6 51724646 ISEdirecto e

METTLER TOLEDO Titrators
Na
+ K+
Cl - -
F- NO3
Direct Measurement
with Ion Selective Electrodes
Application brochure 6
Editorial
Dear Reader
Using ion selective electrodes (ISE) to determine ion contents, today’s analyst has a simple, reliable
and versatile method at hand.
It pleases us to present these applications to you. Using lots of examples, they will show you how you
can use the METTLER TOLEDO DX ion selective electrode series, together with titrators DL67 /
DL70ES / DL77, to solve many of your analysis tasks. This builds up on the many possibilities for
adapting methods offered by titrators DL67 / DL70ES / DL77. This, of course, together with the clear
user guidance offered by alphanumeric and grafic displays in plain language.
The applications examples are mostly taken from the area of foods and beverages. However, they also
represent samples from other areas such as chemicals, cosmetics and environmental protection.
Matrix effects and the influence of interfering ions (cross sensitivity) are explained. Hints for pre-
venting or reducing these are given wherever possible. Also included is a list of references which we
mention explicitly in this context.
A load of practical tips and hints are included with the individual measurements. These are summa-
rized in the chapter on trouble-shooting.
A further benefit of the use of ion selective electrodes is the minimal use of chemicals and the avoid-
ance of environmentally damaging wastes, ecologically as well as economically an important consid-
eration.
Unless the sample must be buffered, the method is also non-destructive.
The analyses were mostly performed with perserverance and success in our lab by Anke Stock, as a
part of the work required for her to attain her chemical engineering Masters degree.
Albert Aichert, Market Support AnaChem, included numerous additions and edited this brochure.
Many thanks to both authors.
A further brochure will describe the addition procedures also used in measurements with ion selective
electrodes.
We are convinced that the inclined reader, thanks to the broad scope of information, will soon feel at
ease using ion selective electrodes. The new tools should help him/her readily solve new problems.
We wish you lots of luck using ion selective electrodes together with our titrators .
Georg Reutemann Rolf M. Rohner

Manager Market Support Marketing Manager
Page 2 / 68 METTLER TOLEDO DL5x and DL7x Titrators Direct Measurement with Ion Selective Electrodes
Contents
1. Fluoride Selective Electrode ........................................................................................ 4

M101 Calibrating the Fluoride Electrode ............................................................................... 6
M102 Fluoride Determination with Fluoride Ion Selective Electrode ................................... 8
M071 Fluoride Determination in Water ............................................................................... 12
2. Chloride Selective Electrode...................................................................................... 14

M103 Calibrating the Chloride Electrode ............................................................................ 16
M104 Chloride Determination with Ion Selective Chloride Electrode ................................ 18
M105 Chloride Determination in Canned Vegetables .......................................................... 22
3. Nitrate Selective Electrode ........................................................................................ 24

M106 Calibrating the Nitrate Electrode ............................................................................... 26
M107 Automatic Three-point Calibration of the Nitrate Electrode ..................................... 28
M108 Nitrate Determination with Ion Selective Electrode .................................................. 30
M109 Nitrate Determination in Reference Samples ............................................................ 34
4. Potassium Selective Electrode ................................................................................... 36

M110 Calibration of the Potassium Electrode...................................................................... 38
M111 Potassium Determination with Ion Selective Electrode............................................. 40
5. Sodium Selective Electrode ....................................................................................... 44

M112 Calibration of the Sodium Electrode.......................................................................... 46
M113 Sodium Determination with Ion Selective Electrode................................................. 48
6. Trouble-shooting ........................................................................................................ 52
7. Summary of the Ion Selective Electrodes and Reagents Used .................................. 54
8. Literature .................................................................................................................... 56
9. Sample index ...............................................................................................................63
Direct Measurement with Ion Selective Electrodes METTLER TOLEDO DL5x and DL7x Titrators Page 3 / 68
1. Fluoride Selective Electrode
Theory The fluoride electrode is a solid state membrane electrode. The active electrode
phase is a nearly water insoluble lanthanide fluoride monocrystal which is in
direct contact with the measurement solution. The potential difference derived
from the equation
LaF3 ⇔ La+3 + 3 F- is conducted by the electrolyte and a noble metal wire.
The theoretical detection limit of the fluoride electrode is determined by the low
solubility of the LaF3 crystal (10-26). Using TISAB to adjust the pH value and the
ionic strength, linear calibration curves of 0.1 – 10-6 mol/L are attained; the
detection limit lies slightly higher than 10-7 mol/L. The slope, theoretically
calculated from the Nernst equation to be 58.16 mV at 20 °C, usually lies at
58 mV in practice.
Electrodes
Bridging electrolyte As bridging electrolyte for the reference electrode, a 1 mol/L KNO solution is
3
used.
Conditioning For the determination of concentrations under 1 mg/L, the electrode should be
conditionied in deionized water for approx. 30 minutes.
Storage Store electrodes dry or in a dilute fluoride solution. The electrolyte should not be
submerged for long in solutions containing TISAB, as the crystal surface is
damaged by complexing agents.
Handling The lanthanide fluoride crystal is sensitive to mechanical impact. Cracks and
scratches render the electrode useless. Avoid fat deposits on the crystal; do not
touch with bare fingers.
Contamination A sluggish or no response indicates that the sensor is contaminated. Deposits on
the crystal can be removed carefully by wiping with a soft tissue. Afterwards it
is advantageous to condition for several minuts in a dilute fluoride solution.
Repolish non-regenerable modules with an aqeous slurry of aluminum oxide or
with toothpaste.
Reagents
TISAB solutions: (Total Ionic Strength Adjustment Buffer)
METTLER TOLEDO TISAB 3 Art. No. 51 340 064 (mix 1:10 with sample)
MERCK TISAB I Art. No. 153668 (1:1 mix with sample), contains NaCl
TISAB III Art. No. 116770 (1:10 mix with sample), contains NH Cl
4
Self made In 700 mL deion. water are dissolved 58 g NaCl p.a. and 5 g CDTA (1,2-
diaminocyclohexane-N,N,N’,N’-tetraacetate, Titriplex IV from MERCK, No.
108424, or Complexon IV p.a.) by adding 5 mol/L NaOH solution.
Add 57 mL glacial acetic acid p.a and adjust to pH 5.5 using sodium hydrox-
ide c(NaOH) = 5 mol/L at 20 °C. Adjust volume to 1000 mL using deion wa-
ter. The pH value of this solution should be 5.3 (20 °C).
F- stock solution: Fluoride standard solution (potassium fluoride in water) 1.000 g ± 0.002 g F-
MERCK Art. No. 109869
Fill to 1000 mL with deion. water and decant to plastic bottle.
1 mL = 1 mg fluoride.
Appropriate standard solutions are made from this stock.
Remarks
pH Value At pH values under pH=5, HF and HF2- are formed. Both are not detected by the
fluoride electrode. At pH values over pH=8, La(OH)3 is formed and the electrode
responds increasingly to OH- ions.
Interfering ions Metal ions such as Al3+, Fe3+, Si4+, Ca2+, Fe2+, and other polyvalent ions form
complexes with fluoride, some of which are stable. The fluoride bound in this
manner can be released for determination by adding Complexon IV (found in
TISAB solution) for preferential complexing.
Ionic strength The total activity of calibration and measurement solutions must be constant. By
adding a constant amount of TISAB solution, the pH is buffered sufficiently and
the solution is adjusted to a constant ionic strength.
Samples Samples and standard solutions should be stored only in PE or PP bottles with
fluoride-saturated walls.
Glass utensils Any glass utensils used should first be rinsed with sodium hydroxide (0.01 mol/
L) to block glass against fluoride ions.
Deion. water The deion. water used to make solutions should be made basic using sodium
hydroxide. This prevents fluoride loss.
Application and Use

Application The fluoride electrode is used for fluoride determination in air, water, beverages,
foods, dental hygiene articles, organic compounds, vegetation, soil and rock
samples.
Use Direct measurement with an ion selective electrode is the method of choice for
fluoride determination. The high selectivity and large concentration range make
this method universally applicable .
Alternatives Ion chromatography.

Potentiometric titration using a fluoride electrode and lanthanide nitrate as
titrant at pH=6.
3 F- + La(NO3)3 = LaF3 + 3 NO3-
This method is applicable only for higher fluoride concentrations (more than
20 mg/L). It is rarely used in practice.
Advantages - wide application range (1000 - 0.01 mg/L)

- the determination is fast and simple
- no heavy metal wastes
- small investment (compared to ion chromatography)
Disadvantages none
METTLER TOLEDO
M101 Calibrating the Fluoride Electrode
Sample: 50 mL fluoride solution Instruments: METTLER TOLEDO DL70ES

10-1 g/L, 10-2 g/L, 10-4 g/L HP Deskjet 500 Printer
MT AT261 Balance
Substance: Fluoride
M = 18.998 g/mol , z = 1 Method: F007
Preparation: 5 mL TISAB III MERCK Accessories: Titration beaker ME-101974

DT120 (temp. sensor Pt100)
Titrant: --
Standard: -- Indication: DX219 Fluoride ISE

DX200 Reference electrode
(bridge electrolyte: 1 M KNO3)
Results: METTLER DL70ES Titrator V3.0 Mettler-Toledo AG

AA01 Market Support Laboratory
Method F007 Calibration F- -sensor 09-Nov-1993 17:46

User aa
Measured 10-Nov-1993 10:27
RESULTS
No ID1 ID2 Sample amount and results
1/1 10-4 g/L 50.0 mL pH,pM,pX 4.000

R1 = 158.267 mV Potential
1/2 10-2 g/L 50.0 mL pH,pM,pX 2.000
1/3 10-1 g/L 50.0 mL pH,pM,pX 1.000
R1 = -15.540 mV Potential
CALIBRATION
Sensor F--sensor
Buffer type pH,pM,pX
Zero point 1.269 pX0
Slope 57.94 mV/pX
Calibration temperature 21.7 °C
Method Remarks
Method F007 Calibration F--sensor
Version 09-Nov-1993 17:46 1) Calibration and measurement solutions should
Title always be at the same temperature.
Method ID . . . . . . . . . . . . . F007
Title . . . . . . . . . . . . . Calibration F--sensor
Date/time . . . . . . . . . . . . . 09-Nov-1993 17:46 2) All measurements should be performed using
Sample
Number samples . . . . . . . . . . 3 the same stirring conditions. This means the
Titration stand . . . . . . . . . . Stand 1
Entry type . . . . . . . . . . . . . Fixed volume U same speed, stirrer type, distance to electrode
Volume [mL] . . . . . . . . . . . 50.0
ID1 . . . . . . . . . . . . . . . . etc.
Molar mass M . . . . . . . . . . . . 0.0
Equivalent number z . . . . . . . . 1
Temperature sensor . . . . . . . . . TEMP A 3) The calibration parameters are automatically
Stir
Speed [%] . . . . . . . . . . . . . 50 stored in the installation data by the titrator.
Time [s] . . . . . . . . . . . . . . 300
Measure They are then referred to the sensor indicated
Sensor . . . . . . . . . . . . . . F--sensor
Unit of meas . . . . . . . . . . . . mV in the method and are applicable only for this
∆E [mV] . . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . . 2.0 sensor.
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . .
t(max) [s] . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
10.0
30.0
4) Up to 8 standard solutions can be used for the
Calculation
Result name . . . . . . . . . . . . Potential
calibration. If only one standard is used, the
Formula . . . . . .
Constant . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
R=E
titrator will correct only the zero point.
Result unit . . . . . . . . . . . . mV
Decimal places . . .
Calibration
. . . . . . . . 3 5) Rinse electrode with deion. water after each
Sensor . . . . . . .
Buffer type . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
F--sensor
pH,pM,pX
measurement and remove adhering water
First buffer . .
Second buffer . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
4.0
2.0
drops with a soft paper tissue.
Third buffer . . . . . . . . . . 1.0
Fourth buffer . . . . . . . . . . 0.0 6) It is necessary to stir for approx. 5 minutes each
Fifth buffer . . . . . . . . . . 0.0
Sixth buffer . . . . . . . . . . 0.0 measurement to attain a stable measured value.
Seventh buffer . . . . . . . . . 0.0
Eighth buffer . . . . . . . . . . 0.0
Ri (i=index) . . . . . . . . . . . . R1 7) For a three-point calibration with automatic
Minimal slope . . . . . . . . . . . 50.0
Maximal slope . . . . . . . . . . . 60.0 production of the standard solutions, see the
Record
Output unit . . . . . . . . . . . . Printer nitrate electrode.
All results . . . . . . . . . . . . Yes
Typical calibration curve of a fluoride selective electrode with TISAB solution
Disposal
--
Other titrators
DL50 Graphix, DL53/55/58, DL77 titrators. Author: Albert Aichert
METTLER TOLEDO
M102 Fluoride Determination with Fluoride Ion Selective Electrode
Sample: 50 mL sample solution with Instruments: METTLER TOLEDO DL70ES

1000 to 0.01 mg/L fluoride Printer (HP Desk Jet 500)
Substance: Fluoride Method: F00A, F00B

M = 18.998 g/mol , z = 1
Accessories: Titration beaker ME-101974
Preparation: 5 mL TISAB III MERCK DT120 (temp. sensor Pt100)
Titrant: - Indication: DX219 Fluoride ISE

Standard: - (bridge electrolyte: 1 M KNO3)
Repeatability and Recovery Rate
1. For these measurements, aqueous fluoride solutions from the fluoride standard solution (potas-
sium fluoride in water) 1.000 g± 0.0002 g fluoride, MERCK Art. No. 109869, were used.
2. The fluoride electrode was recalibrated at least once a day using 10 mg/L and 0.1 mg/L standard
solutions (sometimes necessary after 3-4 series).
3. Preparation: Add 5 mL TISAB III to 50 mL sample solution and measure.
Concentration Recovery srel from several series (n=6)

mg / L % Method A Method B
1000 100 - 105 % 0.09 - 0.20 % 0.15 - 0.26 %
100 100 - 103 % 0.06 - 0.20 % 0.11 - 0.20 %
10 99 - 101 % 0.13 - 0.26 % 0.18 - 0.24 %
1 98 - 100 % 0.15 - 0.31 % 0.19 - 0.36 %
0.1 99 - 102 % 0.15 - 0.45 % 0.27 - 0.51 %
0.05 97 - 101 % 0.10 - 0.84 % 0.12 - 0.91 %
0.01 155 - 181 % 0.38 - 4.6 % 0.42 - 2.47 %
Result:
Method (A) allows to obtain a a better repeatability, expressed as relative standard deviation srel.
However, the adjstment time prior to the measurement is crucial for good repeatability. At high
concentrations (1000 - 0.1 mg/L) the stirring time is 5 minutes. At low concentrations, longer times are
necessary: for 0.05 g/L approx. 10 minutes, and for 0.01 g/L approx. 20 minutes.
The concentration 0.01 mg/L is not in the linear range (see calibration curve page 7). The range of
concentrations for fluoride sensitive electrodes was therefore limited from 100 to 0.05 mg/L.
Method A Method B
Method F00A F--content Method F00B F--content
Version 10-Sep-1993 16:05 Version 16-Sep-1993 10:21
Title Title
Method ID . . . . . . . . . . . . . F00A Method ID . . . . . . . . . . . . . F00B
Title . . . . . . . . . . . . . F--content Title . . . . . . . . . . . . . F--content
Date/time . . . . . . . . . . . . . 10-Sep-1993 16:05 Date/time . . . . . . . . . . . . . 16-Sep-1993 10:21
Sample Sample
Number samples . . . . . . . . . . 6 Number samples . . . . . . . . . . 6
Titration stand . . . . . . . . . . Stand 1 Titration stand . . . . . . . . . . Stand 1
Entry type . . . . . . . . . . . . . Fixed volume U Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . . . . . . 50.0 Volume [mL] . . . . . . . . . . . 50.0
ID1 . . . . . . . . . . . . . . . . ID1 . . . . . . . . . . . . . . . . F-
Molar mass M . . . . . . . . . . . . 0.0 Molar mass M . . . . . . . . . . . . 18.99840
Equivalent number z . . . . . . . . 1 Equivalent number z . . . . . . . . 1
Temperature sensor . . . . . . . . . TEMP A Temperature sensor . . . . . . . . . TEMP A
Stir Stir
Speed [%] . . . . . . . . . . . . . 50 Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 300 Time [s] . . . . . . . . . . . . . . 300
Measure Measure
Sensor . . . . . . . . . . . . . . F--sensor Sensor . . . . . . . . . . . . . . F--sensor
Unit of meas . . . . . . . . . . . . As installed Unit of meas . . . . . . . . . . . . As installed
∆E [mV] . . . . . . . . . . . . . . 0.2 ∆E [mV] . . . . . . . . . . . . . . 0.3
∆t [s] . . . . . . . . . . . . . . 5.0 ∆t [s] . . . . . . . . . . . . . . 2.0
t(min) mode . . . . . . . . . . . . Fix t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . . . . . . 10.0 t(min) [s] . . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . . . . 90.0 t(max) [s] . . . . . . . . . . . . . 30.0
Measure Calculation
Sensor . . . . . . . . . . . . . . F--sensor Result name . . . . . . . . . . . .
Unit of meas . . . . . . . . . . . . mV Formula . . . . . . . . . . . . . . R=E
∆E [mV] . . . . . . . . . . . . . . 0.2 Constant . . . . . . . . . . . . . .
∆t [s] . . . . . . . . . . . . . . 2.0 Result unit . . . . . . . . . . . . p(F-)
t(min) mode . . . . . . . . . . . . Fix Decimal places . . . . . . . . . . . 4
t(min) [s] . . . . . . . . . . . 1.0 Calculation
t(max) [s] . . . . . . . . . . . . . 2.0 Result name . . . . . . . . . . . . F--content
Measure Formula . . . . . . . . . . . . . . R2=pw(-E)*1000*f
Sensor . . . . . . . . . . . . . . F--sensor Constant . . . . . . . . . . . . . .
Unit of meas . . . . . . . . . . . . mV Result unit . . . . . . . . . . . . mg/L
∆E [mV] . . . . . . . . . . . . . . 0.2 Decimal places . . . . . . . . . . . 3
∆t [s] . . . . . . . . . . . . . . 2.0 Statistics
t(min) mode . . . . . . . . . . . . Fix Ri (i=index) . . . . . . . . . . . . R2
t(min) [s] . . . . . . . . . . . 1.0 Standard deviation s . . . . . . . . Yes
t(max) [s] . . . . . . . . . . . . . 2.0 Rel. standard deviation srel . . . . Yes
Measure Outlier test . . . . . . . . . . . . Yes
Sensor . . . . . . . . . . . . . . F--sensor Record
Unit of meas . . . . . . . . . . . . mV Output unit . . . . . . . . . . . . Printer
∆E [mV] . . . . . . . . . . . . . . 0.2 All results . . . . . . . . . . . . Yes
∆t [s] . . . . . . . . . . . . . . 2.0
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . . . . . . 1.0
t(max) [s] . . . . . . . . .
Measure
Sensor . . . . . . . . . .
.
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2.0
F--sensor
Remarks
Unit of meas . . . . . . . . . . . . mV
∆E [mV] . . . . . . . . . . . . . . 0.2
∆t [s] . . . . . . . . . . . . . . 2.0
t(min) mode . . . . . . . .
t(min) [s] . . . . . . .
.
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.
Fix
1.0
Method A
t(max) [s] . . . . . . . . . . . . . 2.0
Measure
Sensor . . . . . . . . . . . . . . F--sensor
1) Stirring during 5 minutes.
Unit of meas . . . . . . . . . . . . mV
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
.
.
.
.
.
.
.
.
0.2
2.0
2) Acquisition of six values (six Measure-func-
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . . . . . . 1.0 tions) at an interval of 1-2 s.
t(max) [s] . . . . . . . . . . . . . 2.0
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
. R1=E[1]
3) The fluoride concentration is calculated from
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
. p(F-) the mean of these six values.
Decimal places . . . . . . . . . . . 4
Calculation
Result name . . . . . . . . . . . . F--single
Formula . . . . . . . . . . . . . . R2=pw(-E[1])*1000
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
.
.
.
.
.
.
.
.
mg/L
4
Method B
Calculation
Result name . . . . . . . . . . . . 1) Stirring during 5 minutes.
Formula . . . . . . . . . . . . . . R3=(C3+E[5]+E[6])/6
Constant . . . . . . . . . . . . . . C3=E[1]+E[2]+E[3]+E[4]
Result unit . . . . . . . .
.
.
.
.
.
.
.
. 3
2) Acquisition of one value.
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
F--x of 6
R4=pw(-R3)*1000
3) If the sample is diluted for the measurement,
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mg/L the dilution factor can be entered as a correc-
Decimal places . . . . . . . . . . . 4
Statistics
Ri (i=index) . . . . . . . . . . . . R2
tion factor (f) for each sample. This will be
Standard deviation s . . . .
Rel. standard deviation srel
.
.
.
.
.
.
.
.
Yes
Yes used in the calculation.
Outlier test . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R4
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Outlier test . . . . . . . .
Record
Output unit . . . . . . . .
. . . .
. . . . Printer
Yes
Disposal
All results . . . . . . . . . . . . Yes
--
Other titrators
DL53+, DL55+, DL58, DL77 titrators. Author: Albert Aichert
Results
Sample Direct measurement with ISE Nominal content

