) are
present in the test solution. Figure 8.4h represents the possi-
ble response curves that illustrate this concept.

© 2003 by Béla Lipták

1204 Analytical Instrumentation

(a) Thermistors Connector

Ao and Ar Body
Anode
Current

End Fill Port

Point
Cap

Ro and Rr
Electrolyte

Ao Only
t0 Time t1
O-Rings

(b) Ao and Ar
Teflon Membrane Cathode

FIG. 8.4i
End
Current

Point Membrane-type amperometric probe.

Ar Only Polarography

Polarography is a process for monitoring the diffusion current

Ao Only
flow between working and auxiliary electrodes as a function
t0 Time t1 of applied voltage as it is varied systematically. The diffusion
current that results is linearly dependent on the concentration
(c)
of the analyte. Polarography can be applied using direct cur-
rent, pulsed direct current, or alternating current (AC) voltage
End
excitation waveforms. Dissolved oxygen determination is an
Current

Point
example of an application for which polarography is used
Rr Only
Rr and Ro (Figure 8.4e).
Nobel Prize winner Jaroslav Heyrovsky developed direct
current polarography in 1922. Polarography is performed by
t0 Time t1 measuring the current flow, which is a function of the sys-
tematically varied electrode potential. Different types of
FIG. 8.4h polarographies can be performed as a function of the voltage
Response curves for two-solid electrode system, showing curve A, variation patterns, voltage sweep rates, and the choice of
when analyte and reagent are reversible; curve B, when only the working electrode materials.
analyte is reversible; and curve C, when only the reagent is reversible. Figure 8.4j shows a typical polarographic response curve.

Diffusion Plateau
In curve (a) of Figure 8.4h, the absence of current at to
is due to the lack of A r . For values of t so that to < t < t1, the
current response is the result of varying concentrations of Ao
and Ar as Rr is added. At t = t1, the current returns to zero
because of the absence of Ao and Rr. Finally, for t > t1, the
continuous addition of Rr, coupled with the Ro present from (E 1 , i 1 )
id
the redox reaction with Ao, results in a continuously increas-
Current

2 2

ing current flow.

Curve (b) indicates the response when only the analyte
reaction is reversible. The curve from to < t ≤ t1 is identical
to the same portion of curve (a) for the same reasons. How-
ever, for t > t1, no current is detected because the reagent
half-reaction is irreversible.
Curve (c) shows the results when the analyte reaction is
0 Cathode Potential −1.0 V
irreversible but the reagent half-reaction is reversible. Current
is not detected until Rr remains in the solution. This case is often FIG. 8.4j
called a dead-start titration because the current does not begin Polarogram showing typical current vs. cathode potential response.
until all the analyte has been removed. Figure 8.4i illustrates the The diffusion current, id; the half-wave potential, E1/2; and the half-
design of another membrane-type amperometric sensor. wave current, i1/2, are all illustrated.

© 2003 by Béla Lipták

 8.4 Analyzers Operating on Electrochemical Principles 1205

For this curve, the K term in Equation 8.4(1) is defined as

1 /2
K = nFC°(7/3Do) 8.4(4)

and

1/2
(nF/KT)(E − E° − ln(fo /fr(Do /Dr) ) = ln(id − i/i) 8.4(5)

