Libro Analisis de Agua Cromatografía

Peter A.
Bruttel and Nadine Seifert

Analysis of water samples
and water constituents
with Metrohm instruments
Monograph
Peter A. Bruttel and Nadine Seifert
Analysis of water samples and water
constituents with Metrohm
instruments
All rights reserved, including translation rights.
Printed in Switzerland by Metrohm Ltd., CH-9101 Herisau.
8.038.5003 2007-06
I
Preface
Water is essential for all living organisms
without water no life is possible!
Water is needed for dissolving, transporting and soaking, making possible the
most varied chemical and colloid-chemical cell reactions.
About 71% of the earth's surface are covered by water. The distribution of the
water volumes is approximately as follows:
Occurrence Percentage
Sea water and salt lakes 97.335%
Polar ice and glaciers 2.04%
Ground water 0.61%
Lakes and rivers 0.009%
Soil humidity 0.005%
Atmosphere (water vapor) 0.001%
1% corresponds to 14'000 km
3
We all need pure, healthy and clean water. Keeping it clean is not only the task of
nature and environmental protection organizations or of the water authorities
each and every individual is concerned. The most diverse regulations and
guidelines have been developed worldwide and given rise to an independent
branch of analytical science. The aim of this monograph is to show you which
parameters and water constituents can be analyzed with Metrohm instruments.
No attempt will be made, however, to evaluate the analytical results.
II
Contents
1
A Physical parameters......................................................................................... 1
Temperature ....................................................................................................... 1
pH value.............................................................................................................. 2
Redox potential ................................................................................................... 4
Electrical conductivity.......................................................................................... 6
B Overall parameters......................................................................................... 13
Permanganate index (oxidizability) ................................................................... 13
Acid and base capacity ..................................................................................... 17
Water hardness................................................................................................. 22
Kjeldahl nitrogen ............................................................................................... 32
Hydrogen peroxide and its adducts................................................................... 35
Complexing capacity......................................................................................... 38
C Gaseous water constituents........................................................................... 40
Free and total chlorine ...................................................................................... 40
Dissolved oxygen.............................................................................................. 43
Ozone ............................................................................................................... 48
D Anions............................................................................................................ 51
D1 Titration: Chloride ..................................................................................... 51
D1 Titration: Cyanide ..................................................................................... 55
D1 Titration: Sulfate ....................................................................................... 59
D1 Titration: Sulfides and hydrogen sulfide.................................................... 63
D2 Ion chromatography: Introduction............................................................. 66
D2 Anion determination with IC...................................................................... 68
D2 Oxyhalides with IC: Chlorate, chlorite, bromate........................................ 73
D2 Bromate with IC........................................................................................ 77
D2 Perchlorate with IC................................................................................... 84
D2 Chromate Cr(VI) with IC........................................................................ 89
D2 Silicate dissolved silicic acid with IC...................................................... 94
D2 Sulfite, sulfate and thiosulfate with IC....................................................... 97
D2 Organic acids with IC.............................................................................. 100
D3 Chromate/dichromate Cr(VI) with VA .................................................. 104

1
Please find a more comprehensive list of contents at the end of this monograph.
III
D3 Cyanide with VA..................................................................................... 108
D3 Sulfides and hydrogen sulfide with VA................................................... 111
D3 Sulfite with VA........................................................................................ 113
E Cations......................................................................................................... 116
E1 Titration: Calcium and magnesium......................................................... 116
E2 Cation determination with IC .................................................................. 116
E2 Amines, for example methylamine, ethanolamine with IC...................... 124
E2 Transition metals zinc, manganese etc. with IC .................................. 128
E3 VA methods: Introduction ....................................................................... 134
E3 Determination of Cu, Cd, Pb, Zn with VA ............................................... 139
E3 Determination of Co and Ni with VA....................................................... 144
E3 Determination of Fe with VA................................................................... 146
E3 Determination of Mo with VA.................................................................. 148
E3 Determination of U with VA .................................................................... 150
E3 Determination of Ti with VA.................................................................... 153
E3 Determination of Sb with VA................................................................... 155
E3 Determination of Se with VA................................................................... 157
E3 Determination of Pt and Rh with VA....................................................... 160
F Specific water constituents........................................................................... 164
F1 Ion chromatography: NTA, EDTA and DTPA.......................................... 164
F2 VA method: NTA and EDTA in wastewater ............................................ 167
Automation examples......................................................................................... 173
Potentiometric/titrimetric analyses .................................................................. 173
Ion chromatography........................................................................................ 182
TitrIC............................................................................................................... 190
Appendix ............................................................................................................ 193
Metrohm monographs dealing with the analytical methods used.................... 193
Drinking water quality requirements................................................................ 193
Element traces in water .................................................................................. 195
Sweet water: typical values of the relevant parameters.................................. 196
Detailed list of contents .......................................................................................197
IV
Temperature
Analysis of water samples and water constituents with Metrohm instruments 1
A Physical parameters
Temperature
General remarks
The temperature is required for every water analysis. During sampling, the water
temperature and usually also the temperature of the ambient air are measured
(the solubility of gases, the pH value and any reaction rates are all temperature-
dependent quantities). With all temperature measurements the value is recorded
only when the display of the measured value remains stable.
Recommended accessories
6.1110.100 Pt 1000 temperature sensor with 6.2104.110 cable
Water temperature
The temperature sensor has to be immersed at sufficient depth into the sample. If
this is not possible, a water sample is taken with a recipient of at least 1 liter vol-
ume (which beforehand has assumed the water temperature) and the temperature
sensor is immersed (do not expose to direct sunlight).
The temperature is given with an accuracy of 0.1 C.
Air temperature
The air temperature is measured with a dry temperature sensor approximately 1 m
above the water or the ground.
The temperature is given with an accuracy of 0.5 C.
2 Metrohm Monograph 8.038.5003
pH value
General remarks
Free protons (H
+
ions) are not present in solution. They adhere to water forming
hydronium ions.
H
+
+ H
2
O H
3
O
+
The pH value is the negative common logarithm of the concentration of free, disso-
ciated hydronium ions in mol/L:
pH = log [H
3
O
+
]
The pH scale ranges from 0 to 14 and the neutral point lies at pH = 7.0. Water
autodissociates into H
3
O
+
and OH
ions. At the neutral point, these ions are

present in equal amounts. Acidic pH values are measured if there is an excess of
H
3
O
+
whereas basic pH values are obtained if there is an excess of OH
. As the
pH scale is logarithmic, small pH differences correspond to large differences of the
H
3
O
+
concentration. As an example, in a given solution there are twice as many
H
3
O
+
ions at pH = 3.1 than at pH = 3.4.
