Ion-selective electrodes (ISE)

Manual
8.109.8042EN

Metrohm AG
CH-9100 Herisau
Switzerland
Phone +41 71 353 85 85
Fax +41 71 353 89 01
info@metrohm.com
www.metrohm.com

Ion-selective electrodes (ISE)

Manual

8.109.8042EN

10.2013 ebe

Teachware
Metrohm AG
CH-9100 Herisau
teachware@metrohm.com

This documentation is protected by copyright. All rights reserved.

Although all the information given in this documentation has been
checked with great care, errors cannot be entirely excluded. Should you
notice any mistakes please send us your comments using the address
given above.
Documentation in additional languages can be found on
http://documents.metrohm.com.

Table of contents

Table of contents
1 Introduction
1.1

General .................................................................................. 1

1.2
Design of ion-selective electrodes (ISE) .............................. 1
1.2.1
Electrodes without exchangeable tip ........................................ 1
1.2.2
Electrodes with separate electrode tip ...................................... 2
1.3

Reference electrodes ............................................................ 2

2 Measuring

2.1
Preparing the electrodes ...................................................... 4
2.1.1
Crystal membrane electrodes ................................................... 4
2.1.2
Polymer membrane electrodes ................................................. 5
2.1.3
Glass membrane electrodes ..................................................... 5
2.2

Titration ................................................................................. 5

2.3

Direct measurement with calibration ................................. 6

2.4

Standard addition / standard subtraction .......................... 6

2.5

Cleaning the electrode ......................................................... 7

2.6

ISA/TISAB solutions .............................................................. 7

3 Storing electrodes
4 Troubleshooting

9
10

4.1

Problems with the reference electrode ............................ 10

4.2

Problems with the ion-selective crystal membrane electrode .................................................................................... 10

4.3

Problems with the ion-selective polymer membrane

electrode ............................................................................. 11

4.4

Application-related problems ............................................ 11

4.5

Interfering ions ................................................................... 11

5 Technical specifications

13

5.1

Measured data .................................................................... 13

5.2

Lifetime of polymer membrane electrodes ...................... 14

Glossary

15

Index

18

III

1 Introduction

1 Introduction
1.1

General
Immediately after receiving the electrode, check to make sure that it
works properly. Electrodes that do not work properly must be sent back
for warranty processing within two months (starting from the day of delivery). If the defect is proven to be due to a material or manufacturing
defect, the electrode will be replaced at no charge. The transport costs are
to the customer's account.

1.2

Design of ion-selective electrodes (ISE)

1.2.1

Electrodes without exchangeable tip

Examples: Ca2+ polymer membrane electrodes, Na+ polymer membrane
electrodes, crystal membrane electrodes.

Protective cap
Screw off and connect electrode cable.

SGJ sleeve SGJ 14/15, movable

Slide the SGJ sleeve all the way up for sample changer applications.

Sensor surface
Do not touch with your fingers.

Filler opening
For filling in electrolyte solution.

1.3 Reference electrodes

1.2.2

Electrodes with separate electrode tip

Examples: K+ polymer membrane electrode, NO3 polymer membrane
electrodes.

Protective cap
Screw off and connect electrode cable.

SGJ sleeve SGJ 14/15, movable

Slide the SGJ sleeve all the way up for sample changer applications.

Electrode tip incl. flat seal

For screwing onto the electrode shaft.

Sensor surface
Do not touch with your fingers.

1.3

Reference electrodes
The reference system is integrated into the electrode body for measuring
with combined ion-selective electrodes; for ion-selective electrodes without integrated reference system, you will need a separate reference electrode. We recommend the 6.0750.100 LL ISE Reference as external reference electrode. Owing to its fixed ground-joint diaphragm, this electrode
is not sensitive to contamination and offers low-noise measuring signals.
The LL ISE Reference contains KCl 3 mol/L as reference and bridge electrolyte.
If K+ or Cl are interfering (e.g. because it is the measuring ion or because
of cross-sensitivity), the LL ISE Reference has to be filled with a suitable
bridge electrolyte, e.g. KNO3, NaCl or NH4Cl. Please keep in mind that,

1 Introduction

after an exchange of electrolyte, the sensor requires some time until the
system is stable again.

