Solid-state sensors

prepared by Katarzyna Wygladacz

In the conventional ion-selective electrodes (ISE), the ion-selective membrane is in

electrical contact with the inner reference electrode through the inner reference solution.
The convertion from ionic conductivity (in the membrane and the inner reference
solution) to electron conductivity (in the inner reference electrode and external
instrumentation) is provided by the reversible reaction of the inner reference electrode
resulting in an ISE exhibiting a stable and reproducible standard potential.

The desire to miniaturise and mass fabricate sensors has led to the development of
potentiometric solid-state sensors with new sensing systems, namely solid contact
electrodes (SCEs) [1] such as solid crystal membranes and coated wire electrodes
(CWEs) [2,3].

Coated-wire electrodes refer to a type of ISE in which an electroactive species is

incorporated in a thin polymeric support film coated directly on a metallic conductor.
This move to the total elimination of the internal filling solution provides new
advantages. The substrate in the wire type electrodes is usually platinum wire, but silver,
copper and graphite rods have also been used. CWEs are manufactured by dipping a
metal wire into a solution of the membrane mixture [3]. The scheme of CWE is presented
in the Fig. 1.
Fig. 1. The scheme of coated wire electrode

Dalam konvensional elektroda ion-selektif (ISE), ion-selektif membran dalam kontak

listrik dengan elektroda referensi batin melalui referensi dalam solusi. Konversi dari
konduktivitas ionik (di dalam membran dan referensi dalam solusi) untuk konduktivitas
elektron (di pusat elektroda referensi dan instrumentasi eksternal) ini disediakan oleh
reaksi reversibel dari elektrode acuan dalam menghasilkan suatu pameran ISE diulang
yang stabil dan potensial standar .

Keinginan untuk mengarang miniaturise dan sensor massa telah mengarah ke

pengembangan potentiometric solid-state sensor dengan sistem penginderaan baru, yaitu
kontak padat elektroda (SCEs) [1] seperti kristal padat dilapisi membran dan kawat
elektroda (CWEs) [2,3 ].

Kawat elektroda berlapis merujuk pada jenis ISE di mana spesies electroactive tergabung
dalam sebuah film yang tipis dilapisi polimer dukungan langsung pada konduktor logam.
Ini pindah ke penghapusan total internal menyediakan solusi mengisi keuntungan baru.
Substrat pada kawat elektroda jenis ini biasanya platinum kawat, tetapi perak, tembaga
dan grafit batang juga telah digunakan. CWEs dibuat dengan mencelupkan kawat logam
ke dalam larutan campuran membran [3]. Skema cwe disajikan dalam Gambar. 1.

Sensors for Ca2+, NO3-, K+, Cl-, Li+ and ClO4- have been developed and sometimes these
electrodes exhibited better selectivity than conventional type electrodes with an internal
solution. Simplicity of design, lower costs, mechanical flexibility of miniaturisation and
microfabrication widened the application for wire type electrodes, especially in the fields
of medicine and biotechnology.
However, the configuration of CWE involves some crucial drawbacks. Commonly
observed phenomena in such solid-state ion-sensors are a poor mechanical adhesion of
the PVC-based sensitive layer to the transducer surface and insufficient electrochemical
stability i.e. shift and drift of the EMF [4]. The standard potential of CWEs is often
unstable varying for the electrode during its lifetime. These systems cannot provide very
reproducible potentials due to the poorly defined charge transfer process at the interface
between the ionically conducting membrane and the electrically conducting substrate. In
the case of CWEs, drift characteristics were reported to be dependent on the kind of
solids used [5,6] and on dissolved oxygen [6]. It has been found that usually an oxygen
half-cell is set up on the metal surface so that the electrodes are susceptible to the oxygen
content of the solution [7,8].

ISEs with direct contact of the membrane to a metal substrate constructed in a different
manner have also been described. Some improvement has been made for this type of
electrode with regard to the adhesion of the membrane by using a metal loaded epoxy as
substrate [9], but these electrodes also did not possess a defined interface and were found
to suffer from oxygen interface.