The pH measurement is done with a pH meter equipped with a combined pH glass
electrode. This electrode (pH sensor) has to be calibrated first in order to inform
the measuring instrument about its properties. For the calibration so-called buffer
solutions are used. In practical work a two-point calibration is usually sufficient
(buffer solutions pH = 7.00 and pH = 4.00 or pH = 9.00).
An ideal pH glass electrode has a slope of 1.00 (100% of the Nernst slope) and an
electrode zero point pH
as
of 7.0 or an U
as
of 0 mV. In practice, the electrode zero
point U
as
should be situated within 15 mV (corresponding to pH
as
= 6.75...7.25)
and the slope should be >0.95 (>56.2 mV per pH at 25C).
The pH value of water samples is a very important parameter. Thus, it determines
to a large extent the corrosion-chemical effects of the water type concerned.
Knowledge of the pH also allows to draw conclusions regarding chemical and/or
biological processes.
- Combined Aquatrode Plus pH glass electrode with integral Pt 1000 tempera-
ture sensor 6.0257.000
- Ready-to-use buffer solutions pH = 7.00 and pH = 4.00 or pH = 9.00 (Metrohm
no. 6.2307.110 and 6.2307.100 or 6.2307.120)
pH value
Two-point calibration of a pH glass electrode
- Connect the electrode to the measuring instrument, open the electrolyte filling
aperture and refill electroyte if necessary.
- Thoroughly rinse the electrode with dist. H
2
O and dab dry with a soft paper
towel (do not rub).
- Fill buffer solution pH = 7.00 into a beaker and add a magnetic stirring bar.
- Immerse the electrode and stir for approx. 1 min.
- Under stirring, start calibration with buffer 1 on the measuring instrument. Me-
trohm instruments are equipped with automatic buffer recognition and read
the pH values corresponding to the prevailing temperature from tables stored in
its memory.
- After the instrument has taken over the measured value, remove the electrode
from the buffer solution, rinse thoroughly with dist. H
2
O and dab dry.
- Fill buffer solution pH = 4.00 or pH = 9.00 into a second beaker, add a magnetic
stirring bar, immerse the electrode and stir for approx. 1 min (the second buffer
solution must be at the same temperature as the first).
- Continue calibration on the measuring instrument under stirring.
- After the instrument has taken over the measured value, terminate the calibra-
tion. Remove the electrode from the buffer solution, rinse thoroughly with dist.
H
2
O and dab dry.
Measuring the pH value
The pH value of the sample solution (water) depends on the temperature. This
temperature dependence cannot be compensated by the measuring instrument,
which only compensates the Nernst slope of the electrode.
For this reason, with each pH value measured the temperature at which it was
obtained must also be given.
Example of a water sample: pH = 6.92 at 15.2 C
Immerse the electrode to a sufficient depth into the water sample and gently move
the electrode to an fro, or carry out the measurement under stirring. Take over the
measured value as soon as the displayed value remains stable.
Record the pH value with an accuracy of 0.01, the temperature with an accuracy
of 0.1 C.
Relevant Metrohm literature
- Application Bulletin no. 188 pH measurement technique
- Metrosensor Electrodes catalog
Redox potential
General remarks
The redox potential is caused by reducing or oxidizing substances dissolved in the
water that are able to exchange electrons on the electrode surface. Changes of
the redox potential towards positive values indicate the presence of an excess of
oxidizing substances, whereas changes towards negative values indicate an
excess of reducing substances. Platinum is generally used as the inert electrode
material. The measured potential is referred to the standard hydrogen electrode.
The so-called loaded redox systems (e.g. wastewaters containing sulfite or
chromate) usually cause no difficulties. With unloaded redox systems, however,
this is completely different, examples being ground water, surface water or even
demineralized water. In these cases one has to expect long to very long adjust-
ment times of the electrode to the point that measurements may make little sense.
Redox potentials depend on temperature and pH value. The pH dependence can
be used for certain calculations whereas the effect of temperature is largely un-
known or cannot be calculated.
- 6.0451.100 combined Pt-ring electrode with 6.2104.020 electrode cable
- 6.2306.020 redox buffer, +250 mV
Checking and treatment of the combined Pt electrode
Fill redox buffer solution and a magnetic stirring bar into a beaker. Immerse the
combined Pt electrode into the redox buffer and measure under stirring. Record
the potential as soon as the measured value is stable. The electrode is suitable for
redox measurements if the measured value lies within 5 mV of the value given in
the table, which refers to a reference electrode of type Ag/AgCl c(KCl) = 3 mol/L.
If the measured value lies in the above range, it must be assumed that the plati-
num surface is oxidized or otherwise altered. In these cases, degrease the elec-
trode with a paper tissue soaked in alcohol and then immerse it under stirring
and for approx. 15 min in a solution of approx. 0.5 g Na
2
SO
3
in 50 mL w(HCl) =
15%. After thorough rinsing with distilled H
2
O, control the electrode again using
the redox buffer solution.
Redox potential
Redox potential values for 6.2306.020 redox buffer
Temperature
C
Redox
potential
pH value
10 265 mV 7.06
20 250 mV 7.02
25 243 mV 7.00
30 236 mV 6.99
40 221 mV 6.98
50 207 mV 6.97
Measuring the redox potential
If possible, carry out this measurement in a sealed flow-through vessel at a flow
rate of approx. 10 mL/s. The measured value is recorded as soon as its drift is
below 1 mV/min. This can take up to one hour with unloaded systems. Also
measure the temperature and the pH value of the water.
Calculating the redox potential
The measured value is referred to the potential of the standard hydrogen electrode
(defined as 0 mV). As mentioned above, the combined Pt electrode is equipped
with an Ag/AgCl c(KCl) = 3 mol/L reference system. This latter's standard poten-
tial is added to the measured value.
Standard potential of Ag/AgCl reference system with c(KCl) = 3 mol/L
Temperature
C
Standard
potential
0 224 mV
10 217 mV
15 214 mV
20 211 mV
25 207 mV
30 203 mV
Accordingly, the redox potential is calculated as follows:
U
H
= U
M
+ U
ref
U
M
= measured value / mV
U
ref
= reference potential from the table / mV (depends on temperature)
Example
At a water temperature of 15 C, a potential of 455 mV and a pH value of 7.02
were measured.