where id is the diffusion current. The curve shows an S-shaped

current response as the potential at the cathode, the working
electrode where analyte reduction occurs, becomes more neg-
ative. Current limited by diffusion occurs at cathodic poten-
tials beyond the potential required to initiate reduction. Thus,
id is sufficient to reduce the diffusion-supplied analyte con-
centration to zero.
The significance of this is that the diffusion rate is con-
trolled by the concentration gradient established between the
concentration at the surface of the working electrode, which
is held to zero as a result of the electrode reaction, and the
concentration existing in the bulk of the solution. The current
observed for the Faradic process of interest is directly pro-
portional to the concentration of the desired analyte.
Subsequently, this technique was modified by changing
the voltage excitation waveform to alternating current (AC
polarography) or to pulsed direct current (pulse polarography
or differential pulse polarography); these modifications
resulted in increased sensitivity and better discrimination for
the detection of the desired analyte in a background matrix
of interferences.
Advantages One of the valuable aspects of a polarographic
determination is that the potential observed at the point
i1/2 = id/2 is unique to the analyte in the solution matrix. This
occurs because the potential at i1/2 is independent of the
reactant concentrations but directly related to the standard
potential for the analyte half-reaction. This inflection point
potential is defined as the half-wave potential, E1/2, and is a
common parameter for qualitative identification of electro-
active components in a solution.
When the reaction is fast and reversible and the diffusion
coefficients of the oxidized and reduced forms of the analyte
are virtually identical, E1/2 becomes E°. Another value of
polarography is that the diffusion current is linearly related
to the concentration of the analyte.
Coulometry
Coulometry is the process of monitoring analyte concentration
by detecting the total amount of electrical charge passed
between two electrodes that are held at a constant potential or
when constant current flow passes between them. Because the
coulomb provides a direct connection through Faraday’s law
between reaction current and analyte concentration during a
redox process, coulometry offers a direct method of determin-
ing analyte concentration.
Current
t1idt
t0
t0 Time t1
FIG. 8.4k
Response curve for controlled potential coulometry, showing the
relationship among current, i; time, t; and coulombs, QF , in the
Faradic portion of the curve.
Two types of coulometry are possible: constant current
and controlled potential. Constant current coulometry depends
on analyte oxidation–reduction to support the specified cur-
rent flow. When the supply of material is insufficient to carry
this current, the electrode potential drifts until another reac-
tion begins. The result of this process is a potential time
relationship similar to the results obtained in chronopotenti-
ometry, and the amount of charge passed is simply the product
of the constant current and electrolysis time.
Controlled Potential Coulometry By contrast, controlled poten-
tial coulometry is conducted by maintaining a constant elec-
trode potential while a current flow is measured. The number
of coulombs is determined by integration of the reaction
current as a function of electrolysis time. Figure 8.4k illus-
trates the current–time relationship for controlled potential
coulometry.
The choice of integration time is important because the
current is the sum of the Faradic component and a capacita-
tive component. As a result of this dual contribution, current
integration is not started until the capacitative-charging con-
tribution is minimal.
CONCLUSIONS
Although instruments are available for all types of voltamet-
ric analysis, currently only the potentiometric, polarographic,
amperometric, and coulometric designs are available as on-
line process analyzers. This is likely to change.

© 2003 by Béla Lipták

1206 Analytical Instrumentation
Limitations
The limitations of this category of sensors are mostly
related to the membranes. One major problem with the thin
permeable membranes is the fact that the electrode
response to the analyte is directly dependent on the con-
dition of the membrane. Once the potential has been
applied across the electrodes and the concentration deple-
tion wave has reached the inner membrane wall, the amount
of analyte that reaches the electrode depends on the diffu-
sion of the analyte through the membrane. This situation
is usually acceptable because the membrane condition is
stable. The membrane itself is also subject to failure, and
the surface of the membrane is exposed to the process fluid,
which can alter its permeability to the analyte. These con-
ditions make the long-term reliable use of electrolytic
probes problematical, because they require constant main-
tenance and recalibration.
Amperometric end points pose another problem. To date,
provisions for the various end points possible are not avail-
able, and care must be taken when determining analysis end
points. Finally, instrumentation for coulometric methods
requires that the working electrode be physically separated
from the auxiliary electrode so that the reaction products do
not migrate to the opposite electrode. Sintered glass discs are
used to restrict the migration of reaction products between
the electrodes, but they permit electrical conduction through
the cell. Table 8.4a provides a summary of voltametric meth-
ods and applications.
Advances
Significant advances have been made by the introduction of
equilibrium-state voltametric probes. These have the advan-
tage of analyte sensitivities that are relatively independent of
membrane coating and consume so little of the analyte as a
result of the measurement process that they are able to work
in processes where the sample flow rate past the face of the
sensor is small.
Reference
1. Reimmuth, Analytical Chemistry, 32:1509, 1960.
© 2003 by Béla Lipták
Bibliography
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1990.
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