A more stable electrode potential can be obtained by contacting the ion-selective

membrane to the solid substrate via an intermediate layer. Polymeric materials exhibiting
mixed ionic and electronic conductivity, containing extended p-conjugated back-bones,
such as poly(pyrrole) [10], poly(aniline) [11-13], poly(thiophene) [12] can be applied for
this purpose. These materials may be prepared electrochemically by oxidation of their
monomer.

Owing to the introduction of such electrically conducting polymers (CPs) t he ionic

response of an ion-selective membrane (ISM) is converted to an electric signal.

To facilitate the charge transfer across the interface in solid contact ISE (SC-ISE),
improve the potential stability and prevent oxygen interference the introduction SAM of a
lipophilic redox-active compound was also proposed [14]. The structures of compounds
used for this aim are presented in the Fig. 2.

Sensor untuk Ca2 +, NO3-, K +, Cl-, Li + dan ClO4-telah dikembangkan dan kadang-
kadang dipamerkan elektroda konvensional lebih baik daripada tipe selektivitas elektroda
dengan solusi internal. Kesederhanaan desain, biaya rendah, fleksibilitas mekanik
microfabrication melebar miniaturisation dan aplikasi untuk jenis kawat elektroda,
terutama di bidang kedokteran dan bioteknologi.
Namun, konfigurasi cwe melibatkan beberapa kekurangan penting. Fenomena yang
biasa terlihat di solid-state seperti ion-sensor adalah adhesi mekanis miskin PVC
berbasis lapisan sensitif ke permukaan transduser elektrokimia dan kurangnya
stabilitas yaitu shift dan drift dari EMF [4]. Potensi standar sering tidak stabil
CWEs bervariasi untuk elektroda selama masa pakai baterai. Sistem ini tidak dapat
menyediakan potensi yang sangat diulang karena kurang proses transfer biaya
didefinisikan pada antarmuka antara melakukan ionically membran dan substrat
listrik. Dalam kasus CWEs, karakteristik arus dilaporkan tergantung pada jenis
padatan digunakan [5,6] dan pada oksigen terlarut [6]. Telah ditemukan bahwa
biasanya oksigen setengah-sel ditetapkan pada permukaan logam sehingga
elektroda rentan terhadap isi oksigen solusi [7,8].
ISEs dengan kontak langsung antara membran ke substrat logam dibangun melalui cara
yang berbeda juga telah dijelaskan. Beberapa perbaikan telah dibuat untuk jenis elektroda
yang berkaitan dengan adhesi membran dengan menggunakan epoxy dimuat logam
sebagai substrat [9], tetapi ini juga elektroda tidak memiliki antarmuka yang ditetapkan
dan yang ditemukan menderita oksigen antarmuka.
Yang lebih stabil potensial elektroda dapat diperoleh dengan menghubungi ion-selektif
membran ke substrat padat melalui lapisan perantara. Campuran bahan polimer
menunjukkan konduktivitas ionik dan elektronik, yang mengandung p-conjugated
diperpanjang kembali-tulang, seperti poli (Pirola) [10], poli (anilina) [11-13], poli
(thiophene) [12] dapat diterapkan untuk ini tujuan. Semua materi dapat disiapkan
elektrokimiawi oleh oksidasi monomer mereka.
Karena pengenalan listrik seperti polimer (CPS) t dia respons ion ion-selektif membran
(ISM) dikonversikan ke sinyal listrik.
Untuk memfasilitasi transfer muatan pada antarmuka kontak padat ISE (SC-ISE),
meningkatkan stabilitas dan mencegah potensi gangguan oksigen SAM pengenalan
redoks yang lipofilik senyawa aktif juga diusulkan [14]. Struktur senyawa yang
digunakan untuk tujuan ini disajikan dalam Gambar. 2.

Fig. 2. The structures used compounds for SAM preparation

In such case a lipophilic and redox-active compound is attached by self-assembly to the

inner gold electrode. The redox properties of the SAM guarantee a stable potential, while
their lipophilicities prevent the formation of an aqueous layer between membrane and the
metal electrode.