U
H
= 455 mV + 214 mV = 669 mV, which is rounded
2
to 670 mV
Water sample
Redox potential 670 mV
Temperature 15 C
pH value 7.02
- Application Bulletin no. 48 Checking the condition of platinum and gold
electrodes used for redox potential measurements
- Metrosensor Electrodes catalog
Electrical conductivity
General remarks
The electrical conductivity of a solution depens on:
- The number of ions: the more ions a solution contains, the higher its electrical
conductivity.
- In general on the ionic mobility, which in turn depends on:
The type of ion: the smaller the ion, the more mobile it is and the better it
conducts. H
3
O
+
, OH
, K
+
and Cl
are good conductors. If hydration occurs

(the ion surrounds itself with water molecules that make it larger) then the
conductivity is reduced.
The solvent: the more polar a solvent is, the better the dissolved compounds
it contains can ionize. Water is an ideal solvent for ionic compounds.

2
The redox potential values are always rounded to the next 10 mV.
The temperature: in contrast to solids, in solutions the electrical conductivity
increases as the temperature increases by 1...9% per K, depending on the
ion (water samples: 1.8...2.6% per K).
The viscosity: as the viscosity increases, the ionic mobility and therefore the
electrical conductivity decreases.
Definitions
The electrical conductivity is equal to the reciprocal value of the electrical resis-
tance (conductance G) multiplied by the cell constant c:
Quantity Symbol Unit
Conductivity S cm
1
(S m
1
)
Resistance R Ohm (O)
Conductance G = 1/R S (Siemens) = O
1
Separation between measuring electrodes l cm (m)
Measuring electrode area A cm
2
(m
2
)
Cell constant c = l/A cm
1
(m
1
)
The electrical conductivity is normally given in S/cm or mS/cm (12.88 mS/cm =
1288 mS/m; 5 S/cm = 500 S/m). In American usage the terms mhos and hos
are frequently encountered.
The cell constant c
In principle most instruments for measuring the electrical conductivity are instru-
ments for measuring the resistance R
X
or the conductance G
X
= 1/R
X
of a meas-
uring cell filled with the sample.
The relationship to the electrical conductivity , the real subject of interest, is
provided by the cell constant c, which depends on the geometrical dimensions of
the measuring cell:
= c/R
X
= c x G
X
(S/cm)
In a two-plate measuring cell the cell constant c is obtained from the area A and
the distance l between the plates:
c = l/A (cm/cm
2
)
[c] = cm
1
Because the distribution of the lines of current is not ideal, this calculated value
does not agree exactly with the effective cell constant of the measuring cell. The
effective value of c can only be determined by calibration with conductivity
standards, for example KCl solutions.
The measuring frequency
For conductivities the measuring frequency has a decisive influence on the cor-
rectness of the measured conductance G. Interfering polarization effects can be
eliminated by increasing the measuring frequency. At the same time the usable
measuring range is extended. The following are time-proven settings:
- At low conductances (not electrical conductivity) measurements are made at a
frequency of 300 Hz.
- At high conductances measurements are made at a frequency of >1 kHz (e.g.
2.4 kHz).
The temperature coefficient
The temperature coefficient depends primarily on the ions contained in the solution
and seldom shows a linear behavior. We recommend that you determine the tem-
perature coefficient of your water samples yourself or carry out the measurements
at the reference temperature. The temperature coefficient is given in % per C and
is used to convert the measured value to the electrical conductivity at the refer-
ence temperature, which for water is usually 25 C (occasionally 20 C).
The conductivity measuring cell
These measuring cells, which are also known as Kohlrausch cells, normally have
two platinized platinum electrodes. By selecting the area of and the distance
between the two electrodes it is possible to vary the cell constant of such elec-
trodes throughout a wide range. Platinizing the electrodes greatly reduces the risk
of obtaining incorrect measured values because of polarization. This also has a
favorable effect on the usable measuring range. This means that a conductivity
cell with a cell constant of c = 1 cm
1
can be used at a measuring frequency of
1 kHz from 10 S/cm to 100 mS/cm, i.e. in a range spanning four orders of mag-
nitude. Smooth, i.e. non-platinized measuring cells should only be used for low
electrical conductivities (<20 S/cm).
However, platinization also has its disadvantages. Platinized measuring cells are
susceptible to encrustation, inclusion and also growth of algae, bacteria or mold.
They also dry out during long storage or the platinization slowly breaks down. As a
result of these effects the cell constant changes and has to be redetermined from
time to time (and, of course, after every replatinization process).
Some suggestions for treating and preparing the conductivity cells:
- Place measuring cells that have been stored dry in acetone for approx. 30 min.
Then thoroughly rinse with dist. H
2
O and place in dist. H
2
O for 2...3 h.
- Frequently used measuring cells should be stored in dist. H
2
O.
- Less frequently used measuring cells should be stored in 70% ethanol or stored
dry (prevents biological growth).
- Always thoroughly rinse the measuring cell with dist. H
2
O after use.
- Conductometric measuring cell, e.g. 6.0912.110 immersion cell in PP shaft
with integral Pt 1000 temperature sensor
- 6.2301.060 conductivity standard c(KCl) = 0.1000 mol/L
Measuring the electrical conductivity
The cell constant c is chosen according to the expected measuring range:
Cell constant Measuring range
0.1 cm
1
0.1 S/cm...20 S/cm
1 cm
1
1 S/cm...10 mS/cm
10 cm
1
10 S/cm...100 mS/cm
100 cm
1
100 S/cm...10 S/cm
Water samples
at
Measuring cell Cell constant Measuring
frequency
<20 S/cm smooth small 300 Hz
<1 mS/cm platinized medium 300 Hz
>1 mS/cm platinized high >1 kHz
Together with the electrical conductivity the measuring temperature and any temp-
erature correction applied (reference temperature) are also registered.
Example
25
= 485 S/cm
Measuring temperature = 12.1 C
Reference temperature = 25 C
Automatic temperature correction (TK = 2.24% per C)
Determination of the cell constant c
The cell constant c is determined by measurements carried out with conductivity
standards. These usually are KCl solutions of exactly defined concentration that
should be bought with the corresponding certificate.
The measurement is carried out in a thermostatted and closed measuring vessel.
The correctly prepared and conditioned measuring cell is pre-rinsed with the
conductivity standard and then immersed. The measured value is registered as
soon as the temperature is constant. Always use the standard with the lowest
concuctivity first!