Filler opening
For filling in the bridge electrolyte, e.g. KCl
3 mol/L. Refill weekly and replace from time
to time.

Ground-joint diaphragm

Reference system
Ag/AgCl with KCl gel.

2.1 Preparing the electrodes

2 Measuring
CAUTION

Do not use the ultrasonic bath for electrodes, as they may be damaged
by such a treatment.
CAUTION

2.1

Do not touch the sensor surface with your fingers.

Do not leave the electrode in distilled water for prolonged periods.
Do not rub the electrode dry after rinsing.
Avoid any contact of polymer membrane electrodes (e.g. Na+, K+,
Ca2+, NO3) with organic solvents.
Crystal membrane electrodes may be used in organic solvents (acetone, methanol, benzene) for short periods of time.
Protect the Cu electrode against direct sunlight and do no use it in
environments with changing illumination (the electrode is light-sensitive).
The Pb electrode must not be used in solutions containing acetate
(interferences with the membrane material).

Preparing the electrodes

Ion-selective electrodes should be prepared before the first usage, after
longer pauses and between precipitation titrations.

2.1.1

Crystal membrane electrodes

F electrode: Clean the sensor surface with a strongly alcaline detergent
such as Deconex universal or with toothpaste. Do not clean with the polishing set!
Other crystal membrane electrodes (electrodes 6.0502.XXX: Ag+, Cu2+,
Cd2+, Pb2+, Cl, Br, I, CN, SCN, S2): Polish with the 6.2802.000 polishing set. Put powder on the polishing pad, moisten and polish the sensor
surface using light pressure.
One polishing set may be used for only one ISE type. If various ion-selective electrodes are to be polished, one dedicated polishing set should be
reserved for each ISE type.

2.1.2

2 Measuring

Polymer membrane electrodes

Electrodes with separate electrode tip (e.g. K+, NO3): Tighten the electrode tip using only your hands (do not use any tools). Make sure that the
flat seal is in the correct position (see figure page 2). Place the electrode in
distilled water for approx. 15 minutes and then for approx. 30 minutes in
a solution containing the measuring ion of interest (c = 102 mol/L).
Electrodes without exchangeable tip (e.g. Na+, Ca2+): Rinse the electrode
with distilled water.
Combined polymer membrane electrode Ca2+: The combined ion-selective
electrode (ISE) is ready for direct use in most samples and requires no special preliminary treatment.
The electrode is shipped with NH4NO3 1 mol/L (6.2327.000) as reference
electrolyte. This reference electrolyte contains no chloride, which could
interfere in applications with parallel chloride titrations.
If necessary, e.g. for direct potentiometric measurements, KCl 3 mol/L can
also be used as reference electrolyte. It is, however, recommended not to
use NH4NO3 1 mol/L again in an ISE that has been filled with KCl 3 mol/L
as a reference electrolyte, because traces of chloride could lead to mixed
potentials.

2.1.3

Glass membrane electrodes

6.0501.100 Na+ electrode: Place in a solution of NaCl 1 mol/L for several
hours.

2.2

Titration
Ion-selective electrodes are well-suited for potentiometric titrations. The
resulting titration curves are usually S-shaped and can be evaluated well in
automatic titration systems.
For application advice on working with ion-selective electrodes, please go
to www.metrohm.com.