Dalam kasus seperti ini yang lipofilik dan redoks-senyawa aktif terpasang oleh diri
perakitan ke dalam elektroda emas. Sifat-sifat redoks SAM menjamin potensi yang stabil,
sementara mereka lipophilicities mencegah pembentukan lapisan yang berair antara
membran dan elektroda logam.
MINIATURISED SOLID-STATE
SENSORS BASED ON SILICON
TECHNOLOGY
The first miniaturized potentiometric solid-state sensors based on silicon technology were
developed at University of Michigan several years ago [15,16]. Silicon structures
employed for this purpose possessed both: the sensing and electrical contact sites on the
front side of the chip (FSC). The scheme of such a sensor is presented in the Fig. 3.

Miniatur pertama potentiometric sensor solid-state yang didasarkan pada teknologi

silikon sedang dikembangkan di University of Michigan beberapa tahun yang lalu
[15,16]. Struktur silikon digunakan untuk tujuan ini memiliki keduanya: yang sensing
dan situs kontak listrik di sisi depan chip (FSC). Skema sensor seperti disajikan dalam
Gambar. 3.

Fig. 3. The scheme of the front-side solid-state miniaturized sensor

Such sensors' design requires an additional encapsulation layer that covers the electrical
contact pads. Insufficient quality of this encapsulation layer might cause a solid problem
when sensors are used in an electrolyte solution. In order to eliminate this problem,
potentiometric sensors with a back-side electrical contact (BSC) and front-side sensing
site, fabricated with silicon technology, have been designed and applied for the
fabrication of miniaturized BSC ion-sensors [17]. The structure of BSC sensor is
presented in the Fig. 4.

Semacam sensor 'desain enkapsulasi membutuhkan tambahan lapisan yang menutupi

bantalan kontak listrik. Kualitas memadai lapisan enkapsulasi ini dapat menyebabkan
masalah yang solid ketika sensor digunakan dalam larutan elektrolit. Untuk
menghilangkan masalah ini, potentiometric sensor dengan sisi back-kontak listrik (BSC)
dan front side situs sensing, dibuat dengan teknologi silikon, telah dirancang dan
diterapkan untuk miniatur BSC fabrikasi ion-sensor [17]. Struktur sensor BSC disajikan
dalam Gambar. 4.

Fig. 4.The structure of BSC sensor

The back-side contact silicon-based chips were fabricated using IC technology, by

photolithography processes. The structures possess the miniaturised Ag/AgCl sensing site
situated on the front of the chip. Such Ag/AgCl electrode shows the changes in EMF as a
function of chloride concentration according to the Nernst equation:

Sisi belakang kontak chip berbasis silikon yang direkayasa menggunakan teknologi IC,
oleh proses Fotolitografi. Memiliki struktur miniaturised Ag / AgCl situs penginderaan
terletak di bagian depan chip. Seperti Ag / AgCl elektroda menunjukkan perubahan dalam
EMF sebagai fungsi dari konsentrasi klorida menurut persamaan Nernst:

E = E0 - 59.16 lg aCl-

The potentiometric response (the calibration curves) of 10 randomly chosen sensors

toward changes in chloride concentration is presented in the Fig. 5.
Fig. 5. The response of 10 randomly chosen BSC sensors toward changes in chloride
concentration

Based on the potentiometric characteristics of BSC chip it can be concluded that

Ag/AgCl sensing site can play role of the internal reference electrode. Such sensors are
useful for miniaturised ion-selective sensor preparation.

However it was found that both kinds of sensors with front and back-side electrical
contact suffer from instabilities of potential values. Several approaches (e.g. the
incorporation of lipophilic silver-ligand complexes within polymeric films, the
intermediate pHEMA layer introduction) have been suggested to improve the stability of
such sensors by establishing a reversible electron transfer pair at the membrane/solid
contact interface. The scheme of miniaturised solid-state chemically modified BSC
sensor with intermediate pHEMA layer and polymeric membrane is presented in the Fig.
6.