-
(number) F content srel (Producer specification)
Drinking water 0.056 mg/L 0.79 % not over 1.5 mg/L *

(n = 5)
Snow 0.0066 mg/L 14.9 % none given

(n = 5)
Mineral water 0.109 mg/L 0.5 % 0.13 mg/L

(n = 5) (analysis 1983)
Wine 0.176 mg/L 2.0 % none given

(n = 5)
Milk 0.023 mg/L 2.1 % none given

(n = 3)
Table salt 233 mg/kg 1.2 % 250 mg/kg

(n = 10) ± 20 %
Toothpaste 0.117 % 0.9 % 0.113 %

(n = 2)
Fluoride tablet 1.064 mg/tab. 2.4 % 1 mg / tablet

(n = 5)
Mouth wash 236 mg/kg 0.27 % 220 mg/kg

(n = 5)
th
* Obtained from: Schweizerisches Lebensmittelbuch, 5 Edition, Table 8.
Sample Preparation and Remarks
Drinking water To 50 mL add 5 mL TISAB III solution and measure.

For this determination, a calibration with concentrations 0.1 and 0.05 mg/L
was performed. The stir time before measuring is 10 minutes. Fluoride con-
tents above 1.5 mg/L can be damaging to the health.
Snow Melt snow. To 50 mL add 5 mL TISAB III solution and measure.For this
determination, a calibratiion with concentrations 0.01 and 0.005 mg/L was
undertaken. The stir time before measuring is 15 minutes.
Mineral water To 50 mL add 5 mL TISAB III solution and measure.
Wine To 50 mL add 5 mL TISAB III solution and measure.
Milk To 50 mL add 5 mL TISAB III solution and measure.

Before measuring, the sample was stirred rapidly (75%) for 4 minutes to
disperse fat droplets.
Remove fat residues from electrode after each measurement.
Table salt Dissolve 20 g table salt in 100 mL deion. water and measure.
The same amount of table salt (fluoride free) was added to the calibration
solutions.
Toothpaste Stir 2.5 g in 50 mL deion. water thoroughly. Add 5 mL TISAB III solution
and measure.
Clean electrode after each measurement because the toothpaste sticks to the
menbrane. Calibrate prior to each measurement series since the cleaning in-
fluences the electrode.
Mouthwash Dilute 10 mL sample with 40 mL deion. water, add 5 mL TISAB III solu-
tion and measure.
General Remarks:
1. All measurements were performed using the simple direct method (B).
2. Rinse electrode with deion. water after each measurement and remove clinging water drops with
a soft paper tissue.
3. All measurements should be performed using the same stirring conditions. This means the same
speed, stirrer type, distance to electrode etc.
METTLER TOLEDO
M071 Fluoride Determination in Water
Sample: 50 mL drinking water Instruments: METTLER TOLEDO DL70ES

"Schwerzenbach" HP Deskjet 500 Printer
Sample changer ST20A
Substance: Fluoride
M = 18.998 g/mol , z = 1 Method: F00W
Preparation: 5 mL TISAB III MERCK Accessories: Titration beaker ME-101974

Titrant: Fluoride solution 1.0 mg/L 1 additional burette drive DV90
1 peristaltic pump
Standard: --
Indication: DX219 Fluoride ISE
Results:
METTLER DL70ES Titrator V3.0 Mettler-Toledo AG
Method F00W Auto.Calib+conc.det of F- 22-Nov-1993 12:49

User aa
Measured 22-Nov-1993 13:05
RESULTS
1/1 5*10-5 g/L 50.0 mL pH,pM,pX 4.301

1/2 10-4 g/L 50.0 mL pH,pM,pX 4.000
2/1 Water tap 50.0 mL Fixed volume U
R2 = 4.113 pX F- Potential
R3 = 0.0772 mg/L F--content
2/2 Water 50.0 mL Fixed volume U
CALIBRATION
Sensor F--sensor
Slope 48.37 mV/pX
STATISTICS
Number results R3 n = 4
Mean value x = 0.0773 mg/L F--content
Standard deviation s = 0.000254 mg/L F--content
Rel. standard deviation srel = 0.329 %
Method Remarks
Method F00W Auto.Calib+conc.det of F-
Version 22-Nov-1993 12:49 1) The calibration and fluoride concentration de-
Title
Method ID . . . . . . . . . . . . . F00W
termination of each sample is automatically per-
Title . . . . . . . . .
Date/time . . . . . . . . .
. . . . Auto.Calib+conc.det of F-
. . . . 22-Nov-1993 12:49
formed in a method.
Auxiliary value
ID text . . . . . . . . . .
Formula . . . . . . . . . .
. . . . Counter
. . . . H10=1 2) The standard solutions 0.1 and 0.05 mg F-/L for the
Sample
Number samples . . . . . . . . . . 2 calibration were made by dispensing fluoride solu-
Titration stand . . . . . . . . . . ST20 1
Entry type . . . . . . . . . . . . . Fixed volume U tion (1 mg/L) and TISAB solution into 50 mL
Volume [mL] . . . . . . . . . . . 50.0
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
.
.
.
.
.
.
.
. 0.0
deion. water.
Equivalent number z . . . . . . . . 1
Temperature sensor . . . . .
Dispense
. . . . TEMP A 3) Subsequently, the fluoride concentrations of the
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
. . . . F--solution
. . . . 1.0 water samples are measured. The 5 mL TISAB so-
Volume [mL] . . . . . . . . . . . . H10*0.251256
Dispense lution were dispensed using the function DIS-
Titrant . . . . . . . . . . . . . . TISAB
Concentration [mol/L] . . . . . . . 1.0 PENSE.
Volume [mL] . . . . . . . . . . . . (H10*0.0251256)+5.0
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 50
. . . . 900
4) Between calibration and measurement, the elec-
Measure
Sensor . . . . . . . . . . . . . . F--sensor
trode is conditioned for 5 minutes in deion. water to
Unit of meas . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
.
.
mV
0.5
prevent contamination with fluoride ions.
∆t [s] . . . . . . . . . . . . . . 2.0
t(min) mode . . . . . . . .
t(min) [s] . . . . . . .
.
.
.
.
.
.
.
.
Fix
10.0 5) The measurement requires the following succes-
t(max) [s] . . . . . . . . . . . . . 30.0
Calculation sion of beakers on the sample changer ST20A:
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R=E
5.1 Two beakers with 50.0 mL deion. water for
Result unit . . . . . . . . . . . . mV
Decimal places . . . . . . . . . . . 3 the calibration,
Calibration
Sensor . . . . . . . . . . .
Buffer type . . . . . . . .
.
.
.
.
.
.
.
.
F--sensor
pH,pM,pX
5.2 One beaker with deion. water for condition-
First buffer . . . . . .
Second buffer . . . . . .
.
.
.
.
.
.
.
.
4.301
4.0
ing,
Third buffer . . . . . .
Fourth buffer . . . . . .
.
.
.
.
.
.
.
.
0.0
0.0
5.3 At the end, a beaker with deion. water (red
Fifth buffer . . . . . .
Sixth buffer . . . . . .
.
.
.
.
.
.
.
.
0.0
0.0 stopper), so that the electrode comes to rest in
Seventh buffer . . . . . . . . . 0.0
Eighth buffer . . . . . . . . . . 0.0 deion. water (The electrode should not re-
Ri (i=index) . . . . . . . . . . . . R1
Minimal slope . . . . . . .
Maximal slope . . . . . . .
.
.
.
.
.
.
.
.
40.0
60.0
main submerged in solutions containing TI-
Record
Output unit . . . . . . . . . . . . Printer
SAB for a long time).
Raw results last sample . . . . . . Yes
All results . . . . . . . . . . . . Yes
Conditioning
Interval . . . . . . . . . . . . . . 1
Sample Mean / mg/L srel / % Remarks
Time [s] . . . . . . . . . .
Sample
. . . . 300
n=
Number samples . . . . . . . . . . 5
Titration stand . . . . . . . . . . ST20 1
Entry type . . . . . . . . . . . . . Fixed volume U Drinking water 0.0773 0.33 % Sampling:
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
.
.
.
.
.
.
.
.
50.0
Water
“Schwerzenbach” 4 22.11.93
Molar mass M . . . . . . . . . . . . 100.0
Equivalent number z . . . . . . . . 1 Drinking water 1.067 0.23 % Sampling:
Temperature sensor . . . . . . . . . TEMP A
Dispense “Basel” 4 3.12.93
Titrant . . . . . . . . . . . . . . TISAB
Concentration [mol/L] . . . . . . . 1.0 (enriched
Volume [mL] . . . . . . . .
Stir
. . . . 5.0
with F-)
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . .
Measure
. . . . 600
River water 0.0669 0.51 % Sampling:
Sensor . . . . . . . . . . . . . . F--sensor “Töss” 3 11.10.93
Unit of meas . . . . . . . . . . . . mV
∆E [mV] . . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . . 2.0
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . . . . . . 10.0 Spring water 0.0748 1.03 % Sampling:
t(max) [s] . . . . . . . . . . . . . 30.0
Rinse “Bachtel” 4 28.11.93
Auxiliary reagent . . . . . . . . . H2O
Volume [mL] . . . . . . . . . . . . 10.0
Calculation
Formula . . . . . . . . . . . . . . R2=E[2]
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
. pX F-
Other titrators
Decimal places . . . . . . . . . . . 3
Calculation
Result name . . . . . . . . . . . . F--content
DL55+, DL58, DL77 titrators.
Formula . . . . . . . . . . . . . . R3=pw(-R2)*1000
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mg/L
Decimal places . . . . . . . . . . . 4
Statistics
Ri (i=index) . . . . . . . . . . . . R3
Outlier test . . . . . . . .
Record
. . . . Yes
Disposal
All results . . . . . . . . . . . . Yes
--
Author: Albert Aichert

2. Chloride Selective Electrode
Theory The chloride electrode has a solid state membrane composed of a pressed Ag2S
and AgCl composite. The active electrode phase is a nearly water insoluble solid
membrane pasted in the electrode adapter. It is in direct contact with the solution
to be measured.
Measurement range The measurement range of a pressed Ag2S and AgCl composite electrode is
limited by the relatively high solubility product of AgCl (2•10-10). Deviations
from the Nernst equation are already observed at chloride concentrations under
2• 10-5 mol/L.
Using ISA to adjust the ionic strength, linear calibration curves were attained
from 1.0 - 5•10-5 mol/L; the detection limit lies somewhat above 10-6 mol/L. The
slope, theoretically calculated from the Nernst equation to be 58.16 mV at 20°C,
lies at 58 mV in practice.
Electrodes
Bridge electrolyte The bridge electrolyte for the reference electrode is KNO3 (1 mol/L).
Storage Store electrode dry or in deion. water.
The electrode should not be submerged for long in concentrated chloride-
containing solutions because the crystal membrane surface will be damaged.
Handling The solid membrane is sensitive to mechanical impact. Cracks and scratches
render the electrode useless. Avoid fat deposits on the crystal; do not touch with
bare fingers.
Contamination A sluggish or no response indicates that the sensor is contaminated. Deposits on
the crystal can be removed carefully by wiping with a soft tissue.
Repolish non-regenerable modules with an aqeous slurry of aluminum oxide or
with toothpaste. Polishing can shift the electrode zero point by several mV. This
shift subsides within several days. During this time, however, the electrode must
be calibrated more frequently.
Reagents
ISA solution: (Ionic Strength Adjustment)
Sodium nitrate solution 5.0 mol/L
Dissolve 42.5 g sodium nitrate (p.a.) in deion water and adjust to 100 mL in a
volumetric flask.
Citrate buffer Dissolve 100 g citric acid p.a. in about 800 mL deion. water.
Add 40 g NaOH p.a. (low in chloride) and dissolve. Cool to room temperature
and adjust to 1000 mL. The pH value should be about 5.
Sulfide oxidation Put 62 g boric acid in 800 mL deion water. Add 10 % sodium hydroxide until
solution the boric acid has dissolved completely and a pH value of 8.5 is reached.
Add 100 mL hydrogen peroxide 30 % and fill to 1000 mL with deion. water.
Cl- stock solution Chloride standard solution (sodium chloride in water) 1.000 g± 0.002 g Cl- ,
MERCK Art. No. 119897. Fill to 1000 mL with deion. water. 1 mL = 1 mg
chloride. This solution is used to make appropriate standards.
Remarks
Ionic strength To prevent differences in the ionic strength among samples, add to each
calibration and measurement solution a constant amount of ISA solution.
Interfering ions Ions that form poorly soluble silver salts, e.g. bromide, iodide, sulfide. Com-
plexing agents for silver ions, such as cyanide or thiosulfate, cause falsification
of measured values. The same holds for strong reducing agents. These convert
AgCl to metallic silver.
Sulfide containing To prevent the sulfide from interfering with the chloride determination, it must
be oxidized. All calibration and measurement solutions are mixed 1:1 with the
sulfide oxidation solution instead of with the ISA solution. To allow for complete
sulfide oxidation, let samples stand for 10 minutes before measuring.
Alkaline earth ions Alkaline earth ions can interfere by depositing hydroxide and carbonate on the
membrane. This can be prevented by adding citrate buffer 1:1, rather than the ISA
solution.
Extending By mixing 1:1 with e.g. acetone or isopropanol, the AgCl solubility and thus the
detection limit can be lowered and the linear measurement range extended.
Range The same effect is attained by cooling calibration and measurement solutions
below room temperature. Combining both methods allows an extension of the
measurement range to < 10-6 mol/L.
Application and Use

Application The chloride electrode is used for chloride determinations in air, water, foods, soil
and rock samples.
Use The chloride determination is useful for routine analyses in which the exact
content is not as interesting as finding a standard or limiting value.
Alternatives Chloride determinations can also be performed using argentometric titration.