Standard c(KCl) = at 20 C at 25 C TK % per C
0.1000 mol/L 11.67 mS/cm 12.88 mS/cm 2.07
0.0100 mol/L 1.28 mS/cm 1.41 mS/cm 2.03
0.0010 mol/L 133 S/cm 147 S/cm 2.11
The cell constant is obtained by dividing the theoretical value (from the table) by
the measured value.
Example
Standard c(KCl) = 0.0100 mol/L
Measuring temperature = 25 C
Measured value = 1.535 mS
c = 1.41 / 1.535 = 0.919 cm
1
Waste, ground and surface water, mineral and drinking water
The reference temperature is normally 25.0 C. In order to avoid errors by
incorrectly selecting the temperature coefficient (TC) it is either recommended to
thermostat the sample solution at 25.0 C. If this is not possible then a TC can be
entered as given in the table below, or TC Ident: DIN can be selected when
using Metrohm instruments. The table is only to be used for water samples that
contain mainly calcium and hydrogen carbonate ions as well as small amounts of
magnesium, sulfate, chloride and nitrate ions, i.e. for drinking, lake, ground and
river water samples.
Sample
temperature
C
TC
% per C
5...10 2.62
10...15 2.41
15...20 2.23
20...25 2.08
25...30 1.94
30...35 1.79
Demineralized water
Water has an intrinsic conductivity that cannot be reduced by purification methods.
The reason for this is the self-dissociation of water, which is also called auto-
protolysis:
2 H
2
O
H
3
O
+
+ OH
-
The self dissociation of water is strongly temperature-dependent and its
temperature coefficients are extremely high between 18 and 25 :
Temperature
C
Conductivity
S/cm
0 0.010
18 0.038 9.06
25 0.060 8.27
34 0.090 5.56
50 0.170 5.56
Because of possible interferences, a special procedure must be selected for water
with a conductivity of <5 S/cm. The most important interferences result from:
- Absorption of CO
2
(or other conducting gases) from the atmosphere.
- Leaching of traces of Na and Ca from the glassware used.
Both interferences cause the measured value to drift and finally high-bias
conductivities are measured. We recommend the following procedures to eliminate
such interferences to as great an extent as possible:
Version 1
Perform flow-through measurements. Because of the small volume of the
measuring setup we recommend to use the 6.0912.110 conductivity cell (PP shaft,
built-in Pt 1000 temperature sensor) screwed into the 6.1420.100 flow-through
vessel. The water is allowed to flow through the measuring setup and the
conductivity is determined in the usual way.
Version 2
The measurement is carried out in as large a volume as possible. Nitrogen or
argon should be passed through and over the solution, which should also be
stirred. If possible, use a closed or covered setup.
Please note the high temperature coefficient of these water samples (see table
above).
TC
% per C
- Application Bulletin no. 102 Conductometry
- Monograph 8.028.500X Conductometry
- Metrosensor Electrode catalog
Permanganate index (oxidizability)
B Overall parameters
General remarks
The permanganate index, given as mg/L O
2
, is a standard parameter for the
determination of the content of organic and inorganic water constituents that are
oxidized by permanganate under the test conditions. It cannot be regarded as a
measure for the theoretical oxygen demand since many organic compounds are
not completely oxidized. Its primary purpose is to evaluate water supplies for
human or domestic use (drinking, mineral, source water, water from swimming
pools). The procedure is applicable to water samples with a chloride content
<300 mg/L. The lower application limit is about 0.5 mg/L O
2
. Water samples with a
permanganate index >10 mg/L O
2
must be diluted before the determination.
- Titrino or Titrando with Dosino or Dosimat
- Magnetic stirrer
- 6.0431.100 Pt Titrode with 6.2104.020 electrode cable
- Wide-neck Erlenmeyer flask, 300 mL
Reagents
Deionized water from water purification plants with organic ion exchangers is not
suitable for preparing the reagents. Use either distilled water or water from a
reverse-osmosis plant.
- Permanganate stock solution: c(KMnO
4
) = 0.02 mol/L
This solution should not be prepared in the lab. Whenever possible obtain it
ready-for-use from a reagent manufacturer.
- Titrant 1: c(KMnO
4
) = 0.002 mol/L
Dilute 100 mL permanganate stock solution to 1 liter with dist. H
2
O. The solution
can be stored for approx. 3 months.
- Sodium oxalate stock solution: c(Na
2
C
2
O
4
) = 0.05 mol/L
Dry the sodium oxalate overnight in the drying oven at 120 C and leave to cool
in the desiccator for at least 2 h. Weigh 6.700 g Na
2
C
2
O
4
into a 1000-mL volu-
metric flask, dissolve in dist. H
2
O, make up to the mark with dist. H
2
O and mix.
- Titrant 2: c(Na
2
C
2
O
4
) = 0.005 mol/L
Dilute 100 mL sodium oxalate stock solution to 1 liter with dist. H
2
O. The
solution can be stored for approx. 2 weeks.
- Sulfuric acid: c(H
2
SO
4
) = 3.75 mol/L
Under stirring add 206 mL w(H
2
SO
4
) = 98% to 500 mL dist. H
2
O in a glass
beaker. Add permanganate stock solution drop by drop until a slight pink color
remains. When the mixture has cooled down, make up to 1 liter with dist. H
2
O
and mix.
Analysis
Transfer 100 mL water sample into an Erlenmeyer flask, add 5 mL sulfuric acid
and some boiling beads and rapidly heat to boiling, then add 10.00 mL c(KMnO
4
)
= 0.002 mol/L (titrant 1). After the solution starts boiling again, keep boiling under
moderate heating for exactly 10 min. If the mixture turns brownish during boiling or
if it becomes completely discolored, repeat the determination with a smaller
sample volume, which is made up to 100 mL with dist. H
2
O.
After the 10-min boiling time, rapidly add 10.00 mL c(Na
2
C
2
O
4
) = 0.005 mol/L
(titrant 2) and mix. If the solution does not become discolored immediately, boil it
again for a short time until it is completely discolored. Titrate the warm solution
with c(KMnO
4
) = 0.002 mol/L (titrant 1) past the endpoint. If the titrant consumption
exceeds 5 mL, repeat the determination with a correspondingly diluted water
sample.