Berdasarkan karakteristik potentiometric BSC chip dapat disimpulkan bahwa Ag / AgCl

situs penginderaan dapat memainkan peran elektroda referensi internal. Semacam sensor
berguna untuk miniaturised sensor ion-selektif persiapan.
Namun ditemukan bahwa kedua jenis sensor depan dan belakang dengan sisi kontak
listrik menderita dari ketidakstabilan nilai-nilai potensial. Beberapa pendekatan (misalnya
penggabungan ligan lipofilik perak polimer kompleks dalam film, pengenalan lapisan
menengah pHEMA) telah menyarankan untuk meningkatkan stabilitas sensor tersebut
dengan membentuk pasangan reversibel transfer elektron pada membran / padat
antarmuka kontak. Skema miniaturised solid-state BSC dimodifikasi secara kimia
pHEMA sensor dengan lapisan menengah dan membran polimer disajikan dalam
Gambar. 6.

Fig. 6.The structure of BSC chemically modified sensor

Such configuration involves the charge transfer processes at both sides of the IS
membrane well thermodynamically.
Ion-selective miniaturised BSC sensors with polymeric membranes are typically
investigated in a galvanic cell:

Ag/AgCl/KCl(sat)/1M CH3COOLi//sample solution//liquid membrane/

/internal filing solution (pHEMA)/Ag/AgCl

It is common to divide the membrane potential (EM) into several separate potential
contributions, namely the phase boundary potentials at both interfaces and the diffusion
potential within the ion-selective membrane. The potential at the membrane/inner filling
solution (pHEMA layer) interface can usually be assumed to be independent of the
sample. The boundary potential (membrane/sample solution) depends on the ion-
exchange processes between the solution and membrane phase. The diffusion potential
within the membrane may become significant if considerable concentration gradients of
ions with different mobilities arise in the membrane.

The selectivity of classical ISE and miniaturised sensors in the presence of the primary
and interfering ions can be described by the selectivity coefficient according to the
Nicolskii-Eisenman equation:

Adalah umum untuk membagi potensial membran (EM) menjadi beberapa kontribusi
potensial yang terpisah, yaitu fase potensi batas di kedua interfaces dan potensi dalam
difusi ion-selektif membran. Potensial pada membran / batin solusi mengisi (pHEMA
lapisan) antarmuka biasanya dapat diasumsikan independen dari sampel. Batas potensial
(membran / sampel larutan) tergantung pada proses pertukaran ion antara larutan dan fase
membran. Potensial difusi dalam membran bisa menjadi cukup signifikan jika gradien
konsentrasi ion-ion dengan mobilitas yang berbeda muncul dalam membran.
Yang selektivitas klasik dan miniaturised sensor ISE dalam kehadiran dan campur utama
ion dapat digambarkan oleh koefisien selektivitas menurut Eisenman Nicolskii-
persamaan:

Where: E - the membrane potential; E0 - constant; aI, aJ - the activity of primary and
interfering ions, respectively; ZI, ZJ - charge of primary and interfering ions,
respectively; I - primary ions; J - interfering ion;

The miniaturised chemically modified back-side contact chips can be designed as anions
as well as cations selective sensors. The calibration curves for NO2- - selective sensors
with membranes based on linear polyurethane (Tecoflex) and containing the tetraphenyl
porphyrin nitrite (CoTPPNO2) as a nitrite-selective ionophore are presented in the Fig. 7.

Di mana: E - potensial membran; E0 - konstan; AI, aJ - kegiatan utama dan campur ion,
masing-masing; ZI, ZJ - tuduhan primer dan campur ion, masing-masing; aku - ion
utama; J - campur ion;
The miniaturised kimia diubah kembali-sisi chip kontak dapat dirancang sebagai anion
maupun kation selektif sensor. Kurva kalibrasi untuk NO2-- sensor dengan membran
selektif berdasarkan linear poliuretan (Tecoflex) dan berisi porfirin tetraphenyl nitrit
(CoTPPNO2) sebagai nitrit-selektif ionophore tersebut disajikan dalam Gambar. 7.