AgNO3 + Cl- = AgCl + NO3-
This method is often more selective, more exact and gives more reproducible
results than the chloride electrode.
For these reasons, argentometric titration is frequently used.
Advantages The chloride determination has the following advantages over argentometric
titration:
- the determination is faster (with ISE approx. 2 min; titration 3-4 min)
- no heavy metal wastes (AgCl)
Disadvantages The chloride determination has the following disadvantages compared to

argentometric titration:
- not selective for some samples (erroneous results)
- poor reproducibility
METTLER TOLEDO
M103 Calibrating the Chloride Electrode
Sample: 50 mL chloride solution Instruments: METTLER TOLEDO DL77

1 g/L and 10-2 g/L HP Deskjet 500 Printer
MT AT261 Balance
Substance: Chloride
M = 35.45 g/mol , z = 1 Method: Cl07
Preparation: 3 mL ISA solution Accessories: Titration beaker ME-101974

Titrant: --
Standard: -- Indication: DX235 Chloride ISE

Results: METTLER DL77 Titrator V3.0 Mettler-Toledo AG

Norma 4766 Market Support Laboratory
Method Cl07 Calibration Cl- -Sensor B 19-Aug-1993 8:53

User AS
Measured 15-Sep-1993 18:02
RESULTS
1/1 2 50.0 mL pH,pM,pX 2.000

1/2 0 50.0 mL pH,pM,pX 0.000
CALIBRATION
Sensor Cl--Sensor B
Zero point -2.055 pX0
Slope 57.33 mV/pX
Method Remarks
Method Cl07 Calibration Cl--Sensor B
Version 19-Aug-1993 8:53 1) Calibration and measurement solutions should
Method ID . . . . . . . . . . . . . Cl07
Title . . . . .
Date/time . . . . .
. . . . . . . . Calibration Cl--Sensor B
. . . . . . . . 19-Aug-1993 8:53
2) All measurements should be performed using
Sample
Number samples . . . . . . . . . . 2
the same stirring conditions. This means the
Titration stand . .
Entry type . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Stand 1
Fixed volume U
same speed, stirrer type, distance to electrode
Volume [mL] . . .
ID1 . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
50.0
etc.
Molar mass M . . . . . . . . . . . . 0.0
Equivalent number z
Temperature sensor .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
1
TEMP A
3) The calibration parameters are automatically
Stir
Speed [%] . . . . . . . . . . . . . 50
stored in the installation data by the titrator.
Time [s] . . . . . .
Measure
. . . . . . . . 180 They are then referred to the sensor indicated
Sensor . . . . . .
Unit of meas . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Cl--Sensor B
mV
in the method and are applicable only for this
∆E [mV] . . . . . .
∆t [s] . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
0.5
2.0
sensor.
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . . . . . . 10.0 4) Up to 8 standard solutions can be used for the
t(max) [s] . . . . . . . . . . . . . 30.0
Calculation calibration. If only one standard is used, the
Formula . . . . . . . . . . . . . . R=E titrator will correct only the zero point.
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mV
Decimal places . . . . . . . . . . . 3 5) Rinse electrode with deion. water after each
Calibration
Sensor . . . . . . . . . . . . . . . -
Cl -Sensor B measurement and remove adhering water
Buffer type . . . . . . . . . . . . pH,pM,pX
First buffer . . . . . . . . . . 2.0 drops with a soft paper tissue.
Second buffer . . . . . . . . . . 0.0
Third buffer . . . . . . . . . . 0.0
Fourth buffer . . . . . . . . . . 0.0 6) Each measurement requires at leat three min-
Fifth buffer . . . . . . . . . . 0.0
Sixth buffer . . . . . . . . . . 0.0 utes of stirring time for a stable measured
Seventh buffer . . . . . . . . . 0.0
Eighth buffer . . . . . . . . . . 0.0 value.
Ri (i=index) . . . . . . . . . . . . R1
Minimal slope . . . . . . . . . . . 55.0
Maximal slope . . . . . . . . . . . 65.0
Record
All results . . . . . . . . . . . . Yes
Typical calibration curve of a chloride selective electrode with ISA solution
Disposal
--
Other titrators
METTLER TOLEDO
M104 Chloride Determination with Ion Selective Chloride Electrode
Sample: 50 mL sample solution with Instruments: METTLER TOLEDO DL77

1.0 to 0.005 g/L chloride Printer (HP Desk Jet 500)
Substance: Chloride Method: Cl0A, Cl0B

M = 35.45 g/mol , z = 1
Preparation: 3 mL ISA solution DT120 (temp. sensor Pt100)
Titrant: - Indication: DX235 Chloride ISE

Standard: - (bridge electrolyte: 1 M KNO3)
1. For these measurements, aqueous chloride solutions were made with NaCl.
2. The chloride electrode was calibrated daily with 1000 mg/L and 10 mg/L chloride standard .
3. Preparation: Add 3 mL ISA solution to 50 mL sample and measure.
Concentration Recovery srel from several series (n=6 .. 10)

mg / L % Method A Method B
1000 100 - 104 % 0.3 - 0.6 % 0.3 - 0.7 %
100 99 - 104 % 0.3 - 0.7 % 0.3 - 0.9 %
10 95 - 108 % 0.2 - 0.3 % 0.3 - 0.5 %
5 107 - 114 % 0.3 - 1.1 % 0.5 - 1.2 %
Result:
Method (A) gives a better reproducibility. The differences between (A) and (B) are not, however,
decisive in practice.
The concentration 5 mg/L is not in the linear range (see calibration curve page 17). Thus, the range of
useful concentrations for the chloride electrode is hereafter limited from 1000 to 10 mg/L.
Method A (direct meaurement with mean value) Method B (Single direct measurement)
-
Method Cl0A Cl -content Method Cl0B Cl--Content
Version 13-Jul-1993 10:25 Version 26-Jul-1993 10:35
Title Title
Method ID . . . . . . . . . . . . . Cl0A Method ID . . . . . . . . . . . . . Cl0B
Title . . . . . . . . . . . . . Cl--content Title . . . . . . . . . . . . . Cl--Content
Date/time . . . . . . . . . . . . . 13-Jul-1993 10:25 Date/time . . . . . . . . . . . . . 26-Jul-1993 10:35
Sample Sample
ID1 . . . . . . . . . . . . . . . . ID1 . . . . . . . . . . . . . . . .
Stir Stir
Speed [%] . . . . . . . . . . . . . 50 Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 180 Time [s] . . . . . . . . . . . . . . 180
Measure Measure
Sensor . . . . . . . . . . . . . . Cl--Sensor B Sensor . . . . . . . . . . . . . . Cl--Sensor B
∆E [mV] . . . . . . . . . . . . . . 0.2 ∆E [mV] . . . . . . . . . . . . . . 0.2
∆t [s] . . . . . . . . . . . . . . 5.0 ∆t [s] . . . . . . . . . . . . . . 5.0
t(min) [s] . . . . . . . . . . . 10.0 t(min) [s] . . . . . . . . . . . 10.0
t(max) [s] . . . . . . . . . . . . . 90.0 t(max) [s] . . . . . . . . . . . . . 90.0
Measure Calculation
Sensor . . . . . . . . . . . . . . Cl--Sensor B Result name . . . . . . . . . . . .
∆E [mV] . . . . . . . . . . . . . . 0.2 Constant . . . . . . . . . . . . . .
∆t [s] . . . . . . . . . . . . . . 5.0 Result unit . . . . . . . . . . . . p(Cl-)
t(max) [s] . . . . . . . . . . . . . 90.0 Result name . . . . . . . . . . . . Cl--content
-
Sensor . . . . . . . . . . . . . . Cl -Sensor B Constant . . . . . . . . . . . . . .
Unit of meas . . . . . . . . . . . . mV Result unit . . . . . . . . . . . . g/L
∆t [s] . . . . . . . . . . . . . . 5.0 Calculation
t(min) mode . . . . . . . . . . . . Fix Result name . . . . . . . . . . . . NaCl-content
t(min) [s] . . . . . . . . . . . 10.0 Formula . . . . . . . . . . . . . . R3=R2*1.648
t(max) [s] . . . . . . . . . . . . . 90.0 Constant . . . . . . . . . . . . . .
Measure Result unit . . . . . . . . . . . . g/L
Sensor . . . . . . . . . . . . . . Cl--Sensor B Decimal places . . . . . . . . . . . 5
Unit of meas . . . . . . . . . . . . mV Statistics
∆E [mV] . . . . . . . . . . . . . . 0.2 Ri (i=index) . . . . . . . . . . . . R2
∆t [s] . . . . . . . . . . . . . . 5.0 Standard deviation s . . . . . . . . Yes
t(min) mode . . . . . . . . . . . . Fix Rel. standard deviation srel . . . . Yes
t(min) [s] . . . . . . . . . . . 10.0 Outlier test . . . . . . . . . . . . Yes
t(max) [s] . . . . . . . . . . . . . 90.0 Statistics
Measure Ri (i=index) . . . . . . . . . . . . R3
Sensor . . . . . . . . . . . . . . Cl--Sensor B Standard deviation s . . . . . . . . Yes
Unit of meas . . . . . . . . . . . . mV Rel. standard deviation srel . . . . Yes
∆E [mV] . . . . . . . . . . . . . . 0.2 Outlier test . . . . . . . . . . . . Yes
∆t [s] . . . . . . . . . . . . . . 5.0 Record
t(min) mode . . . . . . . . . . . . Fix Output unit . . . . . . . . . . . . Printer
t(min) [s] . . . . . . . . . . . 10.0 All results . . . . . . . . . . . . Yes
t(max) [s] . . . . . . . . . . . . . 90.0
Measure
Sensor . . . . . . . . . . . . . . Cl--Sensor B
Unit of meas . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
.
.
mV
0.2
Remarks
∆t [s] . . . . . . . . . . . . . . 5.0
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . . . . . . 10.0
t(max) [s] . . . . . . . . . . . . . 90.0
Calculation Method A
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R1=E[1]
Result unit . . . . . . . . . . . . p(Cl-)
Decimal places . . . . . . . . . . . 4
Calculation
Result name . . . . . . . . . . . . Cl--single
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R2=pw(-E[1])*1000
tions) at an interval of at least 10 s.
Result unit . . . . . . . . . . . . mg/L
Calculation
. . . . 4
3) The chloride concentration is calculated from
Result name . . . . . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
. R3=(C3+E[5]+E[6])/6
. C3=E[1]+E[2]+E[3]+E[4]
the mean of these six values.
Result unit . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 3
Calculation
Result name . . . . . . . . . . . . Cl--x of 6
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R4=pw(-R3)*1000
Method B
Result unit . . . . . . . . . . . . mg/L
Statistics
. . . . 4 1) Stirring during 3 minutes.
Ri (i=index) . . . . . . . . . . . . R2
.
.
.
.
.
.
.
.
Yes
Yes 2) Acquisition of one value.
Outlier test . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . .
.
.
.
.
.
.
.
.
R4
Yes
Outlier test . . . . . . . .
.
.
.
.
.
.
.
.
Yes
Yes
the dilution factor can be entered as a correc-
Record
Output unit . . . . . . . . . . . . Printer tion factor (f) for each sample. This will be
All results . . . . . . . . . . . . Yes
used in the calculation.
Disposal
Other titrators --
Results
Sample Direct meas’ment with ISE Nominal content Titration with AgNO3
(Number) Content srel Producer specification Amount
Tomato juice 7.92 g NaCl/L 5.4 % — 2 mL 7.5 g NaCl/L

(n = 5)
Tomato ketchup 40.0 g NaCl/kg 1.3 % 33-35 g NaCl/L 2g 33.0 g NaCl/L

(n = 5)
Carrot juice 690 mg Cl-/L 0.7 % 207-771 mg Cl-/L* 25 mL 669 mg Cl-/L

(n = 10)
Mayonnaise 12.3 g NaCl/kg 1.0 % 12.3 g NaCl/kg 2g 11.6 g NaCl/kg

(n = 5) ±3%
Salad dressing 32.5 g NaCl/kg 1.0 % — 0.5 g 30.9 g NaCl/L

(n = 4)
Cheese 12.6 g NaCl/kg 1.5 % — 2g 13.5 g NaCl/kg

(n = 3)
Milk 1.16 g Cl-/L 0.9 % 0.97-1.05 g Cl-/L* 5 mL 1.16 g Cl-/L

(n = 5)
Baby food 975 mg NaCl/kg 3.1 % — 10 g 934 mg NaCl/

kg
(n = 4)
Beans 11.5 g NaCl/kg 5.6 % 8.0 g NaCl/L 5g 8.4 g NaCl/kg

canned ± 2 g/l
(n = 5)
Peas 7.4 g NaCl/kg 1.1 % 8.0 g NaCl/L 5g 7.4 g NaCl/kg

canned ± 2 g/l
(n = 5)
th
* Obtained from: Schweizerisches Lebensmittelbuch, 5 Edition Table 8
Tomato juice Dilute sample with deion. water 1:10. To 50 mL add 3 mL ISA solution and
measure.
Matrix effects cause the somewhat higher values obtained with ISA.
Tomato ketchup Mix 2 g sample with 100 mL deion. water, add 6 mL ISA solution and measure.
Carrot juice Dilute 25 mL sample with 25 mL HNO 3 (0.1 mol/L), add 3 mL ISA solution and
measure.
The calibration solutions contained 0.05 mol/L NHO3.
Mayonnaise Dilute 0.5 g sample with 100 mL HNO 3 0.1 mol/L, add 6 mL ISA solution
Salad dressing and measure. Higher sample weights are disadvantageous because the risk of fat
adhering to the membrane increases with the amount of fat in solution. This results
in a poorer slope. The sample was stirred vigorously (70 %) for 4 minutes prior to
measurement to disperse fat droplets.
Cheese Heat 2.5 g cheese in 100 mL deion. water for 30 minutes with stirring. After
cooling, adjust volume to 250 mL using HNO3 (0.1 mol/L). To 50 mL add 3 mL
ISA solution and measure. The sample was stirred more vigorously (70 %) for
4 minutes before measuring.
Milk Dilute sample with HNO3 (0.1 mol/L) 1:8. To 100 mL of this add 6 mL ISA so-
lution and measure.
The sample was stirred more vigorously (70%) for 3 minutes before measuring
to disperse fat droplets.
Baby food Stir 5 g sample in 100 mL HNO 3 (0.1 mol/L), add 6 mL ISA solution and mea-
sure.
Beans, peas Homogenize can contents with mixer. Stir 10 g resp. 5 g sample into 100 mL
canned deion. water, add 6 mL ISA solution and measure.
General Remarks:
1) All measurements were performed using the simple direct (method B) measurement.
2) Rinse electrode with deion. water after each measurement and remove clinging water drops with
3) All measurements should be performed using the same stirring conditions. This means the same
speed, stirrer type, distance from stirrer to electrode etc.
METTLER TOLEDO
M105 Chloride Determination in Canned Vegetables
Sample: 5 g Peas Instruments: METTLER TOLEDO DL77

HP Deskjet 500 Printer
Substance: Sodium chloride, NaCl
M = 35.45 g/mol , z = 1 Method: Cl0C
Preparation: 100 mL deion. water Accessories: Titration beaker ME-101974

6 mL ISA solution DT120 (temp. sensor Pt100)
Titrant: -- Indication: DX235 Chloride ISE

Standard: -- (bridge electrolyte: 1 M KNO3)
METTLER DL77 Titrator V3.0 Mettler-Toledo AG

Results: Norma 47466 Market Support Laboratory
Method Cl0C NaCl in canned peas 11-Aug-1993 9:53

User AS
Measured 11-Aug-1993 10:03
RESULTS
1/1 Cl- 5.3601 g Weight m

R1 = 0.6285 p(Cl-) Cl--content
R2 = 0.2352 g/L Cl--content
R3 = 7.233 g/kg NaCl-content
STATISTICS
Mean value x = 0.2363 g/L Cl--content
Standard deviation s = 0.007718 g/L Cl--content
STATISTICS
Mean value x = 7.364 g/kg NaCl-content
Standard deviation s = 0.081698 g/kg NaCl-content
Method Remarks
Method Cl0C NaCl in canned peas
Version 11-Aug-1993 10:03 1) Calibration and measurement solutions should
Title always be at the same temperature. All mea-
Method ID . . . . . . . . . . . . . Cl0C
Title . . . . . . . . . . . . . NaCl in canned peas surements should be performed using the same
Date/time . . . . . . . . . . . . . 11-Aug-1993 10:03
Sample stirring conditions. This means the same
Number samples . . . . . . . . . . 5
Titration stand . . . . . . . . . . ST20 1 speed, stirrer type, distance from stirrer to elec-
Entry type . . . . . . . . . . . . . Weight m
Lower limit [g] . . . . . . . . . 0.0 trode etc.
Upper limit [g] . . . . . . . . . 15.0
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
.
.
.
.
.
.
.
.
Cl-
35.453
2) Rinse electrode with deion. water after each
Equivalent number z . . . .
Temperature sensor . . . . .
.
.
.
.
.
.
.
.
1
TEMP A
measurement and remove clinging water drops
Dispense
Titrant . . . . . . . . . . . . . . TISAB
with a soft paper tissue.
Concentration [mol/L] . . . . . . . 5.0
Volume [mL] . . . . . . . .
Stir
. . . . 6.0 3) In this method the chloride concentration in
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 50
. . . . 120
g/L (=R2) of the sample solution and the NaCl
Measure
Sensor . . . . . . . . . . . . . . Cl--Sensor A
content in g/kg (=R3) of the actual sample
Unit of meas . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
.
.
mV
0.3
(canned peas) are calculated.
∆t [s] . . . . . . . . . . . . . . 2.0
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . .
Calculation
. . . . 30.0
Sample Preparation
Result name . . . . . . . . . . . . Cl-content
Formula . . . . . . . . . . . . . . R=E 1) Purée and homogenize contents of the whole
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . p(Cl-) can.
Decimal places . . . . . . . . . . . 4
Calculation 2) Stir 5 g of this with 100 mL deion. water.
Result name . . . . . . . . . . . . Cl-content
Formula . . . . . . . . . . . . . . R2=pw(-R1) 3) Add 6 mL ISA solution (ISA solution addi-
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . g/L tion is performed automatically as part of
Decimal places . . . . . . . . . . . 4
Calculation the method).
Result name . . . . . . . . . . . . NaCl-content
Formula . . . . . . . . . . . . . . R3=R2*C3*100/m
Constant . . . . . . . . . . . . . . C3=1.648
Result unit . . . . . . . . . . . . g/kg
Decimal places . . . . . . . . . . . 3
Statistics Chloride Determination by Titration with AgNO3
Ri (i=index) . . . . . . . . . . . . R2
.
.
.
.
.
.
.
.
Yes
Yes
1) 5 g homogenized canned peas are stirred in
Outlier test . . . . . . . .
Statistics
. . . . Yes 60 mL deion. water.
Ri (i=index) . . . . . . . .
.
.
.
.
.
.
.
.
R3
Yes
2) 2 mL HNO3 (0.1 mol/L) are added and ti-
Outlier test . . . . . . . .
.
.
.
.
.
.
.
.
Yes
Yes
trated with AgNO3 (0.1 mol/L). Electrode:
Record
DM141-SC
All results . . . . . . . . . . . . Yes
Result:
7.4 g NaCl / kg (n = 2)
Content specified by manufacturer:

8 g NaCl / kg± 2 g/kg
Disposal
--
Other titrators
DL55+, DL58, DL77 titrators. Author: Albert Aichert
3. Nitrate Selective Electrode
Theory The nitrate electrode is a liquid membrane electrode. This type of electrode works
according to the ion exchange principle. The ion to be measured (nitrate) is
embedded in an ion exchanger in the PVC polymer membrane. The ion exchang-
er is water insoluble and forms a nearly water insoluble complex with the nitrate
(e.g. nickel nitrate complex). Therefore, an electrode with a new membrane must
first be conditioned for 5 – 10 minutes in a nitrate solution of approx. 0.01 mol/
L. This procedure makes the electrode nitrate selective. The insolubility of the
nitrate salt allows measurements in aqeous solutions to be performed without
causing the nitrate ions to be dissolved out of the active phase. Thus the selectivity
is retained.
The active ion substance in the nitrate electrode is an o-phenanthroline-nickel-
nitrate complex.
Measurement range When ISA is used to adjust the ionic strength, a linear calibration curve from 0.1
- 10-4 mol/L is obtained.
The detection limit lies somewhat above 10-5 mol/L. The slope, theoretically
calculated from the Nernst equation to be 58.16 mV at 20°C, lies at 58 mV in
practice.
Electrodes
Bridging electrolyte As the bridging electrolyte for the reference electrode, a 0.9 mol/L aluminium
sulphate solution (ME-51 340 072) is used. The solution must be renewed daily.
The inner electrolyte (KCl solution, 3 mol/L, ME-51 340 049) is renewed
monthly.
Conditioning The nitrate electrode is conditioned in a nitrate solution, 0.01 mol/L, for 5-10
minutes prior to measurement.
Storage Store nitrate electrode dry, preferably in protective sleeve.
Reference electrode: drain electrolyte. To store, seal orifice for filling with
rubber stopper. (The longevity of the reference electrode is reduced if the
bridging electrolyte chamber is consistently filled up over the inner diaphragm;
KCl leakage).
Handling The polymer measurement membrane can be damaged by mechanical impact
(e.g. magnetic stirrer, cleaning). If the membrane is damaged, the membrane
module must be replaced. Avoid fat deposits on the membrane; do not touch with
bare hands.
Contamination A sluggish response indicates that the sensor is contaminated. Deposits on the
surface of the membrane module can be removed by placing the nitrate electrode
in deion. water or dilute acid or base (< 0.001 mol/L) for several minutes. After
rinsing with deion water, the electrode is conditioned for several minutes in
approx. 0.01 mol/L nitrate solution.
If the electrode is no longer regenerable, the membrane module must be replaced.
Reagents
ISA solution (Ionic Strength Adjustment)
METTLER TOLEDO ISA Aluminum sulfate solution 0.9 mol/L (METTLER TOLEDO 51 340 072)
The ISA solution can also be prepared as it follows.
600 g Al2(SO4)3 • 18 H2O are dissolved in 800 mL deion. water by heating. After
cooling to room temperature, adjust volume to 1000 mL in flask. The milky,
colloidal solution keeps for several weeks at room temp. In case a sediment
deposits after standing for some time, use only the remaining clear solution by
pipetting from the top.
N03- standard Nitrate standard solution 0.1 mol/L:
8.501 g NaNO3, p.a., (eg: Fluka Art. No. 71758) are dissolved in a 1000 mL
volumetric flask in deion. water. Fill to mark. This solution keeps for several
months.
Hints
Ionic strength The total activity of measurement and calibration solutions must be constant. By
adding to each a constant amount of ISA solution, a constant ionic strength is
attained.
Interfering ions In order to keep the error induced by interfering ions below 10%, the molar
relation (X- / NO3- ) of these ions must be smaller than the value in parenthesis:
ClO4- (<0.0007), NO2- (<0.0005), I- (<0.001); Br- (<0.02); Cl- (<1); HS- (<1);
CN- (<0.01); ClO3- (<0.2), HCO3- (<25); CO3- (<15), PO43- , HPO42-, SCN-,
H2PO4-, F- and SO42- (<100)
Anionic tensides should not be present. Chloride, iodide, bromide, phosphate,
hydrogensulfite and cyanide can be precipitated with silver sulfate (0.01 mol/L).
Carbonate and bicarbonate can be removed by acidifying with sulfuric acid to
pH 4.5.
Nitrite is selectively reduced with sulphamic acid.
Org. Acids Many organic acids that interfere with the nitrate electrode are precipitated by the
aluminium sulfate in the ISA solution.
Application and Use

Application The nitrate electrode is used for nitrate determination in water, beverages, foods
(meat, vegetables), vegetation and fertilizers.
Use The nitrate determination using an ion selective electrode is especially useful for
routine analyses (same samples with known matrix), in which the nitrate content
must be determined quickly and simply.
Alternatives The nitrate determination can also be achieved using chromatography, photo-
metric or potentiometric titration with ferroammonium sulfate.
Advantages - wide application range (0.1 - 10-4 mol/L)
- quick, simple determination
- no heavy metal wastes (titration)
- small investment (compared to chromatography)
Disadvantages - non-selective for a few samples; values are somewhat too high.
METTLER TOLEDO
M106 Calibrating the Nitrate Electrode
Sample: 50 mL nitrate solution Instruments: METTLER TOLEDO DL77

10-2 mol/L and 10-4 mol/L HP Deskjet 500 Printer
MT AT261 Balance
Substance: Nitrate, NO3-
M = 62.00 g/mol , z = 1 Method: N007

(0.9 mol/L Al2(SO4)3 , DT120 (temp. sensor Pt100)
ME-51 340 072)
Titrant: -- Indication: DX262 Nitrate ISE

Standard: -- (bridge electrolyte:
0.9 mol/L Al2(SO4)3 )

Method N007 Calibration NO3-sensor 28-May-1993 13:42

User AS
Measured 02-Jun-1993 8:02
RESULTS
1/1 10-4 mol/L 50.0 mL pH,pM,pX 4.000

1/2 10-2 mol/L 50.0 mL pH,pM,pX 2.000
CALIBRATION
Sensor NO3-Sensor
Slope 57.26 mV/pX
No data
Method Remarks
Method N007 Calibration NO3-sensor
Version 28-May-1993 13:42 1) Calibration and measurement solutions should
Method ID . . . . . . . . . . . . . N007
Title . . . . . . . . . . . . . Calibration NO3-sensor
Date/time . . . . . . . . . . . . . 28-May-1993 13:42 2) All measurements should be performed using
Sample
Volume [mL] . . . . . . . . . . . 50.0
ID1 . . . . . . . . . . . . . . . . etc.
Molar mass M . . . . . . . . . . . . 0.0
Equivalent number z
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
1
TEMP A
Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . .
Measure
. . . . . . . . 300
They are then referred to the sensor indicated
Sensor . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
NO3-sensor
mV
∆E [mV] . . . . . .
∆t [s] . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
0.5
2.0
sensor.
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . .
t(max) [s] . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
10.0
30.0
Calculation
Formula . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
R=E titrator will correct only the zero point.
Result unit . . . . . . . . . . . . mV
Calibration
Sensor . . . . . . . . . . . . . . . NO3-sensor measurement and remove adhering water
Second buffer . . . . . . . . . . 2.0
Third buffer . . . . . . . . . . 0.0
Fourth buffer . . . . . . . . . . 0.0 6) Each measurement requires at least five min-
Fifth buffer . . . . . . . . . . 0.0
Sixth buffer . . . . . . . . . . 0.0 utes stirring time for a stable measured value.
Seventh buffer . . . . . . . . . 0.0
Eighth buffer . . . . . . . . . . 0.0 (see next page for automatic three point cali-
Ri (i=index) . . . . . . . . . . . . R1
Minimal slope . . . . . . . . . . . 55.0 bration).
Maximal slope . . . . . . . . . . . 65.0
Record
All results . . . . . . . . . . . . Yes
Typical calibration curve of a nitrate selective electrode with ISA solution
Disposal
--
Other titrators
METTLER TOLEDO
M107 Automatic Three-point Calibration of the Nitrate Electrode
Sample: 200 mL nitrate solution Instruments: METTLER TOLEDO DL70ES

10-2 , 10-3 and 10-4 mol/L HP Deskjet 500 Printer
are prepared automatically MT AT261 Balance
Substance: Nitrate, NO3- Method: N008

M = 62.00 g/mol , z = 1
Accessories: 250 mL Titr. beaker ME-23515
(0.9 mol/L Al2(SO4)3 , 1 additional burette drive
ME-51 340 072)
Indication: DX262 Nitrate ISE
Titrant: Nitrate solution, DX200 Reference electrode
c(NO3-) = 10-1 mol/L (bridge electrolyte:
0.9 mol/L Al2(SO4)3 )
Standard: --

Method N008 Auto-calibration NO3-sens. 13-Dec-1993 13:53

User aa
Measured 13-Dec-1993 13:56
RESULTS
1/1 10-4 mol/L 200.0 mL pH,pM,pX 4.000

1/2 10-3 mol/L 200.0 mL pH,pM,pX 3.000
1/2 10-2 mol/L 200.0 mL pH,pM,pX 2.000
CALIBRATION
Sensor NO3-Sensor
Slope 56.94 mV/pX
AUXILIARY VALUE
New value H10 = 1.0 Counter
AUXILIARY VALUE
New value H10 = 4.0 Counter
Method Remarks
Method N008 Auto-calibration NO3-sens.
Version 13-Dec-1993 13:53 1) Calibration and measurement solutions
Title should always be at the same temperature.
Method ID . . . . . . . . . . . . . N008
Title . . . . . . . . . . . . . Auto-calibration NO3-sens.
Date/time . . . . . . . . . . . . . 13-Dec-1993 13:53 2) All measurements should be performed using
Dispense
Titrant . . . . . . . . . . . . . . ISA/NO3 the same stirring conditions. This means the
Volume [mL] . . . . . . . . . . . . 20 same speed, stirrer type, distance to electrode
Auxiliary value
ID text . . . . . . . . . . . . . . Counter etc.
Formula . . . . . . . . . . . . . . H10=1.0
Sample
Number samples . . . . . . . . . . 3
Titration stand . . .
Entry type . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Auto stand
Fixed volume U
Volume [mL] . . . .
ID1 . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
200.0
Molar mass M . . . . .
Equivalent number z .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
0.0
1
Temperature sensor . .
Dispense
. . . . . . . TEMP A
sensor.
Titrant . . . . . . . . . . . . . . NO3-solution
Concentration [mol/L]
Volume [mL] . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
0.1
0.2
Condition . . . . . .
Condition . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Yes
H10=1.0
Dispense
Titrant . . . . . . . . . . . . . . NO3-solution
titrator will correct only the zero point.
Volume [mL] . . . . . . . . . . . . 2.0 5) Rinse electrode with deion. water after each
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . . H10=2.0 measurement and remove adhering water
Dispense
Titrant . . . . . . . . . . . . . . NO3-solution drops with a soft paper tissue.
Volume [mL] . . . . . . . . . . . . 20.0
Condition . . . . . . . . . . . . . Yes 6) Each measurement requires at least five min-
Condition . . . . . . . . . . . . H10=3.0
Stir utes stirring time for a stable measured value.
Speed [%] . . . . . . . . . . . . . 70
Time [s] . . . . . . . . . . . . . . 300
Auxiliary value
ID text . . . . . . . . . . . . . . Counter
Formula . . . . . . . . . . . . . . H10=H10+1
Measure
Sensor . . . . . . . . . . . . . . NO3-sensor
Unit of meas . . . . . . . . . . . . mV
∆E [mV] . . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . . 2.0
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . .
t(max) [s] . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
10.0
30.0
Remarks on method
Calculation
Result name . . . . . . . . . . . . Potential 1) The calibration solutions required for this
Formula . . . . . . . . . . . . . . R=E
Constant . . . . . . . . . . . . . . method (10-2, 10-4 and 10-3 mol/L) were made
Result unit . . . . . . . . . . . . mV
Decimal places . . . . . . . . . . . 3 automatically from one nitrate standard solu-
Calibration
Sensor . . . . . . . . . . . . . . . NO3-sensor tion (10-1 mol/L).
First buffer . . . . . . . . . . 4.0
Second buffer . . . . . . . . . . 3.0 2) Have available exactly 200 mL deion. water.
Third buffer . . . . . . . . . . 2.0
Fourth buffer . . . . . . . . . . 0.0 The 20 mL ISA solution and the amount of
Fifth buffer . . .
Sixth buffer . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
0.0
0.0 nitrate standard solution (10-1 mol/L) are dis-
Seventh buffer . . . . . . . . . 0.0
Eighth buffer . . . . . . . . . . 0.0 pensed automatically by the titrator.
Ri (i=index) . . . . . . . . . . . . R1
Minimal slope . . . . . . . . . . . 50.0
Maximal slope . . . . . . . . . . . 60.0
Record
All results . . . . . . . . . . . . Yes
Disposal
--
Other titrators
METTLER TOLEDO
M108 Nitrate Determination with Ion Selective Electrode
Sample: 50 mL sample solution with Instruments: METTLER TOLEDO DL77

100 to 0.01 mmol/L nitrate Printer (HP Desk Jet 500)
Substance: Nitrate, NO3- Method: N00A, N00B

M = 62.00 g/mol , z = 1
0.9 mol/L Al2(SO4)3
(ME-51 340 072) Indication: DX262 Nitrate ISE
Titrant: - (bridge electrolyte:
0.9 mol/L Al2(SO4)3 )
Standard: -
1. Aqueous nitrate solutions were used for these measurements. They were prepared from NaNO3,
p.a., Fluka Art. No. 71758.
2. The nitrate electrode was calibrated daily with standard solutions of 10 and 0.1 mmol nitrate/L,
if necessary already after 2-3 series.
3. Preparation: Add 5 mL ISA solution to 50 mL sample before measuring.
Concentration Recovery srel of several series (n= 6)

