Beruflich Dokumente
Kultur Dokumente
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
Manual
Table of contents
1 Introduction 1
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 4
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 9
4 Troubleshooting 10
4.1 Problems with the reference electrode ............................ 10
4.2 Problems with the ion-selective crystal membrane elec-
trode .................................................................................... 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
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■■■■■■■■■■■■■■■■■■■■■■ 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 deliv-
ery). 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.
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1.3 Reference electrodes ■■■■■■■■■■■■■■■■■■■■■■
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■■■■■■■■■■■■■■■■■■■■■■ 1 Introduction
after an exchange of electrolyte, the sensor requires some time until the
system is stable again.
3 Ground-joint diaphragm
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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
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■■■■■■■■■■■■■■■■■■■■■■ 2 Measuring
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.
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2.3 Direct measurement with calibration ■■■■■■■■■■■■■■■■■■■■■■
NOTE
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■■■■■■■■■■■■■■■■■■■■■■ 2 Measuring
the same conditions apply as for standard addition. However, this method
is rarely used.
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2.6 ISA/TISAB solutions ■■■■■■■■■■■■■■■■■■■■■■
Abbreviations used:
AB: Metrohm Application Bulletin
Na+ (G): Glass membrane electrode
Na+ (P): Polymer membrane electrode
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■■■■■■■■■■■■■■■■■■■■■■ 3 Storing electrodes
3 Storing electrodes
Electrode Type Storage
For short periods For longer periods
Ag+ C dry dry, with protective cap
Br– C KBr 0.1 mol/L dry, with protective cap
Ca2+ P CaCl2 0.01 mol/L dry, in the storage vessel*)
Cd2+ C Cd(NO3)2 0.1 mol/L dry, with protective cap
Cl– C NaCl 0.1 mol/L dry, with protective cap
CN– C dry, with protective cap dry, with protective cap
Cu2+ C Cu(NO3)2 0.1 mol/L dry, with protective cap
F– C NaF 0.1 mol/L dry, with protective cap
I– C KI 0.1 mol/L dry, with protective cap
K+ P KCl 0.1 mol/L Unscrew the electrode tip and
store in the provided vessel.
Na+ (G) G NaCl 0.1 mol/L dry, in the storage vessel
Na+ (P) P dry dry, in the storage vessel
NO3– P KNO3 0.01 mol/L Unscrew the electrode tip and
store in the provided vessel.
Pb2+ C dry dry, with protective cap
S2– C dry dry, with protective cap
SCN– C 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
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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.
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■■■■■■■■■■■■■■■■■■■■■■ 4 Troubleshooting
Measur- Interferences
ing ion
Ag+ Hg2+ must be absent. Proteins should also be absent.
Br– Hg2+ must be absent.
c(OH–) < 3·10; c(Cl–) < 4·10–1; c(I–) < 2·10–7; c(S2–) < 10–9; c(CN–) < 8·10–8;
c(NH3) < 2·10–3; c(S2O32–) < 2·10–2
Ca2+ c(Na+) < 0.26; c(Pb2+) < 5.3·10–6; c(Fe2+) < 6.7·10–5; c(Zn2+) < 2.6·10–6;
c(Cu2+) < 6.7·10–5; c(Mg2+) < 8.3·10–3
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–) < 8·10–2; c(Br–) < 3·10–6; c(I–) < 5·10–10; c(S2–) < 10–9; c(CN–) < 2·10–10;
c(NH3) < 10–4; c(S2O32–) < 10–5
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4.5 Interfering ions ■■■■■■■■■■■■■■■■■■■■■■
Measur- Interferences
ing ion
CN– Substances that complex with S2– and Ag+ must be absent.
c(Cl–) < 10–3; c(Br–) < 5; c(I–) < 10–4
Cu2+ Ag+, Hg2+ and S2– must be absent.
Cl–, Br–, I–, Fe3+ and Cd2+ interfere if their concentration is higher than the concen-
tration of the measuring ion.
F– c(OH–) < 10–4
I– Hg2+ must be absent.
c(Cl–) < 10–3; c(Br–) < 5; c(S2–) < 10–9; c(CN–) < 4·10–4; c(S2O32–) < 102
K+ c(Na+) < 5·10–1; c(TRIS+) < 0.1; c(Li+) < 1; c(NH4+) < 3.3·10–3; c(Cs+) < 10–4;
c(H+) < 10–2
Na+ (G) pH > 4; c(Li+) < 5·10–2; c(K+) < 0.1; c(Rb+) < 3; c(NH4+) < 3; c(Ag+) < 3·10–7
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–) < 7·10–4; c(NO2–) < 7·10–4; c(SO42–) < 1; c(Cl–) < 2.5·10–2; 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–) < 10–1; c(Cl–) < 2·10–2; c(Br–) < 3·10–6; c(I–) < 10–9;
c(S2–) < 10–9; c(CN–) < 7·10–6; c(S2O32–) < 1.3
Abbreviations used:
Na+ (G): Glass membrane electrode
Na+ (P): Polymer membrane electrode
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■■■■■■■■■■■■■■■■■■■■■■ 5 Technical specifications
5 Technical specifications
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5.2 Lifetime of polymer membrane electrodes ■■■■■■■■■■■■■■■■■■■■■■
Abbreviations used:
G: Glass membrane electrode
C: Crystal membrane electrode
P: Polymer membrane electrode
CAUTION
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■■■■■■■■■■■■■■■■■■■■■■ Glossary
Glossary
Activity coefficient
The activity coefficient yi is a measure for the nonideal behavior of a solu-
tion. It can be calculated approximately and is valid up to about
c < 0.1 mol/L. The activity coefficient depends on the solvent, the temper-
ature, the ionic strength and the effective size of the hydrated ion.
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 -6 -5 -4 -3 -2 -1 0
Cross-sensitivity
See interfering ions.
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Double-junction electrode
Electrode which contains another electrolyte solution (so-called bridge
electrolyte solution) between the sample solution and the reference sys-
tem. 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:
2.303·R·T
U = U0 + ·log ai = U 0 + U N ·log ai
z i ·F
U0: Standard potential of the measuring chain
R: Gas constant (8.31441 JK–1mol–1)
T: Absolute temperature
zi: Charge of the measuring ion i (including sign)
F: Faraday constant (96,484.56 Cmol–1)
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.
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■■■■■■■■■■■■■■■■■■■■■■ Glossary
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= · ci ·z i2
2 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.
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Index ■■■■■■■■■■■■■■■■■■■■■■
Index
A Electrode design ......................... 1 R
Activity coefficient .................... 15 Electrode slope ......................... 16 Reference electrode .................... 2
Ag/AgCl reference system ......... 15 Error search .............................. 10
S
C I Standard addition ....................... 6
Calibration curve ...................... 15 Interfering ions ................... 11, 16
Cross-sensitivity .................. 11, 15 Ion activity ................................ 16 T
Ion concentration ..................... 16 Technical specifications ............ 13
D TISAB ................................... 7, 17
Design of the electrodes ............. 1 M Titration ..................................... 5
Direct measurement ................... 6 Measured data ......................... 13 Troubleshooting
Double-junction electrode ........ 16 Applications ....................... 11
N Crystal membrane electrode
E Nernst slope ............................. 16 ........................................... 10
Electrode Polymer membrane electrode
Clean .................................... 7 P ........................................... 11
Prepare ................................. 4 Polymer membrane electrode Reference electrode ............ 10
Store .................................... 9 Lifetime .............................. 14
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