Fig. 7. The calibration curves for the BSC sensors based on Co(III)
[TPP]NO2/TDMACl//PU/o-NPOE
The sodium selective chips based on back-side silicon sensors have also been described
[18]. The potentiometric response of the BSC structures with polymeric membrane
containing isodecyl acrylate/acrylinitryle and calix[4]arene as a sodium selective
ionophore is presented in the Fig. 8.

Fig. 8. The calibration curves of Na+ - selective miniaturised BSC sensors with
intermediate pHEMA layer and membranes based on copolymer isodecyl
acrylate/acrylonitryle and calix[4]arene as a sodium selective ionophore

Plasticised PVC is commonly used as the membrane material for classical ISEs and
CWEs. However it can not be applied as a polymeric matrix for miniaturised silicon-
based sensors due to the lack of its adhesion to Si3N 4 surface. Insufficient adhesion may
cause detachment of ion-selective membrane based on linear polymer and shortening of
sensor's lifetime. The application of the photocurable polymeric matrix is recommended
in order to fulfil the requirements related to membrane adhesion to sensor's support and
its mechanical properties.

Plasticised PVC biasanya digunakan sebagai bahan membran ISEs klasik dan CWEs.
Namun hal itu tidak dapat diterapkan sebagai sebuah matriks polimer untuk miniaturised
sensor berbasis silikon karena kurangnya dari Si3N 4 adhesi ke permukaan. Cukup adhesi
dapat menyebabkan detasemen membran ion-selektif didasarkan pada polimer linier dan
pemendekan masa hidup sensor. Penerapan matriks polimer photocurable dianjurkan
dalam rangka memenuhi persyaratan yang berkaitan dengan adhesi membran untuk
sensor dukungan dan sifat mekanik.

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Ion Selective Electrodes (ISE)

Background -- Ion Selective
Electrodes (ISE) are
membrane electrodes that
respond selectively to ions
in the presence of others.
These include probes that
measure specific ions and
gases in solution. The most
commonly used ISE is the
pH probe. Other ions that
can be measured include
fluoride, bromide, cadmium, and gases in solution such as ammonia, carbon dioxide, and
nitrogen oxide.

The use of Ion Selective Electrodes in environmental analysis offer several advantages
over other methods of analysis. First, the cost of initial setup to make analysis is
relatively low. The basic ISE setup includes a meter (capable of reading millivolts), a
probe (selective for each analyte of interest), and various consumables used for pH or
ionic strength adjustments.

Also see the newest ICE used with PDA.

The expense is considerably less than other methods, such as Atomic Adsorption
Spectrophotometry or Ion Chromatography. ISE determinations are not subject to
interferences such as color in the sample. There are few matrix modifications needed to
conduct these analyses. This makes them ideal for clinical use (blood gas analysis) where
they are most popular; however, they have found practical application in the analysis of
environmental samples, often where in-situ determinations are needed and not practical
with other methods. A large number of indicator electrodes with good selectivity for
specific ions are based on the measurement of the potential generated across a membrane.
Electrodes of this type are referred to as ion-selective electrodes. The membrane is
usually attached to the end of a tube that contains an internal reference electrode. This
membrane electrode and an external reference electrode are then immersed in the solution
of interest. Since the potentials of the two reference electrodes are constant, any change
in cell potential is due to change in potential across the membrane.

Different membrane materials have proved to give optimal responses for certain species.
For example, a glass membrane is unsurpassed for measuring H+ activity, pH. This ISE
may be referred to as a glass or pH electrode.

Liquid membrane electrodes have non-glass, solid-state crystals or pellets as the

membrane component of the electrode. This approach has proved effective for numerous
cations and anions. The most successful example is the excellent electrode for fluoride
ion, which is based on a crystal of LaF3 doped with Eu(II) to create crystal defects to
improve conductivity.

Gas-sensing electrodes or combination electrodes that respond to the concentration of

gases dissolved in aqueous solution. The electrodes consist of an ion-selective electrode,
usually pH, in contact with a thin layer of solution that is held in place with a membrane
permeable to the desired gas such as NH3 or CO2. When the gas passes through the
membrane, the change of pH in the thin layer of solution is sensed by the glass membrane
pH electrode.