2.3 Direct measurement with calibration

2.3

Direct measurement with calibration

The ion activity in the sample is interpolated by means of a calibration
curve. The calibration curve is established with standard solutions. The
expected ion activity in the sample should lie in the mid-concentration
range of the calibration curve.
As usually the concentration of an ion is of interest (rather than its activity), measurements are executed at a fixed ionic strength. The ionic
strength is fixed with a TISAB solution (Total Ionic Strength Adjustment
Buffer). TISAB solutions have a high ionic strength, so that the various
contributions of the measuring ion to the ion strength can be neglected.
In most cases, they also buffer the pH value at the same time.
NOTE

Measure samples and calibration standards under identical measuring

conditions. The temperature of the standard solutions and the sample
solutions should as far as possible be the same during measurements.
Furthermore, the temperature should fluctuate as little as possible during the measurement.
In order to guarantee reliable results, periodically carry out a control
measurement with a calibration standard (e.g. daily). A new calibration
curve should be established if the potential difference is deemed unacceptable.

2.4

Standard addition / standard subtraction

In the standard addition method, a defined quantity of the ion to be
determined is added to a known volume of the sample (possibly in several
increments). Buffered solutions are usually used for this. The unknown
concentration can be calculated from the resulting potential differences
between the sample and the sample with added standard solution. This
calculation is executed automatically by modern ion meters.
The volume of the added standard solution should not exceed 25% of the
sample volume, and the concentration of the standard solution should be
as high as possible (in order to be able to rule out errors due to dilution).
The potential differences between the increments should be roughly constant and amount to at least 10 mV. Temperature differences between
the standard solution and the sample solution should be avoided.
In the standard subtraction method, a solution that eliminates the ion to
be determined is added (complexation or precipitation). Apart from that,

2 Measuring

the same conditions apply as for standard addition. However, this method
is rarely used.

2.5

Cleaning the electrode

Rinse the electrode with distilled water after each measurement or titration. The surface must be kept clean at all times (do not touch).
Further cleaning steps are not necessary as a rule.

2.6

ISA/TISAB solutions
The following table gives examples for possible ISA/TISAB solutions:

Measuring
ion

ISA/TISAB

For 100 mL of solution

Ag+

KNO3 1 mol/L

10.11 g

Br

KNO3 1 mol/L

10.11 g

Remarks

or
NaNO3 2 mol/L

17.00 g

Ca2+

KCl 1 mol/L

7.46 g

Cd2+

KNO3 1 mol/L

10.11 g

Cl

KNO3 1 mol/L

10.11 g

or
KNO3

5.06 g

Ammonium acetate

3.85 g

Glacial acetic acid

2.8 mL

or
NaNO3 2 mol/L

17.00 g

CN

NaOH 0.1 mol/L

0.40 g

Cu2+

KNO3 1 mol/L

10.11 g

NaCl

5.84 g

Glacial acetic acid

5.75 mL

Trans-1,2-diaminocyclohexaneN,N,N',N'-tetraacetic acid monohydrate (CDTA, Komplexon IV)

0.45 g

S2 interferes.

AB 82

2.6 ISA/TISAB solutions

Measuring
ion

ISA/TISAB

For 100 mL of solution

KNO3 1 mol/L

10.11 g

Remarks

or
NaNO3 2 mol/L

17.00 g

K+

NaCl 0.1 - 1 mol/L

0.584 - 5.844 g

Na+ (G)

Tris(hydroxymethyl)aminomethane [(HOH2C)3CNH2] 1 mol/L

12.11 g

or
Triethanolamine
Na+ (P)

CaCl2 1 mol/L

Set to between pH
8 and pH 10 using
HNO3 (AB 83).

7.50 mL
14.70 g

AB 83

CaCl22 H2O
NO3

[(NH4)2SO4] 1 mol/L

13.21 g

or
[Al2(SO4)3] 0.1 mol/L

3.42 g

Pb2+

NaClO4H2O 1 mol/L

14.05 g

At low Pb2+ concentrations, set to

between pH 5 and
pH 9

S2

NaOH 2 mol/L

8.00 g

pH 13

SCN

KNO3 1 mol/L

10.11 g

or
Acetate buffer pH = 6,
CH3COOtot 1 mol/L
Abbreviations used:
AB: Metrohm Application Bulletin
Na+ (G): Glass membrane electrode
Na+ (P): Polymer membrane electrode