Calculations
1 mL c(KMnO
4
) = 0.002 mol/L corresponds to 0.316 mg KMnO
4
1 mg KMnO
4
corresponds to 7.9 mol O
2
= 0.1264 mg O
2
Oxidizability
mg/L KMnO
4
= EP1 x C01 x C02 / C00 (RS1)
Permanganate index
mg/L O
2
= EP1 x C01 x C02 x C03 / C00
or
RS1 x C03
EP1 = mL KMnO
4
consumed to reach the endpoint
C00 = sample size in mL (normally 100)
C01 = 0.316
C02 = 1000 (for 1 liter)
C03 = 0.1264
Remarks
- Use only thoroughly cleaned glassware. Detergent residues will falsify the result
it is best to use always the same Erlenmeyer flasks.
- The 10-min boiling time must be strictly adhered to.
- To accelerate the titration, approx. 0.1 g MnSO
4
can be added to the solution as
a catalyst. The titration can then even be carried out at room temperature.
Example: Permanganate index of tap water (Herisau)
'fr
799 GPT Titrino 01103 799.0010
date 2004-02-03 time 09:27 4
pHc(init) 8.14 DET pH 17DET
sample 100 ml
EP1 11.2264 ml 4.27
stop V reached
============
'pa
799 GPT Titrino 01103
799.0010
date 2004-02-03 time 10:05
5
DET pH 17DET
parameters
>titration parameters
meas.pt.density 4
min. incr. 10.0 l
titr.rate max. ml/min
signal drift 50 mV/min
equilibr.time 26 s
start V: OFF
pause 0 s
dos.element: internal D0
meas.input: 1
temperature 25.0 C
>stop conditions
stop V: abs.
stop V 20 ml
stop pH OFF
stop EP 9
filling rate max. ml/min
>statistics
status: OFF
>evaluation
EPC 5
EP recognition: greatest
fix-EP1 at pH OFF
pK/HNP: OFF
>preselections
req.ident: OFF
req.smpl size: OFF
limit smpl size: OFF
activate pulse: OFF
------------
'cf
799 GPT Titrino 01103 799.0010
date 2004-02-03 time 10:05
DET pH 17DET
C-fmla
------------
'de
799 GPT Titrino 01103 799.0010
date 2004-02-03 time 10:05
DET pH 17DET
def
>formula
>silo calculations
match id: OFF
>common variables
>report
report COM1:param;full;mplist;
>mean
>temporary variables
C70=EP1
------------
Acid and base capacity
General remarks
The acid capacity of a water sample (K
A
) is equal to the amount of hydronium ions
that the sample consumes to reach a given pH value. It is indicated in mmol/L. To
obtain the acid capacity to pH 8.2 (K
A8.2
, previously p value), the sample is titrated
with HCl to pH = 8.2; to obtain the acid capacity to pH 4.3 (K
A4.3
, previously m
value), the sample is titrated to pH = 4.3.
The base capacity of a water sample (K
B
) is equal to the amount of hydroxide ions
that the sample consumes to reach a given pH value. It is indicated in mmol/L. To
obtain the base capacity to pH 4.3 (K
B4.3
), the sample is titrated with NaOH to pH =
4.3; to obtain the base capacity to pH 8.2 (K
B8.2
), the sample is titrated to pH = 8.2.
- Magnetic stirrer
- 6.0257.000 Aquatrode Plus with integral Pt 1000 temperature sensor
Reagents
- Titrant 1: c(HCl) = 0.1 mol/L
This titrant is available ready-for-use from the reagent manufacturers.
3
Dilute 200 mL c(HCl) = 0.1 mol/L to 1 liter with dist. H
2
O.
- Titrant 3: c(NaOH) = 0.1 mol/L
- Titrant 4: c(NaOH) = 0.02 mol/L (see footnote 3)
- Buffer solutions pH = 4.00 and pH = 7.00,
e.g. Metrohm no. 6.2307.100 and 6.2307.110
Analyses
Before starting the measurements, calibrate the Aquatrode Plus pH electrode with
buffer solutions pH = 4.00 and pH = 7.00.
Acid capacity (alkalinity)
Transfer 100 mL water sample into the titration vessel. Measure first the pH value
under stirring. After this, titrate with c(HCl) = 0.1 mol/L or 0.02 mol/L, using a pH
value of 3.5 as the stop criterion.

3
Use this titrant for very soft water.
Calculations
K
A8.2
= EP1 x C01 x C02 (see below: Remarks)
K
A4.3
EP1 = mL HCl consumed to a fixed EP of pH = 8.2 (e.g. C51 [Titrinos])
EP2 = mL HCl consumed to a fixed EP of pH = 4.3 (e.g. C52 [Titrinos])
C01 = concentration of HCl in mol/L (0.1 or 0.02)
C02 = 10 (conversion factor to mmol/L when using 100 mL sample)
The results are given to two decimal places.
Remarks
- The initial pH value of many water samples is below 8.2 and K
A8.2
cannot be
calculated (EP1 shifts to pH = 4.3).
- See next chapter for the calculation of the carbonate hardness.
Example: Acid capacity (alkalinity) of a tap water (Herisau)
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-20 time 16:57 5
pHc(init) 7.61 DET pH ********
smpl size 100 ml
fix-EP1 sample size out
8.20
fix-EP2 5.030 ml
4.30
KS8.2 missing fix EP
KA4.3 5.030 mmol/l
stop V reached
============
'pa
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-20 time 16:57 5
DET pH ********
parameters
meas.pt.density 1
min. incr. 10.0 l
equilibr.time 52 s
start V: OFF
pause 0 s
meas.input: 1
temperature 22.8 C
>stop conditions
stop V: abs.
stop V 7 ml
stop pH OFF
stop EP 9
>statistics
status: OFF
>evaluation
EPC 100
EP recognition: OFF
fix-EP1 at pH 8.2
fix-EP2 at pH 4.3
fix-EP3 at pH OFF
pK/HNP: OFF
>preselections
req.ident: OFF
req.smpl size: OFF
activate pulse: OFF
============
Base capacity (acidity)
Transfer 100 mL water sample into the titration vessel. Measure first the pH value
under stirring. After this, titrate with c(NaOH) = 0.1 mol/L or 0.02 mol/L, using a pH
value of 9.5 as the stop criterion.
Calculations
K
B4.3
K
B8.2
EP1 = mL NaOH consumed to a fixed EP of pH = 4.3 (e.g. C51 [Titrinos])
EP2 = mL NaOH consumed to a fixed EP of pH = 8.2 (e.g. C52 [Titrinos])
C01 = concentration of NaOH in mol/L (0.1 or 0.02)
C02 = 10 (conversion factor to mmol/L when using 100 mL sample)
The results are given to two decimal places.