mmol / L % Method A Method B
100 97 - 102 % 0.33 - 08 % 0.41 - 0.8 %
10 99 - 103 % 0.23 - 1.1 % 0.23 - 1.0 %
1 97 - 103 % 0.11 - 0.9 % 0.30 - 1.0 %
0.1 99 - 102 % 0.09 - 1.7 % 0.15 - 1.8 %
0.05 105 - 109 % 0.42 - 0.75 % 0.61 - 0.75 %
0.01 250 - 260 % 0.7 - 3.0 % 0.9 - 3.2 %
Result
The differences between methods (A) and (B) are not decisive in practice.
The concentration of 0.05 mmol/L is outside the linear range (see calibration curve page 27). Thus, the
range of useful concentrations for the nitrate electrode is limited from 100 to 0.1 mmol/L.
Method N00A NO3--content Method N00B NO3--content
Version 14-Dec-1993 12:59 Version 14-Dec-1993 13:04
Title Title
Method ID . . . . . . . . . . . . . N00A Method ID . . . . . . . . . . . . . N00B
Title . . . . . . . . . . . . . NO3--content Title . . . . . . . . . . . . . NO3--content
Date/time . . . . . . . . . . . . . 14-Dec-1993 12:59 Date/time . . . . . . . . . . . . . 14-Dec-1993 13:04
Sample Sample
ID1 . . . . . . . . . . . . . . . . ID1 . . . . . . . . . . . . . . . . NO3-
Stir Stir
Speed [%] . . . . . . . . . . . . . 50 Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 300 Time [s] . . . . . . . . . . . . . . 900
Measure Measure
Sensor . . . . . . . . . . . . . . NO3--Sensor Sensor . . . . . . . . . . . . . . NO3--sensor
∆E [mV] . . . . . . . . . . . . . . 0.2 ∆E [mV] . . . . . . . . . . . . . . 0.3
∆t [s] . . . . . . . . . . . . . . 5.0 ∆t [s] . . . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . . 10.0 t(min) [s] . . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . . . . 90.0 t(max) [s] . . . . . . . . . . . . . 30.0
Measure Calculation
Sensor . . . . . . . . . . . . . . NO3--Sensor Result name . . . . . . . . . . . .
∆E [mV] . . . . . . . . . . . . . . 0.2 Constant . . . . . . . . . . . . . .
∆t [s] . . . . . . . . . . . . . . 5.0 Result unit . . . . . . . . . . . . p(NO3-)
t(max) [s] . . . . . . . . . . . . . 90.0 Result name . . . . . . . . . . . . NO3--content
-
Sensor . . . . . . . . . . . . . . NO3 -Sensor Constant . . . . . . . . . . . . . .
Unit of meas . . . . . . . . . . . . mV Result unit . . . . . . . . . . . . mmol/L
∆t [s] . . . . . . . . . . . . . . 5.0 Statistics
Sensor . . . . . . . . . . . . . . NO3--Sensor Record
∆t [s] . . . . . . . . . . . . . . 5.0
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . . . . . . 10.0
t(max) [s] . . . . . . . . . . . . . 90.0
Measure
Sensor . . . . . . . . . . . . . . NO3--Sensor
Unit of meas . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
.
.
mV
0.2
Remarks
∆t [s] . . . . . . . . . . . . . . 5.0
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . . . . . . 10.0
t(max) [s] . . . . . . . . .
Measure
. . . . 90.0
Method A
Sensor . . . . . . . . . . . . . . NO3--Sensor
Unit of meas . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
.
.
mV
0.2
1) Stirring during five minutes.
∆t [s] . . . . . . . . . . . . . . 5.0
t(min) mode . . . . . . . .
t(min) [s] . . . . . . .
.
.
.
.
.
.
.
.
Fix
10.0 2) Acquisition of six values (six Measure-func-
t(max) [s] . . . . . . . . . . . . . 90.0
Calculation
Formula . . . . . . . . . . . . . . R1=E[1]
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
. p(NO3-)
Decimal places . . . . . . . . . . . 4
Calculation the mean of these six values.
Result name . . . . . . . . . . . . NO3--single
Formula . . . . . . . . . . . . . . R2=pw(-E[1])*1000
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mmol/L
Decimal places . . . . . . . . . . . 4
Calculation
Result name . . . . . . . . . . . .
Method B
Formula . . . . . . . . . . . . . . R3=(C3+E[5]+E[6])/6
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
. C3=E[1]+E[2]+E[3]+E[4]
.
Decimal places . . . . . . . . . . . 3
Calculation
Result name . . . . . . . . . . . . NO3--x of 6
Formula . . . . . . . . . . . . . . R4=pw(-R3)*1000
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
. mmol/L 3) If the sample is diluted for the measurement,
Decimal places . . . . . . . . . . . 4
Statistics
Ri (i=index) . . . . . . . . . . . . R2
.
.
.
.
.
.
.
.
Yes
Yes
Outlier test . . . . . . . . . . . . Yes
Statistics used in the calculation.
Ri (i=index) . . . . . . . . . . . . R4
Outlier test . . . . . . . . . . . . Yes
Record
All results . . . . . . . . . . . . Yes
Disposal
Other titrators --
Results
Sample Direct measurement with nitrate electrode Number partial samples and
measurements
n Content srel
Lettuce head 5 2033 mg / kg 1.1 % 1 partial sample, 5 meas’ments

supermarket 15 2149 mg / kg 5.4 % 3 partial samples, 5 meas’ments
Lettuce head 10 1753 mg / kg 0.6 % 5 partial samples, 2 meas’ments

garden variety
Iceberg lettuce 7 821 mg / kg 1.1 % 1 partial sample, 7 meas’ments

garden variety 21 924 mg / kg 10.1 % 3 partial samples, 7 meas’ments
Cucumber 6 101 mg / kg 1.5 % 6 partial samples, 1 measurement

supermarket
Potatoes 5 218 mg / kg 1.2 % 1 partial sample, 5 meas’ments

Spinach 4 969 mg / kg 1.4 % 2 partial samples, 2 meas’ments

Silver beet 4 117 mg / kg 2.1 % 2 partial samples, 2 meas’ments

organically grown 10 129 mg / kg 11.3 % 5 partial samples, 2 meas’ments
Cabbage 4 589 mg /kg 5.7 % 2 partial samples, 2 meas’ments

10 692 mg / kg 15.4 % 5 partial samples, 2 meas’ments
Carrots 4 215 mg / kg 0.3 % 2 partial samples, 2 meas’ments

organically grown 8 207 mg / kg 5.2 % 4 partial samples, 2 meas’ments
Carrot juice 10 230 mg / kg 1.8 %
Beet juice 9 2257 mg / kg 0.3 %
Drinking water 3 19 mg / kg 0.6 %
Aquarium water 3 7.2 mg / kg 0.4 %
Sample preparation and remarks
Lettuce head Finely chop whole head with mixer or onion chopper. Mix well. Take 30 g
Iceberg lettuce (=partial sample) and mix for 1 minute with 370 mL deion. water. Filter through
glass frit. To 50 mL filtrate add 5 mL ISA solution and measure. Tolerance value*
lettuce head: 3500 mg / L
Cucumber Finely chop whole cucumber with mixer or onion chopper. Mix well. Take 30 g
(=partial sample) and mix for 1 minute with 370 mL deion. water. Filter through
glass frit. To 50 mL filtrate add 5 mL ISA solution and measure.
Potatoes Finely chop 1 kg potatoes with mixer or onion chopper. Mix well. Mix 250 g of
this (=partial sample) with 250 mL deion. water for 1 minute. Filter through glass
frit. Dilute 25 mL filtrate 1:1 with water, add 5 mL ISA solution and measure.
Spinach Finely chop 500 g sample with mixer or onion chopper. Mix well. Take 30 g.
Silver beet (=partial sample) and mix for 1 minute with 370 mL deion. water. Filter through
glass frit. Dilute 25 mL filtrate 1:1 with deion. water, add 5 mL ISA solution
and measure. Tolerance value* spinach: 3500 mg / L
Cabbage Finely chop whole head with mixer or onion chopper. Mix well. Take 30 g of this
(=partial sample) and mix for 1 minute with 370 mL deion. water. Filter through
glass frit. Dilute 25 mL filtrate 1:1 with deion. water, add 5 mL ISA solution and
measure.
All cabbage varieties are difficult to measure. They contain sulfur compounds
that contaminate the membrane and thus reduce the longevity of the electrode.
Carrots Grate 1 kg and mix well.

Mix 200 g of this (=partial sample) with 200 mL deion. water for 1 min.
Filter through glass frit. Dilute 25 mL filtrate 1:1 with deion. water, add 5 mL
ISA solution and measure.
Carrot juice Dilute 25 mL sample 1:1 with deion. water.

Beet juice Add 5 mL ISA solution and measure.
Producer’s specification for carrot juice: max. 500 mg / L
Tolerance value* beet juice: 2500 mg / L
Drinking water To 50 mL sample add 5 mL ISA solution and measure.

Tolerance value*: 40 mg / L
Aquarium water To 50 mL sample add 5 mL ISA solution and measure.
* Tolerance values indicate the highest allowable concentration of substances. At

higher concentrations, the pertinent authority will intervene. Standing as of Sept
1991 (Switzerland).
General remark
All measurements were performed using the simple direct measurement (Method B).
METTLER TOLEDO
M109 Nitrate Determination in Reference Samples
Sample: 2 g Reference sample Instruments: METTLER TOLEDO DL77

Beet (red beet)) HP Deskjet 500 Printer
Substance: Nitrate, NO3- Method: N00D

M = 62.00 g/mol , z = 1
Preparation: 100 mL deion. water DT120 (temp. sensor Pt100)
5 mL ISA solution
0.9 mol/L Al2(SO4)3 Indication: DX262 Nitrate ISE
(ME-51 340 072) DX200 Reference electrode
(bridge electrolyte:
Titrant: -- 0.9 mol/L Al2(SO4)3 )
Standard: --
Results:
METTLER DL77 Titrator V3.0 Mettler-Toledo AG
Method N00D NO3- dry substance 01-Jul-1993 14:04

User AS
Measured 01-Jul-1993 14:07
RESULTS
1/1 beetroot 2.0643 g Weight m

R1 = 0.763 mmol/L NO3--conc
R2 = 4584 mg/kg content dry
STATISTICS
Mean value x = 4583 mg/kg content dry
Standard deviation s = 16.48865 mg/kg content dry
Outlier test: no outliers!
Method Remarks
Method N00D NO3- dry substance
Version 01-Jul-1993 14:04
Title
Method ID . . . . . . . . . . . . . N00D
Title . . . . . . . . . . . . . NO3- dry substance Sample Preparation
Date/time . . . . . . . . . . . . . 01-Jul-1993 14:04
Sample
Number samples . . . . . . . . . . 3
1) To 2.0 g reference sample are added 100 mL
Titration stand . . . . . .
Entry type . . . . . . . . .
.
.
.
.
.
.
.
.
Stand 1
Weight m
deion. water. Shake for 1 hour.
Lower limit [g] . . . . . . . . . 0.4
Upper limit [g] . . . . . . . . . 4.0 2) Filter through folded filter. Dilute 25 mL fil-
ID1 . . . . . . . . . . . . . . . . beetroot
Molar mass M . . . . . . . .
Equivalent number z . . . .
.
.
.
.
.
.
.
.
62.0049
1
trate with deion. water 1:1.
Temperature sensor . . . . . . . . . TEMP A
Dispense 3) The sample is ready to be measured. 5 mL ISA
Titrant . . . . . . . . . . . . . . ISA
Concentration [mol/L] . . . . . . . 1.0 are added automatically by the titrator before
Volume [mL] . . . . . . . . . . . . 5.0
Stir measuring the potential.
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 180
Measure
Sensor . . . . . . . . . . . . . . NO3--sensor
Unit of meas . . . . . . . . . . . . As installed
∆E [mV] . . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . . 10.0 Method
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . .
t(max) [s] . . . . . . . . .
.
.
.
.
.
.
.
.
10.0
30.0
1) All measurements should be performed using
Calculation
Result name . . . . . . . . . . . . NO3--conc
the same stirring conditions. This means the
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R=pw(-E)*1000 same speed, stirrer type, distance to electrode
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
mmol/L
3
etc.
Calculation
Result name . . . . . . . . . . . . content dry 2) Rinse electrode with deion. water after each
Formula . . . . . . . . . . . . . . R2=R1*M*200/m
Constant . . . . . . . . . . . . . . measurement and remove clinging water drops
Result unit . . . . . . . . . . . . mg/kg
Decimal places . . . . . . . . . . . with a soft paper tissue.
Statistics
Ri (i=index) . . . . . . . . . . . . R2
Standard deviation s . . . . . . . . Yes 3) Each measurement requires about 3 minutes
Outlier test . . . . . . . . . . . . Yes stirring time for a stable measured value to be
Record
Output unit . . . . . . . . . . . . Printer attained.
All results . . . . . . . . . . . . Yes
Reference samples (standards)

The Swiss Federal Research Institute for Fruit, Wine and Garden Produces in Wädenswil, Switzerland
(www.admin.ch/sar/faw) offers reference samples for nitrate determinations. The certified nitrate
content of these samples, which have been mechanically mixed and dried in vacuum over phosphor-
pentoxide, was determined using different analysis methods.
Results
Sample n Direct measurement with ISE Content acc. to certificate
(Number) Content RSD HPLC GC
Lettuce head 10 27.073 mg/kg 0.2 % 26.600 - 27.300 mg/kg 27.400 - 30.000 mg/kg
Spinach 3 6966 mg/kg 1.2 % 6560 - 6750 mg/kg 6380 - 6540 mg/kg
Cabbage, white 2 8428 mg/kg 1.0 % 7350 - 8440 mg/kg 8680 - 8730 mg/kg
Carrots 3 1545 mg/kg 0.6 % 1390 - 1510 mg/kg 1340 - 1510 mg/kg
Red beet 3 4583 mg/kg 0.4 % 4710 - 4970 mg/kg 4300 - 4730 mg/kg
Disposal
Other titrators --
Author: Albert Aichert
4. Potassium Selective Electrode
Theory The potassium electrode is a liquid membrane electrode. This type of electrode
has in its membrane a neutral, cyclic organic compound which binds and can thus
determine cations (such as potassium) due to its structure.
The ion active substance in the potassium electrode is the antibiotic valinomycin.
Valinomycin shows only a very slight cross reactivity with sodium.
Measurement range When ISA is used to adjust the ionic strength, a linear calibration curve from 0.1
– 10-4 mol/L is obtained.
The detection limit lies somewhat above 2•10-6 mol/L. The slope, theoretically
calculated from the Nernst equation to be - 58.16 mV at 20°C, lies at - 58 mV in
practice.
Electrodes
Bridging electrolyte 0.9 mol/L aluminum sulfate solution (ME-51 340 072), 0.1 mol/L NaCl or
0.1 mol/L TEACl can be used as the bridging electrolyte (TEACl = tetraethylam-
moniumchloride). The inner electrolyte (potassium chloride solution, 3 mol/L,
ME-51 340 049) should be replaced monthly.
Storage Store the potassium electrode dry (in protective sleeve) or in a dilute potassium
solution.
Reference electrode: drain electrolyte. To store, seal orofice for filling with
rubber stopper. (The longevity of the reference electrode is reduced if the bridging
electrolyte chamber is consistently filled up over the inner diaphragm).
Handling The polymer measurement membrane can be damaged by mechanical impact
(e.g. magnetic stirrer, cleaning). If the membrane is damaged, the membrane
module must be replaced.
Contamination A sluggish response indicates that the sensor is contaminated. Deposits on the
surface of the membrane module can be removed by placing the potassium
electrode in deion. water or dilute acid or base (< 0.001 mol/L) for several
minutes. After rinsing with deion water, the electrode is reconditioned for several
hours in approx. 0.01 mol/L potassium solution.
If the electrode is no longer regenerable, the membrane module must be replaced.
Reagents
ISA solutions Corresponds with the bridging electrolyte used:
Aluminium sulfate solution 0.9 mol/L (Art. No. 51 340 072) or
NaCl solution 5 mol/L or
TEACl 10 mol/L (tetraethylammoniumchloride)
The ISA solutions can also be freshly made:
aluminum sulfate solution 0.9 mol/L:
Dissolve 600 g Al2(SO4)3 • 18 H2O in 600 mL deion. water while warming. Cool
to room temp. and adjust volume to 1000 mL. The milky colloidal solution keeps
for several weeks at room temp. Should a sediment form upon standing for some
time, use the remaining clear solution by pipetting off the top.
NaCl solution 5 mol/L:
Dissolve 29.22 g NaCl p.a. in 80 mL deion. water in a volumetric flask and
fill to 100 mL.
K+ standard Potassium standard solution 1000 mg/L:
potassium standard solution (KCl in water) 1.000 g± 0.002 g , e.g. from
MERCK No. 109924
or weigh 1.907 g KCl, p.a. MERCK No. 104936 into a 1000 mL volumetric
flask, fill with deion. water to mark.
This solution keeps for several months.
Hints
Ionic strength The total activity of measurement and calibration solutions must be constant. By
adding to each a constant amount of ISA solution, a constant ionic strength is
attained.
Interfering ions In order to keep the error induced by interfering ions below 10 %, the molar
relation (X- / K+ ) of these ions must be smaller than the value in parenthesis:
Rb+ (<0.005), Cs+ (<0.02), NH4+ (<1), Sr+2 (<20), Ca+2 (<500),
H+ (<1000), Na+ (<2000), Mg+2 (<2000)
Cationic tensides should not be present.
Ammonium: can be removed by boiling at pH 12 (with NaOH). Cool and
neutralize prior to measuring.
Application and Use

Application The potassium electrode is used for potassium determination in water, bever-
ages, serum, infusion solutions, soil samples and fertilizers.
Use The potassium determination using an ion selective electrode is especially
useful for routine analyses (same samples with known matrix), in which the
potassium content must be determined quickly and simply.
Alternatives The potassium determination can also be performed using ion chromatography,
flame photometry or atomic absorption.
For higher concentrations,i.e. > 10-3 mol/L, potentiometric titration using sodi-
um tetraphenylborate (Na-TPB) is possible.
Advantages - wide application range (0.1 – 10-4 mol/L)
- rapid and simple determination
- smaller investment
(compared to ion chromatography or atomic absorption)
Disadvantages - pH sensitive
METTLER TOLEDO
M110 Calibration of the Potassium Electrode
Sample: 50 mL potassium solution Instruments: METTLER TOLEDO DL70ES

1 g/L and 10-2 g/L HP Deskjet 500 Printer
MT AT261 Balance
Substance: Potassium, K+
M = 39.0983 g/mol , z = 1 Method: K007

(5 mol/L NaCl solution) DT120 (temp. sensor Pt100)
Titrant: --
Indication: DX239 Potassium ISE
Standard: -- DX200 Reference electrode
0.9 mol/L Al2(SO4)3 )