Other combination electrodes consist of an enzyme immobilized on an ISE. The ISE is

chosen to respond to a product of the enzyme-substrate reaction and the selectivity is
provided by the enzyme.

History -- Credit for the first glass sensing pH electrode is given to Cremer, who first
described it in his 1906 paper (Meyerhoff and Opdeycke). In 1949, George Perley
published an article on the relationship of glass composition to pH function (Frant). In the
interim there were numerous papers dealing with various formulations of and several
important contributions were made (Covington).

The commercial development of ISE began when an engineer by the name of John
Riseman thought he could develop a useful blood-gas analyzer. He teamed up with Dr.
James Ross, an electrochemist from MIT. Together they formed Orion Research (Frant).
By the mid 1960s, the newly formed Orion Research Inc. was producing Calcium
electrodes for use in blood gas analyzers (Frant, 1994). Since then numerous probes have
been developed for the analysis of samples containing many different ions.

How do they work or what is an Ion-Selective Electrode? An Ion Selective Electrode

measures the potential of a specific ion in solution. (The pH electrode is an ISE for the
Hydrogen ion.) This potential is measured against a stable reference electrode of constant
potential. The potential difference between the two electrodes will depend upon the
activity of the specific ion in solution. This activity is related to the concentration of that
specific ion, therefore allowing the end-user to make an analytical measurement of that
specific ion. Several ISE's have been developed for a variety of different ions.

How Does the mV Reading Correspond to the Concentration? Standard solutions of

known concentrations must be accurately prepared. These solutions are then measured
with the pH/mV meter. The mV reading of each solution is noted and a graph of
concentration vs. mV reading must be plotted. Now the unknown solution can be
measured. The mV value of the unknown solution is then located on the graph and the
corresponding solution concentration is determined.

Ion Selective Electrodes (including the most common pH electrode) work on the basic
principal of the galvanic cell (Meyerhoff and Opdycke). By measuring the electric
potential generated across a membrane by "selected" ions, and comparing it to a reference
electrode, a net charge is determined. The strength of this charge is directly proportional
to the concentration of the selected ion. The basic formula is given for the galvanic cell:

Ecell = Eise - Eref

the potential for the cell is equivalent to the potential of the ISE minus the potential of the
reference electrode.
Calibration -- Direct - The electric potentials are determined for a series of standards and
a standard curve is developed. Additional analyses are fit to the standard curve in order to
determine concentration. Direct calibration is the most common and easiest way to
measure concentrations.

Standard Additions - The use of standard additions (the addition of known amounts of a
standard) allows the use of the electrode in very complex matrices, without the need for
direct calibration prior to measurement (Covington).

Titration's - ISEs have also been used as detectors for titration's (Orion). Titration
methods use a titrant (such as EDTA) which will complex or react with the ion to be
analyzed. The concentration of the ion in the sample is back calculated from the volume
of the titrant used in the titration.

Membranes -- The nature of the membrane determines the selectivity of the electrode. A
membrane is considered to be any material that separates two solutions. It is across this
membrane that the charge develops. The term "membrane" is often confuse as implying
permeability. While this is true in many cases, the term here is used denote any material
which the charge can develop across (Covington).

Several types of sensing electrodes are commercially available. They are classified by the
nature of the membrane material used to construct the electrode. It is this difference in
membrane construction that makes an electrode selective for a particular ion.

1. Polymer Membrane Electrodes (Organic Ion Exchangers and Chelating Agents) --

Polymer membrane electrodes consist of various ion-exchange materials incorporated
into an inert matrix such as PVC, polyethylene or silicone rubber. After the membrane is
formed, it is sealed to the end of a PVC tube. The potential developed at the membrane
surface is related to the concentration of the species of interest. Electrodes of this type
include potassium, calcium, chloride, fluoroborate, nitrate, perchlorate, potassium, and
water hardness.