Remarks
- The initial pH value of many water samples is above 4.3 and K
B4.3
cannot be
calculated (EP1 shifts to pH = 8.2).
- Rinse the electrode between runs with dilute HCl followed by dist. H
2
O to re-
move any precipitated CaCO
3
.
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-20 time 17:21 7
pHc(init) 7.76 DET pH Base-kap
fix-EP1 sample size out
4.30
fix-EP2 0.696 ml
8.20
KB4.3 missing fix EP
KB8.2 0.139 mmol/l
stop V reached
============
'pa
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-20 time 17:21 7
DET pH base-cap
parameters
meas.pt.density 1
min. incr. 10.0 l
equilibr.time 52 s
start V: OFF
pause 0 s
meas.input: 1
temperature 22.7 C
>stop conditions
stop V: abs.
stop V 2 ml
stop pH OFF
stop EP 9
>statistics
status: OFF
>evaluation
EPC 100
EP recognition: OFF
fix-EP1 at pH 4.3
fix-EP2 at pH 8.2
fix-EP3 at pH OFF
pK/HNP: OFF
>preselections
req.ident: OFF
req.smpl size: OFF
activate pulse: OFF
============
Water hardness
General remarks
Carbonic acid (CO
2
) dissolves in water. In calcareous water it is present as
carbonate and hydrogen carbonate. In the lime-carbonic acid equilibrium, free
carbonic acid and carbonate are in equilibrium with hydrogen carbonate. If there is
enough free CO
2
, calcium remains dissolved as hydrogen carbonate. If there is an
excess of free CO
2
, these waters become aggressive they leach out calcium
from calcareous materials causing, for example, corrosion of concrete. Upon
warming up or by plant assimilation (e.g. by algae) CO
2
is driven out or consumed
and the equilibrium shifts to the carbonate side. The carbonate then precipitates
as sparingly soluble CaCO
3
(e.g. boiler scale) and the pH value can increase to
values above 9.
The total hardness of a water is defined as the sum of the hardness-causing
species (Ca, Mg, Ba, Sr), whereas the calcium or magnesium hardness refers to
the corresponding ion. The carbonate hardness or temporary hardness is the sum
of the carbonates and hydrogen carbonates, which is determined by the acid
capacity K
A4.3
. The sulfate hardness or permanent hardness is obtained by
subtracting the carbonate hardness from the total hardness. All hardness values
are given in mmol/L.
As Al, Ba, Fe, Mn and Sr ions are present at very low levels in most waters, one
only determines calcium and magnesium.
As user information, for example on detergent packages, expressions such as
soft, hard, dH, fH still have a certain importance. The table below
informs about the existing relationships:
mmol/L mg/L CaCO
3
fH
dH
USH Hardness
0...0.7 0...70 0...7 0...3.92 0...3.77 very soft
0.7...1.5 70...150 >7...15 >3.92...8.4 >3.77...8.07 soft
1.5...2.5 150...250 >15...25 >8.4...14.0 >8.07...9.50 moderately hard
2.5...3.2 250...320 >25...32 >14.0...17.92 >9.5...17.22 rather hard
3.2...4.2 320...420 >32...42 >17.92...23.5 >17.22...22.6 hard
>4.2 >420 >42 >23.52 >22.6 very hard
Water hardness
Conversion factors
mmol/L x 100 mg/L CaCO
3
mmol/L x 10 fH (French hardness degrees)
mmol/L x 5.6 dH (German hardness degrees)
mmol/L x 5.38 USH (US hardness degrees)
- Magnetic stirrer
- 6.0508.110 Ca ISE with 6.2104.020 electrode cable
- 6.0750.100 Ag/AgCl reference electrode with 6.2106.020 electrode cable
Reagents
- Reagents for the determination of the carbonate hardness: see preceding
chapter under acid capacity.
- Titrant: c(Na
2
EDTA) = 0.1 mol/L
- Auxiliary complexing solution:
c(acetyl acetone) = 0.1 mol/L plus c(TRIS) = 0.2 mol/L
Weigh 20.4 g tris(hydroxymethyl)-aminomethane into a 1000-mL volumetric
flask and dissolve in approx. 500 mL dist. H
2
O. Add 12 mL acetyl acetone,
make up to the mark with dist. H
2
O and mix.
Analyses
Carbonate hardness
Use a 100-mL water sample and determine the consumption of HCl in mL to pH =
4.3 (K
A4.3
, see above under acid capacity).
Calculation
Carbonate hardness, mmol/L = EP1 x C01 x C02 (= C31)
EP1 = mL HCl consumed to the fixed EP at pH = 4.3
C01 = concentration of HCl in mol/L (0.1 or 0.02)
C02 = 10 (conversion factor for mmol/L when using a 100 mL sample)
C31 = Common Variable; result storage for subsequent calculations
Calcium, magnesium and total hardness
Pipet 100 mL water sample into the titration beaker, add 15 mL auxiliary complex-
ing solution and titrate with c(Na
2
EDTA) = 0.1 mol/L past the second endpoint.
EP1 corresponds to the Ca and the difference EP2 EP1 to the Mg.
Calculations
RS1; total hardness, mmol/L = EP2 x C01 x C02
RS2; calcium hardness, mmol/L = EP1 x C01 x C02
RS3; magnesium hardness, mmol/L = (EP2 EP1) x C01 x C02
RS4; permanent hardness, mmol/L = RS1 C31
EP1 = mL Na
2
EDTA consumed to reach the first endpoint
EP2 = mL Na
2
EDTA consumed to reach the second endpoint
C01 = concentration of Na
2
EDTA solution in mol/L (0.1 or 0.05)
C02 = 10 (conversion factor for mmol/L when using a 100-mL sample)
C31 = Common Variable (result of carbonate hardness determination)
Remarks
- Soft water is best titrated with c(Na
2
EDTA) = 0.05 mol/L.
- Water that contains little Mg besides a high Ca concentration yields a bad
separation of the titration curve steps. In these cases we recommend to add Mg
standard to the auxiliary complexing solution. This Mg addition must of course
be taken into account in the calculations.