Method K007 Calibration K+-sensor 04-Jan-1994 9:16

User aa
Measured 04-Jan-1994 9:18
RESULTS
1/1 0.01 g/L 50.0 mL pH,pM,pX 2.000

1/2 1 g/L 50.0 mL pH,pM,pX 0.000
CALIBRATION
Sensor K+-Sensor
Slope -56.10 mV/pX
Method Remarks
Method K007 Calibration K+-sensor
Version 04-Jan-1994 9:16 1) Calibration and measurement solutions should
Method ID . . . . . . . . . . . . . K007
Title . . . . . . . . . . . . . Calibration K+-sensor
Date/time . . . . . . . . . . . . . 04-Jan-1994 9:16 2) All measurements should be performed using
Sample
Volume [mL] . . . . . . . . . . . 50.0
ID1 . . . . . . . . . . . . . . . . etc.
Molar mass M . . . . . . . . . . . . 39.0983
Equivalent number z
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
1
TEMP A
Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . .
Measure
. . . . . . . . 300
K+-sensor
Sensor . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. mV
∆E [mV] . . . . . .
∆t [s] . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
0.5
2.0
sensor.
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . .
t(max) [s] . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
10.0
30.0
Calculation
Formula . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Result unit . . . . . . . . . . . . mV
Calibration
Sensor . . . . . . . . . . . . . . . Na+-sensor measurement and remove adhering water
Second buffer . . . . . . . . . . 0.0
Third buffer . . . . . . . . . . 0.0
Fourth buffer . . . . . . . . . . 0.0 6) Each measurement requires 5 minutes stirring
Fifth buffer . . . . . . . . . . 0.0
Sixth buffer . . . . . . . . . . 0.0 time for a stable measured value.
Seventh buffer . . . . . . . . . 0.0
Eighth buffer . . . . . . . . . . 0.0
Ri (i=index) . . . . . . . . . . . . R1 7) For three-point calibration with automatic pro-
Minimal slope . . . . . . . . . . . -45.0
Maximal slope . . . . . . . . . . . -65.0 duction of the standard solutions, a method
Record
Output unit . . . . . . . . . . . . Printer similar to the one for the nitrate ISE can be
All results . . . . . . . . . . . . Yes
used (page 29).
Typical calibration curve of a potassium selective electrode with ISA solution
Disposal
--
Other titrators
METTLER TOLEDO
M111 Potassium Determination with Ion Selective Electrode
Sample: 50 mL Sample solution with Instruments: METTLER TOLEDO DL77

1000 to 1 mg/L potassium Printer (HP Desk Jet 500)
Substance: Potassium, K+ Method: K00A, K00B

M = 39,0983 g/mol , z = 1
(5 mol/L NaCl)
Indication: DX239 Potassium ISE
Titrant: - DX200 Reference electrode
Standard: - 0.9 mol/L Al2(SO4)3 )
1. Aqueous potassium solutions were used for these measurements. They were made from the
potassium standard 1.000 ± 0.002 g K+ (MERCK Art. No. 109924).
2. The potassium electrode was recalibrated daily with standard solutions 1.0 and 0.01 g K+/L, if
necessary after 2-3 series.
3. The potassium and reference electrodes were stored in dilute potassium solution (0.001 g/L)
before and between measurements.
Concentration Recovery RSD of several series (n= 6)

1000 97 - 103 % 0.3 - 1.0 % 0.4 - 1.0 %
100 98 - 103 % 0.2 - 1.4 % 0.3 - 1.4 %
10 99 - 102 % 0.3 - 1.2 % 0.4 - 1.3 %
5 98 - 102 % 0.3 - 0.8 % 0.4 - 0.7 %
1 110 - 115 % 1.1- 4.2 % 1.2 - 4.2 %
Result
The concentration 0.001 mg/L is not in the linear range (see calibration curve page 39). Thus, the range
of useful concentrations for the potassium electrode was limited from 1000 to 5 mg/L.
Method A (direct measurement with mean value) Method B (Single direct measurement)
Method K00A K+-content Method K00B K+-content
Version 04-Jan-1994 9:49 Version 04-Jan-1994 9:09
Title Title
Method ID . . . . . . . . . . . . . K00A Method ID . . . . . . . . . . . . . K00B
Title . . . . . . . . . . . . . K+-content Title . . . . . . . . . . . . . K+-content
Date/time . . . . . . . . . . . . . 04-Jan-1994 9:49 Date/time . . . . . . . . . . . . . 04-Jan-1994 9:09
Sample Sample
ID1 . . . . . . . . . . . . . . . . ID1 . . . . . . . . . . . . . . . . K+
Stir Stir
Speed [%] . . . . . . . . . . . . . 50 Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 300 Time [s] . . . . . . . . . . . . . . 300
Measure Measure
Sensor . . . . . . . . . . . . . . K+-Sensor Sensor . . . . . . . . . . . . . . K+-sensor
∆E [mV] . . . . . . . . . . . . . . 0.2 ∆E [mV] . . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . . 5.0 ∆t [s] . . . . . . . . . . . . . . 5.0
t(min) [s] . . . . . . . . . . . 10.0 t(min) [s] . . . . . . . . . . . 30.0
t(max) [s] . . . . . . . . . . . . . 90.0 t(max) [s] . . . . . . . . . . . . . 60.0
Measure Calculation
Result name . . . . . . . . . . . .
Sensor . . . . . . . . . . . . . . K+-Sensor Formula . . . . . . . . . . . . . . R=E
Unit of meas . . . . . . . . . . . . mV
Constant . . . . . . . . . . . . . .
∆E [mV] . . . . . . . . . . . . . . 0.2
Result unit . . . . . . . . . . . . p(K+)
∆t [s] . . . . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . . . . . . . 90.0 Result name . . . . . . . . . . . . K+-content
Sensor . . . . . . . . . . . . . . +
K -Sensor Constant . . . . . . . . . . . . . .
Unit of meas . . . . . . . . . . . . mV Result unit . . . . . . . . . . . . mg/L
∆t [s] . . . . . . . . . . . . . . 5.0 Statistics
Sensor . . . . . . . . . . . . . . K+-Sensor Record
∆t [s] . . . . . . . . . . . . . . 5.0
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . . . . . . 10.0
t(max) [s] . . . . . . . . . . . . . 90.0
Measure
K+-Sensor
Sensor . . . . . . . . . .
Unit of meas . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
mV
0.2
Remarks
∆t [s] . . . . . . . . . . . . . . 5.0
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . . . . . . 10.0
t(max) [s] . . . . . . . . .
Measure
. . . . 90.0 Method A
Sensor . . . . . . . . . . . . . . K+-Sensor
Unit of meas . . . . . . . . . . . . mV 1) Stirring during five minutes.
∆E [mV] . . . . . . . . . . . . . . 0.2
∆t [s] . . . . . . . . . . . . . . 5.0
t(min) mode . . . . . . . .
t(min) [s] . . . . . . .
.
.
.
.
.
.
.
.
Fix
10.0
t(max) [s] . . . . . . . . .
Calculation
. . . . 90.0
Result name . . . . . . . . . . . .
Formula . . . . . . . . . . . . . . R1=E[1]
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
. p(K+)
Calculation
. . . . 4
the mean of these six values.
Result name . . . . . . . . . . . . K+-single
Formula . . . . . . . . . . . . . . R2=pw(-E[1])*1000
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mg/L
Calculation
. . . . 4
Method B
Result name . . . . . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
. R3=(C3+E[5]+E[6])/6
. C3=E[1]+E[2]+E[3]+E[4]
Result unit . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 3
Calculation 2) Acquisition of one value.
Result name . . . . . . . . . . . . K+-x of 6
Formula . . . . . . . . . . . . . . R4=pw(-R3)*1000
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
. mg/L
Statistics
. . . . 4
Ri (i=index) . . . . . . . . . . . . R2
.
.
.
.
.
.
.
.
Yes
Yes
Outlier test . . . . . . . .
Statistics
. . . . Yes
used in the calculation.
Ri (i=index) . . . . . . . . . . . . R4
Outlier test . . . . . . . . . . . . Yes
Record
All results . . . . . . . . . . . . Yes
Disposal
Other titrators --
Results
Sample Dilution Direct measurement with potassium electrode Content
n Mean value srel (Producer spec.)
Milk 1:20 6 1557 mg/L 0.36 % 1.6 -1.9 g/L *
Orange juice 1:20 6 1698 mg/L 0.12 % 1.4 - 2.7 g/L*
Apple juice 1:20 6 973 mg/L 0.12 % 0.9 - 1.5 g/L*
Grape juice, red 1:20 6 1219 mg/L 0.24 % 0.9 - 2.2 g/L*
Wine, red 1:10 6 739 mg/L 0.34 % 0.4 - 1.6 g/L*

Italian
Wine, white 1:10 6 764 mg/L 0.20 % 0.4 - 1.6 g/L*
Swiss
Carrot juice 1:50 6 3076 mg/L 0.29 % 1.5 - 3.4 g/L*
freshly pressed
Beet juice ** 1:50 6 2745 mg/L 0.22 % —
with sour whey
Beet juice ** 1:50 6 3588 mg/L 0.33 % 3.2 - 7.2 g/L*
org. grown
Beet juice ** 1:50 6 4575 mg/L 0.40 % 3.2 - 7.2 g/L*
wholesale
Elderberry juice 1:50 5 3739 mg/L 0.17 % 4.4 - 5.3 g/L*
70% fruit flesh
Infusion solution 1:5 3 200.8 mg/L 0.20 % 199.2 mg/L
Liquid fertilizer 1:400 4 26.69 g/L 0.30 % 26.6 g/L
Garden soil 1:1 3 33.6 mg/kg 0.29 % —-

from garden
Potting soil 1:2 4 496 mg/kg 0.26 % 290-440 mg/kg
purchased
* Obtained from: Schweizerisches Lebensmittelbuch
** Beet = red beet
General Potassium is important for cell metabolism and for maintenance of the potas-
sium / sodium equilibrium. Excess potassium is excreted by the body, unlike
sodium. Thus, excess sodium can result in such a shift of the equilibrium in
favor of sodium that even with normal potassium values, a potassium deficien-
cy may show up.
Potassium deficiency may lead to muscle weakness and tightness, an irregular
heart rhythm, high pulse rates, oedemas and frequently to cramps, especially of
the rear and leg muscles.
Beverages Are diluted 1:10 to 1:50, depending on the potassium content. To 50 mL diluted
sample are added 1 mL ISA solution before measuring.
Infusion solution Dilute sample 1:5. To 50 mL add 0.5 mL ISA solution and measure. Less ISA
solution is used for this sample as it already contains NaCl.
Fertilizer Dilute sample 1: 400. To 50 mL add 1 mL ISA solution and measure.
Garden soil Dry overnight at 170 – 180 °C. Extraction: to 149 g add 200 mL deion. water,
mix with mixer for 1 minute, let settle for 2 hours. Vacuum filter. To 50 mL
filtrate add 1 mL ISA solution and measure.
Potting soil Dry overnight at 170 – 180 °C. Extraction: to 149 g add 400 mL deion. water,
mix with mixer for 1 minute, let settle for 4 hours. Vacuum filter. To 50 mL
filtrate add 1 mL ISA solution and measure.
General remarks:
1) All measurements were performed using the simple direct measurement (method B).
5. Sodium Selective Electrode
Theory The sodium electrode is a glass electrode. pH glass electrodes show a negligible
alkali error. Amplification of the “alkali error” leads to sodium selective
electrodes which respond only to changes in the sodium ion concentration at pH
values above 7. Besides glass membranes, gel membranes can also be used for
the sodium determination. The ion active substance is the antibiotic actino-
mycene.
Measurement range When ISA is used to adjust the ionic strength and the pH value (over pH 7), a
linear calibration curve from 0.1 – 10-4 mol/L is obtained. The detection limit lies
around 5•10-6 mol/L. The slope, theoretically calculated from the Nernst equa-
tion to be - 58.16 mV at 20°C, lies at - 58 mV in practice.
Electrodes
Bridging electrolyte 0.1 mol/L ammonium chloride, NHCl, is used as bridging electrolyte for the
4
reference electrode.
Conditioning Condition new sodium electrode overnight in a concentrated NaCl solution.
Storage Store sodium electrode with the glass membrane in 0.1 mol/L NaCl solution.
Reference electrode: drain electrolyte. To store, seal orifice for filling with
rubber stopper. (The longevity of the reference electrode is reduced if the
bridging electrolyte chamber is consistently filled up over the inner diaphragm).
Contamination A sluggish response or too small slope (>52 mV/pNa) indicates that the sensor
is contaminated. Deposits on the surface of the glass membrane can be removed
by cleaning with the usual lab cleansers. After each treatment, rinse electrode
with deion water and conditioned for several hours in a concentrated sodium
solution.
Reagents
ISA solution Ionic Strength Adjustment:
basic ammonium chloride solution or triethanolamine solution.
Production Basic ammonium chloride solution (4 m NH4Cl and 1 m NH4OH):

dissolve 213 g NH4Cl and 140 g NH4OH 25 % in 800 mL deion. water. Adjust
volume to 1000 mL using volumetric flask.
Triethanolamine solution:
Dissolve 74.6 g triethanolamine in 800 mL deion. water, adjust to pH 10.2 with
HCl. Fill volumetric flask to 1000 mL mark.
Na+ standard Sodium standard solution 1000 mg/L:

Sodium standard solution (NaCl in water) 1.000 g± 2 mg MERCK No. 109927
fill to 1000 mL with deion water in a volumetric flask.This solution keeps for
several months.
Sodium standard solution 0.1 mol/L:
Dissolve 5.844 g NaCl (titrimetric standard) in 800 mL deion. water and fill to
1000 mL in volumetric flask.
Hints
Ionic strength The total activity of sample and calibration solutions must be constant. The pH
value must be over 7. By adding to each sample a constant amount of ISA
solution, a constant ionic strength is attained.
Interfering ions In order to keep the error induced by interfering ions below 10 %, the molar
relation (X- / Na+ ) of these ions must be smaller than the value in parenthesis:
H+ (<0.001), Li+ (<1), K+ (<5), NH4+ (<50), Mg+2 (<2000)
Silver ions Ag+ should not be present.
Application and Use
Application The sodium electrode is used for sodium determination in water, beverages, diet
foods, serum, soil samples and glass.
Use The sodium determination using an ion selective electrode is especially useful for
routine analyses (same samples with known matrix), in which the sodium content
must be determined quickly and simply.
Alternatives The sodium determination can also be performed using flame photometry or
atomic absorption. A sodium content determination via titration is possible only
indirectly by chloride determination, provided that Na is present as NaCl.
Advantages - wide application range (0.1 - 10-4 mol/L)

- the determination is rapid and simple
Disadvantages - pH value sensitive
METTLER TOLEDO
M112 Calibration of the Sodium Electrode
Sample: 50 mL sodium-containing sol’n Instruments: METTLER TOLEDO DL77

0.1 mol/L and 10-3 mol/L HP Deskjet 500 Printer
MT AT261 Balance
Substance: Sodium, Na+
M = 22.99 g/mol , z = 1 Method: Na07

(4 mL NH4Cl and 1 ml NH4OH) DT120 (temp. sensor Pt100)
Titrant: --
Indication: DX223 Sodium ISE
Standard: -- DX200 Reference electrode
(bridge electrolyte: 0.1 M NH4Cl)

Market Support Laboratory
Method Na07 Calibration Na+-sensor 16-Mar-1994 12:45

User aa
Measured 16-Mar-1994 13:08
RESULTS
1/1 Na+ 10-3 mol/L 50.0 mL pH,pM,pX 3.000

1/2 Na+ 10-1 mol/L 50.0 mL pH,pM,pX 1.000
CALIBRATION
Sensor Na+-Sensor
Slope -57.75 mV/pX
Method Remarks
Method Na07 Calibration Na+-sensor
Version 16-Mar-1994 12:45 1) Calibration and measurement solutions should
Method ID . . . . . . . . . . . . . Na07
Title . . . . . . . . . . . . . Calibration Na+-sensor
Date/time . . . . . . . . . . . . . 16-Mar-1994 12:45 2) All measurements should be performed using
Sample
Volume [mL] . . . . . . . . . . . 50.0
ID1 . . . . . . . . . . . . . . . . Na+ etc.
Molar mass M . . . . . . . . . . . . 0.0
Equivalent number z
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
1
TEMP A
Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . .
Measure
. . . . . . . . 600
K+-sensor
Sensor . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. mV
∆E [mV] . . . . . .
∆t [s] . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
0.2
2.0
sensor.
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . .
t(max) [s] . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
30.0
60.0
Calculation
Formula . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Result unit . . . . . . . . . . . . mV
Calibration
Sensor . . . . . . . . . . . . . . . Na+-sensor measurement and remove adhering water
Second buffer . . . . . . . . . . 1.0
Third buffer . . . . . . . . . . 0.0
Fourth buffer . . . . . . . . . . 0.0 6) Each measurement requires 10 minutes stir-
Fifth buffer . . . . . . . . . . 0.0
Sixth buffer . . . . . . . . . . 0.0 ring time for a stable measured value.
Seventh buffer . . . . . . . . . 0.0
Eighth buffer . . . . . . . . . . 0.0
Ri (i=index) . . . . . . . . . . . . R1 7) For three-point calibration with automatic pro-
Minimal slope . . . . . . . . . . . -45.0
Maximal slope . . . . . . . . . . . -65.0 duction of the standard solutions, a method
Record
Output unit . . . . . . . . . . . . Printer similar to the one for the nitrate ISE can be
All results . . . . . . . . . . . . Yes
used (page 28).
Typical calibration curve of a sodium selective electrode with ISA solution
Disposal
--
Other titrators
METTLER TOLEDO
M113 Sodium Determination with Ion Selective Electrode
Sample: 50 mL Sample solution with Instruments: METTLER TOLEDO DL77

0.1 to 0.001 mol/L sodium Printer (HP Desk Jet 500)
Substance: Sodium, Na+ Method: Na0A, Na0B

M = 22.99 g/mol , z = 1
(4 mL NH4Cl and 1 ml NH4OH)
Indication: DX223 Sodium ISE
Titrant: - DX200 Reference electrode
(bridge electrolyte: 0.1 M NH4Cl)
Standard: -
1. Aqueous sodium solutions were used for these measurements. They were made from NaCl
(titrimetric standard).
2. The sodium electrode was recalibrated daily with standard solutions 0.1 and 0.001 g Na+/L.
3. The soldium electrode was stored in a concentrated sodium solution.
4. Preparation: Add 1 mL ISA solution to 50 mL sample before measuring. The solutions were
produced fresh daily.
Concentration Recovery srel of several series (n= 6)