2. Solid State Electrodes (Insoluble Conductive Inorganic Salts) -- Solid state electrodes
utilize relatively insoluble inorganic salts in a membrane. Solid state electrodes exist in
homogeneous or heterogeneous forms. In both types, potentials are developed at the
membrane surface due to the ion-exchange process. Examples include silver/sulphide,
lead, copper(II), cyanide, thiocynate, chloride, and fluoride.

3. Gas Sensing Electrodes -- Gas sensing electrodes are available for the measurement of
dissolved gas such as ammonia, carbon dioxide, nitrogen oxide, and sulfur dioxide. These
electrodes have a gas permeable membrane and an internal buffer solution. Gas
molecules diffuse across the membrane and react with a buffer solution, changing the pH
of the buffer. The pH of the buffer solution changes as the gas reacts with it. The change
is detected by a combination pH sensor within the housing. Due to their construction, gas
sensing electrodes do not require an external reference electrode.

4. Glass Membrane Electrodes -- Glass membrane electrodes are formed by the doping of
the silicon dioxide glass matrix with various chemicals. The most common of the glass
membrane electrodes is the pH electrode. Glass membrane electrodes are also available
for the measurement of sodium ions.

Sources of Error -- Diffusion - Orion Research points out that differences in the rates of
diffusion of ions based on size can lead to some error. In the example of Sodium Iodide,
sodium diffuses across the junction at a given rate. Iodide moves much slower due to its
larger size. This difference creates an additional potential resulting in error. To
compensate for this type of error it is important that a positive flow of filling solution
move through the junction and that the junction not become clogged or fouled.

Sample Ionic Strength - Covington points out that the total ionic strength of a sample
affects the activity coefficient and that it is important that this factor stay constant. In
order accomplish this, the addition of an ionic strength adjuster is used. This adjustment
is large, compared to the ionic strength of the sample, such that variation between
samples becomes small and the potential for error is reduced.

Temperature - It is important that temperature be controlled as variation in this

parameter can lead to significant measurement errors. A single degree (C) change in
sample temperature can lead to measurement errors greater than 4%.

pH - Some samples may require conversion of the analyte to one form by adjusting the
pH of the solution (e.g. ammonia). Failure to adjust the pH in these instances can lead to
significant measurement errors.
Interferences - The background matrix can effect the accuracy of measurements taken
using ISE's. Covington points out that some interferences may be eliminated by reacting
the interfering ions prior to analysis.

Approved Methods for using ISE -- Standard methods for sample analysis using Ion
Selective Electrodes are published by several agencies. These include the American
Society of Testing and Material (ASTM), United States Environmental Protection Agency
(EPA) , American Public Health Association (APHA), Association of Analytical Chemists
(AOAC), and the United States Geological Survey (USGS). Approved Methods for using
Ion Selective Electrodes are (Species Measured): Acidity, Alkalinity, Ammonia, Bromide,
Carbon Dioxide, Chlorine, Chloride-Leachable, Chloride by Titration, Chloride Total in
Coal, Chlorine-Residual, Chlorine in Organics, Conductivity, Cyanate, Cyanide, Fluoride,
Fluoride in Air, Fluorine in Coal, Iodide, Kjeldahl Nitrogen, Nitrate, ORP (Oxidation-
Reduction Potential), Oxygen, Potassium, Salinity, Sodium, Sulfide, Sulfur in Coal, pH,
and pH Titration's.

Standard procedures may be found in the following references or on their respective

home web page.
(1) "Annual Book of ASTM Standards, Water and Environmental Technology," American
Society for Testing and Materials, (1992).

(2) "Methods for Chemical Analysis of Water and Wastes," Environmental Protection
Agency, Environmental Monitoring Systems Laboratory, EPA-600/4-79-020, 1983.

(3) "Standard Methods for Water and Wastewater Analysis," 18th Edition, 1994.

(4) Official Methods of Analysis of the Association of Official Analytical Chemists,

Methods Manual, 15th edition (1990).

(5) Methods for Analysis of Inorganic Substances in Water and Fluvial Sediments, U.S.
Dept. of the Interior, Techniques of Water Resource Investigations of the U.S. Geological
Survey, Denver, CO, Revised 1989.

(6) "Test Methods for Evaluating Solid Waste, Physical/Chemical Methods", SW-846,
Update III.