Example: Water hardness in tap water (Herisau)
Water hardness
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-21 time 08:35 1
U(init) 10 mV DET U Ca+Mg
EP1 1.871 ml -33 mV
EP2 2.686 ml -103 mV
total hardness 2.686 mmol/L
Ca hardness 1.871 mmol/l
Mg hardness 0.815 mmol/l
stop V reached
============
'pa
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-21 time 08:35 1
DET U Ca+Mg
parameters
meas.pt.density 1
min. incr. 10.0 l
equilibr.time 52 s
start V: OFF
pause 0 s
meas.input: 1
temperature 25.0 C
>stop conditions
stop V: abs.
stop V 8 ml
stop U OFF mV
stop EP 9
>statistics
status: OFF
>evaluation
EPC 5
EP recognition: all
fix-EP1 at U OFF mV
pK/HNP: OFF
>preselections
req.ident: OFF
req.smpl size: OFF
activate pulse: OFF
============
Two alternative titrimetric methods for determining total water
hardness
Potentiometric titration with the Cu ISE
Accessories
- 6.0502.140 Cu ISE with mit 6.2104.020 electrode cable
Reagents
- Titrant: c(Na
2
EDTA) = 0.1 mol/L
- Cu-complex solution: c|Cu(NH
4
)
2
EDTA| = 0.1 mol/L, e.g. Merck no. 105217
- Buffer solution pH = 10:
Dissolve 54 g NH
4
Cl and 350 mL w(NH
3
) = 25% in dist. H
2
O, make up to 1 L
with dist. H
2
O and mix.
Analysis
Pipet 100 mL water sample into the titration beaker. Add 5 mL buffer solution pH =
10, followed by 0.5 mL Cu-complex solution, stir for 20 s and titrate with Na
2
EDTA
past the last, clearly pronounced endpoint.
Calculation
Total hardness; mmol/L = EP1 x C01 x C02
EP1 = mL Na
2
EDTA consumed to reach the endpoint
2
Remarks
- Soft waters are best titrated with c(Na
2
EDTA) = 0.05 mol/L.
- This method cannot be used for sea water.
- Polish the surface of the Cu ISE with aluminum oxide from time to time.
Water hardness
Example: Total hardness of a drinking water (Herisau)
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-08 time 13:57 1
U(init) -74 mV MET U *******
smpl size 200 ml
EP1 5.286 ml -189 mV
Ca & Mg 2.64 mmol/l
stop V reached
============
'pa
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-08 time 13:57 1
MET U ********
parameters
V step 0.05 ml
equilibr.time 26 s
start V: OFF
pause 0 s
meas.input: 1
temperature 25.0 C
>stop conditions
stop V: abs.
stop V 7 ml
stop U OFF mV
stop EP 9
>statistics
status: OFF
>evaluation
EPC 10 mV
fix-EP1 at U OFF mV
pK/HNP: OFF
>preselections
req.ident: OFF
req.smpl size: OFF
activate pulse: OFF
============
Water hardness
Photometric titration with the 610 nm Spectrosense
Accessories
- 6.1109.110 Spectrosense 610 nm with 6.2116.020 electrode cable and
6.2108.130 power cable for Titrinos or 6.2151.070 for Titrandos
Reagents
- Titrant: c(Na
2
EDTA) = 0.1 mol/L
See above, Potentiometric titration with the Cu ISE.
- Mg complex:
K
2
MgEDTA x 2 H
2
O, e.g. Merck no. 108409
- Indicator solution: Eriochrome Black T
0.25 g Eriochrome Black T and approx. 0.3 g ascorbic acid
4
are dissolved in
dist. H
2
O, made up to the mark with dist. H
2
O and mixed.
Analysis
Pipet 100 mL water sample into the titration beaker. Add approx. 0.1 g Mg com-
plex, 10 mL buffer solution pH = 10 and 0.25 mL indicator solution. Degas for
approx. 3 min in an ultrasonic bath. Titrate past the first endpoint with Na
2
EDTA
solution.
Calculation
Total hardness; mmol/L = EP1 x C01 x C02
EP1 = mL Na
2
EDTA consumed to reach the endpoint
2
Remarks
- Soft waters are best titrated with c(Na
2
EDTA) = 0.05 mol/L.
- Make sure that no air bubbles get stuck in the light path of the Spectrosense
during the titration.

4
Stabilizes the indicator dyestuff.
Water hardness
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-08 time 11:00 1
U(init) 503 mV MET U *******
smpl size 200 ml
EP1 5.259 ml 491 mV
Ca & Mg 2.63 mmol/l
stop V reached
============
'pa
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-08 time 11:00 1
MET U ********
parameters
V step 0.05 ml
equilibr.time 26 s
start V: OFF
pause 0 s
meas.input: 1
temperature 25.0 C
>stop conditions
stop V: abs.
stop V 7 ml
stop U OFF mV
stop EP 9
>statistics
status: OFF
>evaluation
EPC 30 mV
EP recognition: all
fix-EP1 at U OFF mV
pK/HNP: OFF
>preselections
req.ident: OFF
req.smpl size: OFF
activate pulse: OFF
============
- Application Bulletin no. 125 Simultaneous determination of calcium and
magnesium in water samples and beverages and the different types of water
hardness by complexometric titration with potentiometric indication
- Application Bulletin no. 101 Complexometric titrations with the Cu ISE
- Ti Application Note no. T-52 Total water hardness by photometric titration
Kjeldahl nitrogen
General remarks
The Kjedahl method determines ammonium nitrogen and a large portion of the
organically bound nitrogen of a water sample. The nitrogen present in the follow-
ing species is not or only partially determined: nitrite, nitrate, azide, cyanide;
hetero-cyclic, nitro, nitroso and diazo compounds.
The sample is digested with sulfuric acid in the presence of a catalyst. This con-
verts organically bound nitrogen to ammonium sulfate. In a distillation apparatus,
an excess of NaOH is added to the digestion solution and the liberated ammonia
(NH
3
) distilled into a vessel containing boric acid. The absorbed ammonia is then
titrated with HCl.
- Magnetic stirrer
- Combined pH glass electrode: 6.0259.100 Unitrode with 6.2104.020 electrode
cable
Reagents
- Sulfuric acid: w(H
2
SO
4
) = 98%
- Catalyst:
5-g tablets of varying composition are available from the reagent manufacturers.
We recommend to use tablets without Se and/or Hg addition.
- Sodium hydroxide solution: c(NaOH) = 10 mol/L
In a glass beaker, dissolve under stirring 400 g NaOH in approx. 600 mL dist.