0.1 98 - 102 % 0.2 - 0.5 % 0.2 - 0.6 %
0.01 95 - 100 % 0.2 - 0.6 % 0.3 - 0.7 %
0.001 97 - 101 % 0.2 - 0.8 % 0.2 - 0.9 %
0.0005 101 - 106 % 0.2 - 0.4 % 0.2 - 0.5 %
0.0001 131 - 129 % 0.2 - 0.9 % 0.2 - 0.9 %
Result
At concentrations under 0.001 mol/L, longer stir times (15 – 20 minutes) were necessary to attain a good
reproducibility.
The concentration 0.0001 mol/L is not in the linear range (see calibration curve page 47). Thus, the
range of useful concentrations for the sodium electrode was limited from 0.1 mol/L to 0.001 mol/L.
Method Na0A Na+-content Method Na0B Na+-content
Version 15-Mar-1994 19:48 Version 22-Mar-1994 13:07
Title Title
Method ID . . . . . . . . . . . . . Na0A Method ID . . . . . . . . . . . . . Na0B
Title . . . . . . . . . . . . . Na+-content Title . . . . . . . . . . . . . Na+-content
Date/time . . . . . . . . . . . . . 15-Mar-1994 19:48 Date/time . . . . . . . . . . . . . 22-Mar-1994 13:07
Sample Sample
Titration stand . . . . . . . . . . Stand 1 Titration stand . . . . . . . . . . ST20 1
ID1 . . . . . . . . . . . . . . . . ID1 . . . . . . . . . . . . . . . .
Stir Stir
Speed [%] . . . . . . . . . . . . . 50 Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 600 Time [s] . . . . . . . . . . . . . . 300
Measure Measure
Sensor . . . . . . . . . . . . . . Na+-Sensor Sensor . . . . . . . . . . . . . . Na+-sensor
∆E [mV] . . . . . . . . . . . . . . 0.2 ∆E [mV] . . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . . 5.0 ∆t [s] . . . . . . . . . . . . . . 5.0
t(min) [s] . . . . . . . . . . . 10.0 t(min) [s] . . . . . . . . . . . 60.0
t(max) [s] . . . . . . . . . . . . . 90.0 t(max) [s] . . . . . . . . . . . . . 120.0
Measure Calculation
Result name . . . . . . . . . . . .
Sensor . . . . . . . . . . . . . . Na+-Sensor Formula . . . . . . . . . . . . . . R=E
Unit of meas . . . . . . . . . . . . mV
Constant . . . . . . . . . . . . . .
∆E [mV] . . . . . . . . . . . . . . 0.2
Result unit . . . . . . . . . . . . p(Na+)
∆t [s] . . . . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . . . . . . . 90.0 Result name . . . . . . . . . . . . Na+-content
Sensor . . . . . . . . . . . . . . +
Na -Sensor Constant . . . . . . . . . . . . . .
Unit of meas . . . . . . . . . . . . mV Result unit . . . . . . . . . . . . mmol/L
∆t [s] . . . . . . . . . . . . . . 5.0 Calculation
t(min) mode . . . . . . . . . . . . Fix Result name . . . . . . . . . . . . Na+-content
t(min) [s] . . . . . . . . . . . 10.0 Formula . . . . . . . . . . . . . . R3=R2*M
t(max) [s] . . . . . . . . . . . . . 90.0 Constant . . . . . . . . . . . . . .
Measure Result unit . . . . . . . . . . . . mg/L
Sensor . . . . . . . . . . . . . . Na+-Sensor Decimal places . . . . . . . . . . . 2
Unit of meas . . . . . . . . . . . . mV Statistics
∆E [mV] . . . . . . . . . . . . . . 0.2 Ri (i=index) . . . . . . . . . . . . R2
∆t [s] . . . . . . . . . . . . . . 5.0 Standard deviation s . . . . . . . . Yes
t(min) mode . . . . . . . . . . . . Fix Rel. standard deviation srel . . . . Yes
t(min) [s] . . . . . . . . . . . 10.0 Outlier test . . . . . . . . . . . . Yes
t(max) [s] . . . . . . . . . . . . . 90.0 Record
Measure Output unit . . . . . . . . . . . . Printer
Sensor . . . . . . . . . . . . . . Na+-Sensor All results . . . . . . . . . . . . Yes
Unit of meas . . . . . . . . . . . . mV
∆E [mV] . . . . . . . . . . . . . . 0.2
∆t [s] . . . . . . . . . . . . . . 5.0
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . .
t(max) [s] . . . . . . . . .
.
.
.
.
.
.
.
.
10.0
90.0
Remarks
Measure
Sensor . . . . . . . . . . . . . . Na+-Sensor
Unit of meas . . . . . . . . . . . . mV
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
.
.
.
.
.
.
.
.
0.2
5.0
Method A
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . .
t(max) [s] . . . . . . . . .
.
.
.
.
.
.
.
.
10.0
90.0
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
. R1=E[1]
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . p(Na+) tions) at an interval of at least 10 s.
Decimal places . . . . . . . . . . . 4
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
Na+-single
R2=pw(-E[1])*1000
3) The sodium concentration is calculated from
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
. mmol/L the mean of these six values.
Decimal places . . . . . . . . . . . 4
Calculation
Result name . . . . . . . . . . . .
Formula . . . . . . . . . . . . . . R3=(C3+E[5]+E[6])/6
Constant . . . . . . . . . . . . . . C3=E[1]+E[2]+E[3]+E[4]
Result unit . . . . . . . .
.
.
.
.
.
.
.
. 3
Method B
Calculation
Result name . . . . . . . . . . . . Na+-x of 6 1) Stirring during five minutes.
Formula . . . . . . . . . . . . . . R4=pw(-R3)*1000
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
mmol/L
4
Statistics
Ri (i=index) . . . . . . . .
.
.
.
.
.
.
.
.
R2
Yes
Outlier test . . . . . . . . . . . . Yes the dilution factor can be entered as a correc-
Statistics
Ri (i=index) . . . . . . . .
.
.
.
.
.
.
.
.
R4
Yes
Outlier test . . . . . . . .
.
.
.
.
.
.
.
.
Yes
Yes used in the calculation.
Record
All results . . . . . . . . . . . . Yes
Disposal
Other titrators --
Results
Sample Dilution Direct measurement with Na electrode Content
n Mean value srel Producer spec.
Milk, full cream 1:10 6 400.8 mg/L 0.20 % 430 -490 mg/L *
pasteurized
Milk, full cream 1:10 6 433.8 mg/L 0.20 % 430 -490 mg/L *
raw
Apple juice none 4 8.2 mg/L 0.64 % < 30 mg/L*
Grape juice,red none 5 23.8 mg/L 0.66 % < 30 mg/L*
Wine, red none 5 12.2 mg/L 0.63 % 10 - 80 mg/L*

Italian
Wine, white none 5 8.4 mg/L 2.0 % 10 - 80 mg/L*

Swiss
Mineral water none 6 8.17 mg/L 0.22 % 8.2 mg/L
Drinking water none 5 3.81 mg/L 0.35 % —

Schwerzenbach
Bouillon 1:20 5 468.5 mg/L 0.35 % < 1.2 g/L

sodium reduced
Bouillon 1:50 5 4110 mg/L 0.41 % ~ 4 g/L

normal
Herb paté 1:8 6 175.9 mg/kg 0.52 % < 0.4 g/kg

sodium reduced
Infusion solution 1:100 5 142.5 mmol/L 0.72 % 141.5 mmol/L
* Obtained from: Schweizerisches Lebensmittelbuch
General Sodium influences cell metabolism. The body cannot get rid of excess sodium.
Therefore, a sodium excess shifts the sodium / potassium equilibrium to the
disadvantage of potassium.
A high blood pressure requires a diet low in sodium.
Milk Dilute sample 1:10. To 50 mL of this add 1 mL ISA solution and measure.
Apple juice To 50 mL undiluted sample add 1 mL ISA solution and 1.5 mL NH 4OH 5 %
and measure. The pH of the sample is adjusted to pH 7.5 with the excess
NH4OH. (For correct measurement with the sodium electrode, the pH must be
over 7.)
Wine, grape juice To 50 mL undiluted sample add 1 mL ISA solution and 1.5 mL NH 4OH 5 %
and measure. The pH of the sample is adjusted to pH 8 with the excess NH4OH.
(For correct measurement with the sodium electrode, the pH must be over 7.)
Mineral water To 50 mL undiluted sample add 1 mL ISA solution and measure.
Drinking water To 50 mL undiluted sample add 1 mL ISA solution and measure.

Due to the low sodium content, the standards 10-3 and 10-4 mol/L were used for
calibration for this sample.
Bouillon Place a bouillon cube in 300 mL deion. water and warm till it has dissolved. Let
cool and use deion. water to adjust volume to 500 mL. Dilute this solution 1:20
resp. 1:50 with deion. water. To 50 mL add 1 mL ISA solution and measure.
Herb paté Mix entire contents of can (125 g) with 700 mL deion. water for about
5 minutes. Decant fat. Fill to 1000 mL with deion. water. To 50 mL of this add
1 mL ISA solution and measure.
Infusion solution Dilute sample 1:100 and to 50 mL of this add 1 mL ISA solution and measure.
General remarks:
1) All measurements were performed using the simple direct measurement (method B).
6. Trouble-shooting
Completely wrong measured values:

Instrument defective. Test with short circuit plug.
Bad contact to electrode plug. Plug in and out a few times.
Reference electrode empty. Fill with electrolyte, control ground joint.
Ground joint diaphragm dried out. Open joint, let electrolyte flow out and
close joint firmly.
Unstable measured value:

Instrument defective. Test with short circuit plug.
Bad contact to electrode plug. Plug in and out a few times.
No ISA solution. Add ISA solution.
Larger air bubble in electrode. Shake vigorously (like a fever thermometer).
Electrode body defective. Replace.
Reference electrode contaminated or defective.Clean or replace reference electrode
Insufficient slope:
Calibration solution contaminated or Make new calibration solutions.
incorrectly diluted.
Membrane module screwed in too Screw in membrane module tightly.
loosely.
Membrane contaminated. Clean or replace membrane module.
Larger air bubble in electrode. Shake vigorously once toward electrode head
(like a fever thermometer).
Electrode not conditioned long enough. Condition in dilute solution of the
selective ion, approx. 0.001mol/L.
(For Na electrode use conc. NaCl solution)
Bridging electrolyte leaked out of the Refill with bridging electrolyte and close ground
reference electrode. joint firmly.
Drift in display (sluggish response):
Temperature not constant. Use thermostat.
Membrane contaminated. Clean or replace membrane module.
Electrode not conditioned long enough. Condition in dilute solution of the
selective ion, approx. 0.001mol/L.
(For Na electrode use conc. NaCl solution)
Reference electrode contaminated or defective.Clean or replace reference electrode.
Wrong bridging electrolyte. Replace with correct bridging electrolyte and
close ground joint firmly.
Measurement membrane exhausted Replace membranme module.
(Na: replace electrode).
Content too low:

Too much time or too many measurements Recalibrate, at least once a day.
since last calibration.
No ISA solution in samples. Add ISA solution.
Incorrect pH value of sample solutions. Control sample pH value.
correct pH value, i.e.: with ISA or buffer solutions
(For Na electrode use ammonium to adjust pH > 7).
Ions to be determined partially complexed. Standard addition instead of direct measurement,
add ISA solution.
Content too high:

Too much time or too many measurements Recalibrate, at least once a day.
since last calibration.
Concentration of interfering ions too high. Eliminate interfering ions (precipitate, complex).
Concentration too low or outside the Dilute less.
calibration range (measurement in the Recalibrate with standards near the sample
non-linear range). concentration.
7. Summary of the Ion Selective Electrodes and Reagents
Used
Electrode Name Type Lin. meas’ment range Lower limit Interfering ions
Fluoride DX219 Solid state 1 - 10-6 mol/L 0.01 ppm OH-

membrane
Chloride DX235 Solid state 1 - 10-4 mol/L 2 ppm no Br-, I-, CN-,
membrane S-2
Nitrate DX262 PVC 1 - 10-5 mol/L 0.1 ppm Br-, I-, F-, Cl-, NO2-
membrane ClO4-, ClO3-, HS-,
CN-, SO4-2, PO4-3,
CO3-, SCN-
no anion. tensides
Potassium DX239 PVC 1- 10-4 mol/L 0.1 ppm Na+, Rb+, Cs+,
membrane Ca+2, Mg+2, NH4+
no cation. tensides
Sodium DX223 Glass 0.1 - 10-4 mol/L 25 ppm Li+, K+, NH4+,
electrode Mg+2, no Ag+
pH ISA solutions Reference electrode
range Type Inner electrol. Bridging electrolyte
5-8 TISAB 3 DX200* KCl 3 mol/L KNO3 1 mol/L
2 -11 NaNO3 5 mol/L DX200 KCl 3 mol/L KNO3 1 mol/L
3 - 10 Al2(SO4)3 0.9 mol/L DX200 KCl 3 mol/L Al2(SO4)3 0.9 mol/L
4-9 Al2(SO4)3 0.9 mol/L DX200 KCl 3 mol/L Al2(SO4)3 0.9 mol/L
NaCl 5 mol/L KCl 3 mol/L NaCl 0.1 mol/L
TEACl** 10 mol/L KCl 3 mol/L TEACl** 0.1 mol/L
7 - 10 NH4Cl 4 mol/L + DX200 KCl 3 mol/L NH4Cl 0.1 mol/L

NH4OH 1 mol/L
Triethanolamine 7.5 g/L KCl 3 mol/L NH4Cl 0.1 mol/L
8. Literature
8.1. General references on ion selective electrodes

8.1.1 K. Cammann, Das Arbeiten mit ionenselektiven Elektroden. Springer Verlag, (1973)
8.1.2. Friedrich Oehme, Ionenselektive Elektroden, Hüthig Verlag, 2. Auflage
8.1.3 Jiri Koryta, Ion-selective electrodes, Cambrige University Press (1975)
8.1.4 Kirk-Othmer, ion selective electrodes, Band 13
8.1.5. Peter L.Bailey, Analysis with ion-selective-electrodes, 2. edition, Heyden, London
8.1.6. Römpp Chemielexikon, 9. Auflage, Band 3 2033-2034, Band 5 3811 und 3844 f
8.1.7. Analytischer Methoden-Führer, Orion Research 9. Ausgabe 1979
8.1.8. F. Weiske; Handling von ionenselektiven Elektroden, LaborPraxis Okt 93
8.2. References for fluoride determination with ion selective electrodes