Measurement Considerations -- This discussion is designed to apply, in general, to all

specific ion electrodes. Typically, the ISE will come with its own instruction manual that
pertains to that particular type of electrode. It is best to read all instructions thoroughly
before using the electrode. When the ISE is received, open up the package immediately
and check all the parts of the electrode. Most ISE's have a pre-treatment procedure that
should be followed prior to operation. Before beginning measurements the following are
a few basic facts that will aid in designing analysis procedure.

What Type of Equipment is Needed for an ISE Measurement? A pH meter that also
measures millivolts can be used to interface with an ISE. Most ISE's are combination
electrodes that have the reference electrode built into the body of the ISE, however, some
ISE's require a separate reference electrode. If this is the case, the pH/mV meter must
have a pin-connector to connect the reference electrode.

Agitation -- When carrying out selective ion measurements, it is important to have good
agitation. This allows a fresh supply of ions to be exposed to the sensing portion of the
ISE. It is best to select a speed that keeps a constant, smooth motion. A turbulent rate
should be avoided.

pH Adjustment -- In many cases pH control is necessary for accurate, repeatable

measurements. Certain ions exhibit different activity when different concentrations of
hydrogen ions are present in solution. This occurrence will not only alter the potential due
to the specific ion that is measured, it may also allow other ions in solution to become
active that otherwise were not. This increased activity from the other ions will interfere
with the ability to evaluate the ion of interest.

Response Time -- ISE's require a much longer time for the readings to stabilize. At least
fifteen minutes should be allowed for equilibrium to be established when measuring
standard solutions.

Establishing a Calibration Curve -- It is recommended to use three standard solutions

when establishing a calibration curve. To choose the concentrations of the standard
solutions it is helpful to know the approximate values of the unknown solutions. For
example, if the unknown solutions are in the 100 ppm range, the choice of standards may
include a 10 ppm, a 100 ppm, and a 1000 ppm solution.

Rinsing -- It is necessary to rinse the ISE between measurements to insure accurate

readings. Use a steady stream of deionized or distilled water. Take care not to rub the
electrode with a cloth to dry the probe. It is usually best to "shake off" any excess water.
Take care not to hit the probe against anything while shaking the electrode.

Conditioning -- The ISE needs to remain moist at all times even when not in use. Consult
the operator's manual that accompanies the electrode for details on cleaning,
conditioning, and storing the ISE.

General Comments on Ion-Selective Electrodes:

1. Electrodes with a polymer membrane must not come in contact with organic
solvents
2. Do not store in water for extended periods—dry before storing
3. Store Combined Ion Selective Electrodes in dilute ISA (ionic strength adjuster)
 solution—for
long term
storage, remove
reference
solution and
store dry.
4. Clean crystal
membranes
with a mild
abrasive, then
rinse with
water.
Toothpaste is
an excellent cleaning agent, for fluoride electrodes use a fluoride toothpaste

What do some ISE look like?

Various ion selective electrodes by one manufacturer are shown at the left. The pHoenix
Electrode Company. All of their ISE's are now available in both glass and plastic body
combination electrodes. pHoenix Electrode Company is a manufacturer of
electrochemical analytical sensors as well as Vernier and hand held data capture devices.
They specialize in manufacturing pH, ORP, Conductivity, Oxygen and Ion Selective
Electrodes designed for Laboratory, Industrial, Biotechnology and Medical applications.

References

Covington, AK. "Introduction: Basic Electrode Types, Classifications, and Selectivity

Considerations." In. Covington, AK (ed.), Ion Selective Electrode Methodology.
Volume 1. CRC Press. Boca Raton. 1-20.

Frant, MS. 1994. "History of the Early Commercialization of Ion-Selective Electrodes."

Analyst 199, 2293-2301.

Meyerhoff, ME and WN Opdycke. 1986. "Ion Selective Electrodes." Advances in

Clinical Chemistry 25, 1-47.

Orion Research, Inc. 1997. Web Site Index. http://www.orionres.com/. or ORION ISE
Bibliography
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