3 Storing electrodes

3 Storing electrodes
Electrode

Type

Storage
For short periods

For longer periods

Ag+

dry

dry, with protective cap

Br

KBr 0.1 mol/L

dry, with protective cap

Ca2+

CaCl2 0.01 mol/L

dry, in the storage vessel*)

Cd2+

Cd(NO3)2 0.1 mol/L

dry, with protective cap

Cl

NaCl 0.1 mol/L

dry, with protective cap

CN

dry, with protective cap

dry, with protective cap

Cu2+

Cu(NO3)2 0.1 mol/L

dry, with protective cap

NaF 0.1 mol/L

dry, with protective cap

KI 0.1 mol/L

dry, with protective cap

K+

KCl 0.1 mol/L

Unscrew the electrode tip and

store in the provided vessel.

Na+ (G)

NaCl 0.1 mol/L

dry, in the storage vessel

Na+ (P)

dry

dry, in the storage vessel

NO3

KNO3 0.01 mol/L

Unscrew the electrode tip and

store in the provided vessel.

Pb2+

dry

dry, with protective cap

S2

dry

dry, with protective cap

SCN

dry

dry, with protective cap

*) A small amount of residual moisture on the electrode helps keep the reference electrode
operational.
Abbreviations used:
G: Glass membrane electrode
C: Crystal membrane electrode
P: Polymer membrane electrode

4.1 Problems with the reference electrode

4 Troubleshooting
The following malfunctions could occur:

Measuring signal is unstable

Sluggish response time ("running" measured value)
Insufficient electrode slope
Shifting of the electrode zero point (E(0))
Reduced linearity range

These problems may arise with the reference electrode or the ion-selective
electrode.

4.1

Problems with the reference electrode

4.2

Problems with the ion-selective crystal membrane

electrode

10

Is sufficient bridge electrolyte filled in?

Are there any air bubbles in the bridge electrolyte?
Loosen the ground-joint diaphragm and clean it in order to increase
the bridge electrolyte flow.
Is the electrode cable screwed on and plugged in correctly?
Is the electrode cable defective?
Did you wait long enough after exchanging the bridge electrolyte?

Polishing the sensor surface according to Chapter 2.1.1, page 4.

Eliminating or masking electrode poisons (see Chapter 4.5, page 11).
Is the electrode cable screwed on and plugged in correctly?
Is the electrode cable defective?
The sensor surface might be destroyed. Use a new electrode.

4.3

4 Troubleshooting

Problems with the ion-selective polymer membrane

electrode

4.4

Application-related problems

4.5

Do not use any organic solvents.

Other components that could destroy the sensor surface must be eliminated from the sample.
Eliminating or masking electrode poisons (see Chapter 4.5, page 11).
Is the electrode cable screwed on and plugged in correctly?
Is the electrode cable defective?
The sensor surface might be destroyed. Use a new electrode tip or a
new electrode.
The electrode might be too old (ionophore leached out). Use a new
electrode tip or a new electrode.

Has the sensor been conditioned long enough?

Did you wait until the measuring signal was stable before reading off
the values?
Are the ISA/TISAB solutions fresh?

Interfering ions
The concentrations in mol/L of the interfering ions, which generate an
analysis error of approximately 10%, are specified in the following table.

Measuring ion

Interferences

Ag+

Hg2+ must be absent. Proteins should also be absent.

Br

Hg2+ must be absent.

c(OH) < 310; c(Cl) < 4101; c(I) < 2107; c(S2) < 109; c(CN) < 8108;
c(NH3) < 2103; c(S2O32) < 2102

Ca2+

c(Na+) < 0.26; c(Pb2+) < 5.3106; c(Fe2+) < 6.7105; c(Zn2+) < 2.6106;
c(Cu2+) < 6.7105; c(Mg2+) < 8.3103

Cd2+

Ag+, Hg2+ and Cu2+ must be absent.

Fe3+ and Pb2+ interfere if their concentration is higher than the concentration of the
measuring ion.