General
8.2.1. Anleitung zur ionenselektiven Fluorid-Elektrode. Ingold AG Urdorf
8.2.2. Hawkings R.C.; Dynamic Responce of the Fluoride Ion-Selective Electrode , Analytical
Chimica Acta, 102, 61-83, (1978)
8.2.3 Villa, A.E.; Rapid method for determination very low fluoride concentrations using an
ion-selective electrode. Analyst 113, 1299-1303, (1988)
Air / Exhaust
8.2.4. Elfter, L.A. and Decker, D.C.; Determination of Fluoride in Air and Stack Gas Samples
by use of an Ion Specific Electrode, Anal. Chem. 40(11),1658 (1968)
8.2.5. Buck, M. and Reusmann, G.; A New Semi-Automatic Method for Fluoride Determina-
tion in Plant and Air Samples, Fluoride 4(1),5. (1971)
Waste water
8.2.6. Ciba, L.; Ion-Selective electrode determination of fluoride ions in products obtained
from industrial waste, Chem. Anal. (Warsaw) 38 (1) 129-131 (1993)
Drinking water
8.2.7. Harwood, J.E.; The use of an Ion-Selective Electrode for Routine Fluoride Analyses on
Water Samples, Water Res. 3, 273 (1969)
8.2.8. Warner, T.B.; Determination of Fluoride Pollutants in Natural Waters Using a Known
Addition Technique, NRL Report 7216, Naval Resarch Laberatory, Washington, D.C.,
December 24, (1969)
8.2.9 Schöller, F. and Kaspar, W.D.; The Fluorid Content of East Austrian Water and its De-
termination by Means of a Specific Ion Electrode.
8.2.10. Gas/Wasser/Wärme/, 24(6), 115 (1970)
8.2.11. Warner, T.B. and Bressan, D.J.; Direct Measurment of less than 1 part per Billion Fluo-
ride in Rain, Fog and Aerosols with Ion Selective Electrode. Anal.Chim. Acta 63(1),
165 (1972).
8.2.12. ASTM D 1179-70
Milk
8.2.13. Konikoff, B.S.; The Bioavailability of Fluoride in Milk. La Dental J. 32/1, (1974)
8.2.14. Ericsson, Y., and Hellstrom, I.; Pilot Studies on the Fluoride Metabolism in Infants on
DifferentFeedings. Acta Paediat. Scand. 61, 459 (1972)
Vitamins
8.2.15. Jones, B.C., Heveran, J.E. and Senkowski, B.Z.; Specific Ion Electrode Determination
of Fluoride in Multivitamin Preparations. J. Pharm. Sci. 58(5), 607 (1969)
Wine
8.2.16. Martin, C. and Brun, S.; Measurement of Fluoride in Wines. Trav. Soc. Pharm. Mont-
pellier 29(3), 161 (1969)
8.2.17. De Baenst, G., Mertens, J., Van den Winkel, P. and Massart, D.L.; Potentiometric De-
termination of Fluorid Ion in Wine. J. Pharm. belg. 28(2), 188 (1973)
Fish
8.2.18. Ke, P.E., Power, H.E. and Regier, L.W.; Flouride Content of Fish Protein Concentrate
and RawFish. J. Sci. Food Ag. 21(2),108 (1970)
8.2.19 Wright, D.A., and Davison, A.W.; The Accumulation of Fluoride by Marine and Inter-
tidal Animals. Environ. Pollut. 8, 1 (1975)
Vegetation
8.2.20 Galloway, H.L., Shoaf, R.E. and Skaggs, C.H.; A Rapid Method for the Determination
of Fluoride in Vegetation. Am. Ind. Hyg. Assoc. J. 721 (1975)
8.2.21 McQuaker, N.R. and Gurney, M.; Determination of Total Fluoride in Soil and Vegeta-
tion Using Alkali Fusion - Selective Ion Electrode Technique. Anal. Chem. 49, 53
(1977)
8.2.22 Villa, A.E.; Rapid Method for Determining Fluorid in Vegetation Using an Ion-Selec-
tive Electrode. Analyst 104, 545 (1979)
8.2.23 Wang, C.Y.; Fluorine Ion Selective Electrode for Micro-Determination of Fluorine in
Organic Compounds. Microchem. J. 27, 455 (1982)
8.2.24 Wang C.Y.; Trace Analysis of Fluorine in Plants and Foods (Gran’sMethod). Fluoride
22(3) 108-111 (1989)
Serum
8.2.25. Singer, L. and Amstrong, W.D.; Total Fluorid Content of Human Serum. Arch. Oral
Biol. 14, 1343 (1969)
8.2.26 Singer, L. and Amstrong, W.D.; Determination of Ionic (plus Ionizable) Fluoride in Bi-
ological Fluids. Anal. Biochem. 42, 350 (1971)
Tooth care
8.2.27 Light, T.S. und Cappuccino, C.C.; Determination of Fluoride in Toothpaste using an
Ion Selective Electrode. Journal of Chemical Education Vol. 52 (4), 247 (1975)
Soil
8.2.28. McQuaker N.R. and Gurney, M.; Determination of Total Fluoride in Soil and Vegeta-
tion using an Alkali Fusion-Selective Ion Electrode Technique.
Anal. Chem. 49, 53 (1977)
8.2.29. Dracheva, L.N. and Stepanets, M.I.; Potentiometric determination of fluorid in soil.
Gig.Sanit. (5-6) 65-67 (1992).
8.3. References for chloride determination with ion selective electrode
General
8.3.1. Anleitung zur ionenselektiven Chlorid-Elektrode. Ingold AG Urdorf
8.3.2. Chapman B.R., Goldsmith I.R.; Determination of Chloride, Sodium and Potassium in
Salted Foodstuffs using Ion-selective Electrodes and the Dry Sample Addition Method.
Analyst 107, 1014-1018 (1982)
Water
8.3.3. Warner, T.B.; Ion Selective Electrodes in Seawater.
Marine Technology Society 6th Annual Preprints, 2, 1495 (1970)
8.3.4. Ogata, N.; Dynamic Property of Chlorid Selective Electrode and ita Application to Sea-
water. Jap. Analyst 21, 780 (1972)
8.3.5. Frost, J.G. An Indirect Potentiometric Determination of Chloride in Cleaning Solutions
for Power Plant Boilers. Anal. Chim. Acta. 48, 321 (1969)
8.3.6. Marshall, G.B., Midgley, D.; Determination of Chloride in High-purity Waters in the
Range 0-20 µg/L of Chloride Using Ion-selective Membran Electrodes Incorporating
Mercury(I)Chloride. Analyst 104, 55-62 (1979)
8.3.7. Fischer, W.; Process of groundwater control regarding possible contaminations after
using brckish water. Nachr. Mensch Umwelt 9(4),15-18 (1981)
8.3.8. Vieira, B.M.;Use of ion selective electrode in chloride determination in aqueous solu-
tion to the 10-6 m level (0.1 ppm). Quim Nova 8 (3), 148-52 (1985)
8.3.9. Chloride in drinking water, waste water and salt soultions.
Schweiz. Lab.Z. 43 (11), 431-2 (1986).
Dairy products
8.3.10 Muldoon, P.J. and Liska, B.J.; Chloride Ion Activity Electrode for the Detection of Ab-
normal Milk. Dairy Sci. 54(1), 117 (1971)
8.3.11. Randell, A.W., Linklater, P.M.; The Rapid Analysis of Cheddar Cheese. The Determi-
nation of Salt Content Using an Electrode Specific for Chloride.
Australien J. Dairy Tech. 27(2), 51 (1972)
8.3.12 Liu, J., Neu, S., Zhang, H.; Use of ion-selective electrodes in determination of chlorides
in milk. Shipin Kenxue (Beijing) 101, 49-50 (1988)
8.3.13 Turyan Y.I., Malyshev, A.M., Skhalyakho, A.Kh.; Potentiometric determination of so-
dium chloride in water-insoluble samples using a chlorid-selective electrode.
Zh.Anal.Khim 47(7), 1334-7 (1992)
Foods
8.3.14. Moody, G.J., Thomas, J.D.R.; The Determination of Chloride in Vegetables Fruits and
Juices with Ion-Selective Electrode. Food Tech 12, 193 (1977)
8.3.15 Sucman, E., Zima, St., Rochova, I.; Determination of the content of chloride ion in sala-
mi with chloride selective electrode.
Sb UVTIZ, Potravin Vedy 3(2), 95-101 (1985)
8.3.16 Dracheva, L.V., Radchenko, A.F.; Determination of chlorid ions in food products using
chloride selective electrode. Zavod Lab 57(1), 14-15 (1991)
Plants
8.3.17. Rosol, M.,Supuka, J.; Evaluation of the use of an ion selective electrode for chloride
determination in plants. Biologia (Bratislava) 39 (1), 41-48 (1984).
Special
8.3.18 Leser, K.H., Sigrist, G.V.; Application of chloride selective microelectrode to renal test
dyes and other food or cosmetic dyes.
Pfluegers Arch. 406(1),88-90 (1986)
8.4. References for nitrate determination with ion selective electrode
General
8.4.1. Anleitung zur ionenselektiven Nitrat-Elektrode. Ingold AG Urdorf
8.4.2. Milham,P.J., Awad,A.S., Paull, R.E.; Analysis of Plants, Soils and Waters for Nitrate by
using an Ion-Selective Electrode.
Analyst, 95 (1133),751 (1970)
Water
8.4.3. Shaw, E.C. and Wiley, P.; Nitrate Ion Concentration in Well Water.
Calif. Agr., 5, 11 (1969)
8.4.4. Sommerfeldt, T.G., Milne, R.A.; Use of Nitrate-Specific Ion Electrode for the Determi-
nation of Nitrate Nitrogen in Surface and Ground Water.
Soil.Sic.Plant.Anal. 2 (6), 415 (1971)
8.4.5. Flasarova M., Novak, J.; Determination of nitrites in mixture with nitrates by using a
nitrate selective electrode. Chem Listy, Vol 80 (3) 328-31 (1986)
(Determination in soil and wastewater)
8.4.6. Huang, C., Yang, L.; Consecutive determination of nitrate, nitrite and ammonium in
rainwater with a nitrate electrode.
Fenxi Shiyanshi, 9 (5), 34-35 (1990)
Vegetables
8.4.7. Bestimmung von Nitrat in Frischgemüse. Flugschrift Nr 106, 3 Auflage 1990, Eidgenös-
sische Forschungsanstalt für Obst-, Wein- und Gartenbau, Wädenswil
8.4.8. Kolbe, H. und Müller, K.; Vergleichende Untersuchung über semiquantitative und
quantitative Methoden zur Bestimmung von Nitrat in Kartoffeln. Institut für Agrikul-
turchemie der Georg-August Universität Göttingen
8.4.9. Kniel, B., Rauh, J. und Gnoth, K.; Potentiometrische Nitratbestimmung in Rote-Bete-
Säfte als routienemässig anwendbare Methode für die Qualitäts-sicherung.
8.4.10. Paul, J.L. and Carlson, R.M.; Nitrat Determination in Plant Extracts by the Nitrat Elek-
trode. J. Agr. Food Chem., 16(5), 766 (1968)
8.4.11. Barker, A.V., Peck, N.H. and MacDonald, G.E.; Nitrate Accumulation in Vegetables.
Spinach Grown in Upland Soils. Argron.J. 63(1), 126 (1971)
8.4.12. McCaslin, B.D., Franklin, W.T. and Dillon, M.A.; Rapid Determination of Nitrate Ni-
trogen in Sugarbeets with the Specific Ion Electrode. Journal .of the A.S.S.B.T. 16 (1),
64 (1970)
8.4.13. Henscheid, T., Schoenrock, K. and Berger, P.; Application of Ion-Selective Electrodes
in the Beet Sugar Industry.
Journal .of the A.S.S.B.T., 16(6), 482 (1971)
8.4.14. Kolbe, H., Müller, K.; Vergleichende Untersuchungen über semiquatitative und quanti-
tative Methoden zur Bestimmung von Nitrat in Kartoffeln.
Potato Resarch 29, 333 - 346 (1989)
8.4.15. Mitrakas, M.G.; Nitrate determination in sugar beet sap extracted with lead acetatelead
monoxide using an ion-selective electrode.
Commun Soil Sci Plant Anal. 22 (5-6), 589-96 (1991)
Meat
8.4.16. .Zhou, X., Zhang, T.; Determination of nitrate and nitrite in meat products with the ni-
trate selective electrode. Wuxi Qinggongye; Xueyuan Xuebao, Vol 10(2) 19-29 (1991)
ISSN:1001-7453
Fruits
8.4.17. Kotova, L.V., Selezneva G.P.; Method for determination of nitrates in apples by a nitrate-
selective electrode. Biokhim Methody Analiza Plodov, Kishinev 90
Soils
8.4.18. Simeonov,V.; Rapid Determination of Nitrate Nitrogen in Soils. Talanta, 24, 199 (1977)
8.5. References for sodium and potassium determinations with ion selective elec-
trodes
General
8.5.1. Anleitung zur ionenselektiven Kalium-Elektrode. Ingold AG Urdorf
8.5.2. Anleitung zur ionenselektiven Natrium-Elektrode. Ingold AG Urdorf
8.5.3. Schindler, J.G.; Natrium selektive Monensin-PVC-Membranelektrode mit Festableitung.
Fresenius Z.Anal. Chem., 320, 258-260 (1985)
8.5.4. Srivastava, S.K.; Determination of Sodium by Ion-selective Potentiometry.
ANALYST, 109, 667 (1984)
Water
8.5.5. Chiu,Y.P., Juang, S.F.; The micellar dissociation concentration of bile salts in water with
a sodium ion electrode. Chim. Oggi, 9, (3), 55-59 (1991)
Foods
8.5.6. McNerney, F.G.; Collaborative Study of the Determination of Sodium in Dietetic Foods
by the Sodium Ion Electrode Method. JAOAC., 59 (5), 1131 (1976)
8.5.7. Kindstedt, P.S., Mattick, L.R.; Simple selective sodium ion electrode measure of sodium
in cheese. J.Dairy Sci., 66(5), 988-93 (1983)
8.5.8. Kindstedt, P.S., Kosikowski, F.V.; Measurement of sodiumchloride in cheese by simple

sodium ion electrode method. J.Dairy Sci., 67(4), 879-83 (1984)
Blood
8.5.9. Reichenbach, K.; Influences of proteins and blood cells on the results of direct potentio-
metric measurements in blood - demonstrated on sodium determination with glass elec-
trode. Bioelectroanal, 1.Symp., Akad Kiado, Budapest, p. 341-51 (1987)
8.5.10. Annan, W., Kirwan, N.A., Robertson W.S.; An evaluation of the NOVA 1 ion selective
analyser for sodium and potassium determination. J.Autom Chem Vol 2(4) 212-20
(1980)
Soil
8.5.11. Puffer, J.H., Cohen, R.S.; Field Determination of Sodium and Potassium in Feldspars
by Ion-Selective Electrodes.
Chem. Geol., 15, 217 (1975)
Glass
8.5.12. Knupp, R.C.; Use of Ion-Selective Electrodes for Analysis of Sodium and Calcium in
Glass Batch.
Chem. Geol., 15, 217 (1977)
Internet:
Titration homepage of METTLER TOLEDO:
http://www.titration.net
Check also the application database at this Internet address.
9. Sample index
Apple juice 42, 50
Aquarium water 32
Baby food 20
Beans (canned) 20
Bouillon 50
Cabbage 32, 33
Cabbage, white 35
Carrot juice 20, 32, 42
Carrots 32, 33
Cheese 20
Cucumbers 32
Drinking water 10, 13, 32, 50
Elderberry juice 42
Fertilizer solution 42
Fluoride tablets 10
Garden soil 42
Grape juice 42, 50
Herb paté 50
Iceberg lettuce, head 32
Infusion solution 42, 50
Lettuce head 32, 33
Mayonnaise 20
Milk 10, 20, 42, 50
Mineral water 10, 50
Mouthwash 10
Orange juice 42
Peas (canned) 20, 22
Potatoes 32
Red beet juice 32, 42
Red beets 35
River water 13
Salad dressing 20
Silver beet 32
Snow 10
Soil 42
Spinach 32, 35
Spring water 13
Table salt 10
Tomato juice 20
Tomato ketchup 20
Toothpaste 10
Wine 10, 42, 48
Notes
Notes
Notes
This applications brochure represents selected, possible application examples. These have been tested with all possible
care in our lab with the analytical instruments mentioned in the bulletin. The experiments were conducted and the
resulting data evaluated based on our current state of knowledge.
However, the applications brochure does not absolve you from personally testing its suitability for your intended meth-
ods, instruments and purposes. As the use and transfer of an application example are beyond our control, we cannot
accept any responsibility for the use or consequences of the applications contained in this brochure.
When chemicals and solvents are used, the general safety rules and the directions of the producer must be
observed.
Mettler-Toledo GmbH METTLER TOLEDO on the WWW
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CH-8603 Schwerzenbach, Schweiz You can also reach us on the World Wide Web. There you
Telefon (01) 806 77 11, Fax (01) 806 73 50 will find information on other products and services of
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METTLER TOLEDO Titrators

Georg Reutemann Rolf M. Rohner

1. Fluoride Selective Electrode ........................................................................................ 4

2. Chloride Selective Electrode...................................................................................... 14

3. Nitrate Selective Electrode ........................................................................................ 24

4. Potassium Selective Electrode ................................................................................... 36

5. Sodium Selective Electrode ....................................................................................... 44

7. Summary of the Ion Selective Electrodes and Reagents Used .................................. 54

9. Sample index ...............................................................................................................63

Application and Use

Alternatives Ion chromatography.

Advantages - wide application range (1000 - 0.01 mg/L)

M101 Calibrating the Fluoride Electrode

Sample: 50 mL fluoride solution Instruments: METTLER TOLEDO DL70ES

Preparation: 5 mL TISAB III MERCK Accessories: Titration beaker ME-101974

Standard: -- Indication: DX219 Fluoride ISE

Results: METTLER DL70ES Titrator V3.0 Mettler-Toledo AG

Method F007 Calibration F- -sensor 09-Nov-1993 17:46

No ID1 ID2 Sample amount and results

1/1 10-4 g/L 50.0 mL pH,pM,pX 4.000

Typical calibration curve of a fluoride selective electrode with TISAB solution

M102 Fluoride Determination with Fluoride Ion Selective Electrode

Sample: 50 mL sample solution with Instruments: METTLER TOLEDO DL70ES

Substance: Fluoride Method: F00A, F00B

Titrant: - Indication: DX219 Fluoride ISE

Repeatability and Recovery Rate

Concentration Recovery srel from several series (n=6)

Sample Direct measurement with ISE Nominal content

Drinking water 0.056 mg/L 0.79 % not over 1.5 mg/L *

Snow 0.0066 mg/L 14.9 % none given

Mineral water 0.109 mg/L 0.5 % 0.13 mg/L

Wine 0.176 mg/L 2.0 % none given

Milk 0.023 mg/L 2.1 % none given

Table salt 233 mg/kg 1.2 % 250 mg/kg

Toothpaste 0.117 % 0.9 % 0.113 %

Fluoride tablet 1.064 mg/tab. 2.4 % 1 mg / tablet

Mouth wash 236 mg/kg 0.27 % 220 mg/kg

Drinking water To 50 mL add 5 mL TISAB III solution and measure.

Mineral water To 50 mL add 5 mL TISAB III solution and measure.

Wine To 50 mL add 5 mL TISAB III solution and measure.

Milk To 50 mL add 5 mL TISAB III solution and measure.

M071 Fluoride Determination in Water

Sample: 50 mL drinking water Instruments: METTLER TOLEDO DL70ES

Preparation: 5 mL TISAB III MERCK Accessories: Titration beaker ME-101974

Method F00W Auto.Calib+conc.det of F- 22-Nov-1993 12:49

No ID1 ID2 Sample amount and results

1/1 5*10-5 g/L 50.0 mL pH,pM,pX 4.301

Author: Albert Aichert

Application and Use

Alternatives Chloride determinations can also be performed using argentometric titration.

Disadvantages The chloride determination has the following disadvantages compared to

M103 Calibrating the Chloride Electrode

Sample: 50 mL chloride solution Instruments: METTLER TOLEDO DL77

Preparation: 3 mL ISA solution Accessories: Titration beaker ME-101974

Standard: -- Indication: DX235 Chloride ISE

Results: METTLER DL77 Titrator V3.0 Mettler-Toledo AG

Method Cl07 Calibration Cl- -Sensor B 19-Aug-1993 8:53

No ID1 ID2 Sample amount and results

1/1 2 50.0 mL pH,pM,pX 2.000