Cl

Hg2+ must be absent.

c(OH) < 8102; c(Br) < 3106; c(I) < 51010; c(S2) < 109; c(CN) < 21010;
c(NH3) < 104; c(S2O32) < 105

11

4.5 Interfering ions

Measuring ion

Interferences

CN

Substances that complex with S2 and Ag+ must be absent.

c(Cl) < 103; c(Br) < 5; c(I) < 104

Cu2+

Ag+, Hg2+ and S2 must be absent.

Cl, Br, I, Fe3+ and Cd2+ interfere if their concentration is higher than the concentration of the measuring ion.

c(OH) < 104

Hg2+ must be absent.

c(Cl) < 103; c(Br) < 5; c(S2) < 109; c(CN) < 4104; c(S2O32) < 102

K+

c(Na+) < 5101; c(TRIS+) < 0.1; c(Li+) < 1; c(NH4+) < 3.3103; c(Cs+) < 104;
c(H+) < 102

Na+ (G)

pH > 4; c(Li+) < 5102; c(K+) < 0.1; c(Rb+) < 3; c(NH4+) < 3; c(Ag+) < 3107

Na+ (P)

SCN and organic lipophile ions (e.g. acetate) should be absent.

c(K+) < 0.15; c(Li+) < 1; c(Ca2+) < 1; c(Mg2+) < 1; c(NH4+) < 1; c(H+) < 1

NO3

c(Br) < 7104; c(NO2) < 7104; c(SO42) < 1; c(Cl) < 2.5102; c(F) < 1;
c(CH3COO) < 0.1

Pb2+

Ag+, Hg2+ and Cu2+ must be absent.

Fe3+ and Cd2+ interfere if their concentration is higher than the concentration of the
measuring ion.

S2

Hg2+ must be absent. Proteins should also be absent.

SCN

c(OH) < 101; c(Cl) < 2102; c(Br) < 3106; c(I) < 109;
c(S2) < 109; c(CN) < 7106; c(S2O32) < 1.3

Abbreviations used:
Na+ (G): Glass membrane electrode
Na+ (P): Polymer membrane electrode

12

5 Technical specifications

5 Technical specifications
5.1

Measured data

Electrode

Type

Measuring
range [mol/L]

Reproducibility

pH range

Temperature
range [C]

Membrane
resistance
[M]

Ag+

1107 - 1

2%

2-8

0 - 80

Br

5106 - 1

2%

0 - 14

0 - 50

0.1

Ca2+

5107 - 1

4%

2 - 12

0 - 40

1-4

Cd2+

1107 - 101

4%

2 - 12 (recommended pH
7)

0 - 80

Cl

5105 - 1

2%

0 - 14

0 - 50

0.1

CN

8106 - 102

2%

10 - 14
(HCN is
present at
pH < 10)

0 - 80

30

Cu2+

1108 - 101

4%

2 - 12 (recommended pH
6)

0 - 80

1106 - sat.

2%

5-7

0 - 80

0.15 - 0.2

5108 - 1

2%

0 - 14

0 - 50

0.1

K+

1106 - 1

2%

2.5 - 11

0 - 40

10 - 20

Na+

1105 - 1

2%

5-9

0 - 80

300

Na+

1106 - 1

2%

3 - 12

0 - 40

< 50

NO3

7106 - 1

2%

2.5 - 11

0 - 40

1-5

Pb2+

1106 - 101

4%

4-7

0 - 80

S2

1107 - 1

2%

2 - 12

0 - 80

SCN

5106 - 1

2%

2 - 10 (recommended pH
4)

0 - 50

0.1

13

5.2 Lifetime of polymer membrane electrodes

Abbreviations used:
G: Glass membrane electrode
C: Crystal membrane electrode
P: Polymer membrane electrode

5.2

Lifetime of polymer membrane electrodes

The average service life in regular laboratory use is approx. half a year.
CAUTION

The chemical properties of the ion-exchange substances embedded in

the membrane limit the storage life. Do therefore not stock up on these
electrodes and do not store them for too long.

14

Glossary

Glossary
Activity coefficient
The activity coefficient yi is a measure for the nonideal behavior of a solution. It can be calculated approximately and is valid up to about
c < 0.1 mol/L. The activity coefficient depends on the solvent, the temperature, the ionic strength and the effective size of the hydrated ion.
Ag/AgCl reference system
The reference system consists of silver, silver chloride and a KCl solution,
usually KCl 3 mol/L.
Calibration curve
The calibration curve shows the measured potential U as a function of the
logarithm of the ion activity. The following diagram shows the calibration
curve of a fluoride ISE (note the negative slope of the calibration curve,
which is due to the ion charge z of F = 1!):
U / mV

100 mV

log ai
-7

Figure 1

-6

-5

-4

-3

-2

-1

Calibration curve of a fluoride ISE

For low ion concentrations, the curve is nonlinear, which means that in
this range the electrode responds not only to the measuring ion but also
to interfering ions (e.g. to OH for the fluoride ISE).
Cross-sensitivity
See interfering ions.

15

Double-junction electrode
Electrode which contains another electrolyte solution (so-called bridge
electrolyte solution) between the sample solution and the reference system. For an example of a double-junction electrode, see figure page 3.
Electrode slope
The potential U of ion-selective electrodes depends on the activity ai of
free ions in the solution. This relation is described by the Nernst equation
as follows:

U = U0 +

2.303RT
log ai = U 0 + U N log ai
z i F

U0:

Standard potential of the measuring chain

R:

Gas constant (8.31441 JK1mol1)

T:

Absolute temperature

zi:

Charge of the measuring ion i (including sign)

F:

Faraday constant (96,484.56 Cmol1)

ai:

Activity of the measuring ion

UN:

Nernst slope

The electrode slope depends on the charge of the ion (including its sign)
as well as on the temperature.
Electrolyte solution
Solution with electric conductivity.
Interfering ions
Ion-selective electrodes often respond to other ions besides the measuring
ion (cross-sensitivity). The lower the concentration of the measuring ion,
the greater the interference of such ions. In cases of low measuring ion
concentrations, the calibration curve is no longer linear.
Ion activity, ion concentration
Many of the laws that apply to solutions lose their validity with rising ion
concentrations ci. These equations are again applicable to the ion activity
if the activity coefficient yi is taken into account. Activity ai and concentration ci of the ion i in solutions containing only free ions are related as follows:

ai = yi ci

16

Glossary

Ion-selective electrodes respond only to ion activities. For low concentrations, yi 1 applies, which means that concentration and activity are
equal.
Ionic strength
A measure for interionic interactions in a solution. The ionic strength I
depends on the concentration ci and the charge zi of the ions:

1
I=
2

ci z i2
i

TISAB
This abbreviation stands for Total Ionic Strength Adjustment Buffer and
designates a buffer solution with high ionic strength that maintains the
ionic strength of a sample solution as well as its pH value at a constant
level. TISAB solutions are mainly used for measurements using calibration
curves.

17

Index

Index
A
Activity coefficient .................... 15
Ag/AgCl reference system ......... 15

Electrode design ......................... 1

Electrode slope ......................... 16
Error search .............................. 10

C
Calibration curve ...................... 15
Cross-sensitivity .................. 11, 15

I
Interfering ions ................... 11, 16
Ion activity ................................ 16
Ion concentration ..................... 16

D
Design of the electrodes ............. 1
Direct measurement ................... 6
Double-junction electrode ........ 16
E
Electrode
Clean .................................... 7
Prepare ................................. 4
Store .................................... 9

18

M
Measured data ......................... 13
N
Nernst slope ............................. 16
P
Polymer membrane electrode
Lifetime .............................. 14

R
Reference electrode .................... 2
S
Standard addition ....................... 6
T
Technical specifications ............ 13
TISAB ................................... 7, 17
Titration ..................................... 5
Troubleshooting
Applications ....................... 11
Crystal membrane electrode
........................................... 10
Polymer membrane electrode
........................................... 11
Reference electrode ............ 10