H
2
O. After the solution has cooled down, make up to the mark with dist. H
2
O
and mix.
- Absorption solution: w(H
3
BO
3
) = 2%
Dissolve 20 g boric acid in dist. H
2
O, make up to 1 L with dist. H
2
O and mix.
This titrant, which is available ready-for-use from the reagent manufacturers, is
only used for determining the Kjeldahl N of strongly loaded wastewaters.
Dilute 200 mL c(HCl) = 0.1 mol/L with dist. H
2
O to 1 L. This titrant is used for
untreated, surface and drinking waters.
- Buffer solutions pH = 4.00 and pH = 7.00,
e.g. Metrohm no. 6.2307.100 und 6.2307.110
Kjeldahl nitrogen
Sample preparation
The sample volume has to be adjusted to the expected nitrogen content. Waste-
waters must be homogenized before digestion, e.g. with a high-frequency mixer.
Use 250 mL dist. H
2
O to determine the blank value of the chemicals. The table
below shows the sample volumes to be used when applying c(HCl) = 0.02 mol/L
as titrant.
mg/L N Sample volume (mL)
<10 250
10...20 100
20...50 50
50...100 25
Add a catalyst tablet and 10 mL sulfuric acid to the water sample in the digestion
flask or digestion tube. Quickly heat to boiling and keep boiling until white SO
3
fumes appear and the solution becomes clear and colorless. Heat for another
10 min and leave to cool down.
Analysis
Before the titration, calibrate the pH electrode with buffer solutions pH = 7.00 and
pH = 4.00.
Attach the digestion flask or digestion tube to the distillation apparatus, add NaOH
solution to the digestion solution and start the distillation together with the titration.
Titrate 50 mL absorption solution with c(HCl) = 0.02 mol/L, using the following
parameter settings:
EP1 at pH 4.5
max. rate 2 mL/min
min. rate 25 L/min
titr. direction auto
Calculations
1 mL c(HCl) = 0.02 mol/L corresponds to 0.28014 mg N
RS1; mg/L N = (EP1 C30) x C01 x C02 / C00
RS2; mol/L N = RS1 x C03
EP1 = mL HCl consumed to reach the endpoint
C00 = sample volume in mL
C01 = 0.28014
C02 = 1000 (for 1 L)
C03 = 71.4 (conversion factor mg/L mol/L)
C30 = Common Variable blank value due to chemicals used in mL HCl,
c = 0.02 mol/L)
The results are given to one decimal place.
'pa
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-18 time 13:39 4
SET pH ********
parameters
>SET1
EP at pH 4.50
dynamics OFF
max.rate 2 ml/min
min.rate 25.0 l/min
stop crit: drift
stop drift 20 l/min
>SET2
EP at pH OFF
titr.direction: auto
pause 1 0 s
start V: OFF
pause 2 0 s
extr.time 0 s
meas.input: 1
temperature 25.0 C
time interval 2 s
>stop conditions
stop V: abs.
stop V 10 ml
>statistics
status: OFF
>preselections
conditioning: OFF
req.ident: OFF
req.smpl size: OFF
activate pulse: OFF
============
'cr
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-18 time 12:04 2
meas.input: 1 CAL ********
cal.date 2004-10-18
pH U/mV
buffer # 1 7.00 0
buffer # 2 4.00 175
cal.temp. 25.0 C
slope(rel.) 0.985 pH(as)
7.00
============
Hydrogen peroxide and its adducts
Inlet:
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-18 time 13:22 3
pHc(init) 6.28 SET pH ********
smpl size 20 ml
EP1 3.229 ml 4.46
nitrogen 45.23 mg/L
nitrogen 3229 mol/L
============
Outlet:
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-18 time 13:39 4
pHc(init) 5.96 SET pH ********
smpl size 50 ml
EP1 1.998 ml 4.46
nitrogen 11.19 mg/L
nitrogen 799 mol/L
============
General remarks
Hydrogen peroxide and its adducts (e.g. perborate, percarbonate, peracetic acid)
can be present in wastewaters from laundries or after the application of disinfec-
tant solutions. All these compounds can be oxidized by permanganate, whereby
the following overall reaction takes place:
2 MnO
4
+ 5 H
2
O
2
+ 6 H
3
O
+
2 Mn
2+
+ 5 O
2
+ 14 H
2
O
- Titrino or Tirando with Dosino or Dosimat
- Magnetic stirrer
- 6.0451.100 combined Pt-ring electrode with 6.2104.020 electrode cable
Reagents
- Titrant 1: c(KMnO
4
) = 0.02 mol/L
This titrant is available ready-for-use from the reagent manufacturers. It is used
for mass concentrations |(H
2
O
2
) = 10...100 mg/L.
- Titrant 2: c(KMnO
4
) = 0.001 mol/L
Pipet 50.0 mL c(KMnO
4
) = 0.02 mol/L into a 1-L volumetric flask and add 1 mL
w(H
2
SO
4
) = 98%. Make up to the mark with dist. H
2
O and mix. This titrant is
used for mass concentrations |(H
2
O
2
) = 0.4...10 mg/L.
- Acid-catalyst solution:
Dissolve 15 g MnSO
4
x H
2
O in approx. 500 mL dist. H
2
O. Under stirring cau-
tiously add 80 mL w(H
2
SO
4
) = 98%. Leave to cool down and make up to 1 L
with dist. H
2
O.
Analysis
Pipet 100 mL water sample into the titration beaker and add 10 mL acid-catalyst
solution. Titrate with KMnO
4
solution past the first endpoint. If c(KMnO
4
) = 0.001
mol/L is used as the titrant, a polarization current of +1 A is applied to the Pt
electrode.
Calculations
1 mL c(KMnO
4
) = 0.02 mol/L corresponds to 1.701 mg H
2
O
2
1 mL c(KMnO
4
) = 0.001 mol/L corresponds to 0.085 mg H
2
O
2
mg/L H
2
O
2
= EP1 x C01 x C02 / C00
EP1 = mL KMnO
4
solution consumed to reach the endpoint
C00 = sample volume in mL (100)
C01 = 1.701 or 0.085
C02 = 1000 (for 1 L)
Remarks
- H
2
O
2
and its adducts are determined together.
- The conversion is complete even at room temperature if Mn(II) ions are added
as a catalyst.
- By polarizing the Pt electrode one obtains, even with a diluted titrant, titration
curves that can be evaluated without any problems.
Example: H
2
O
2
in a laundry wastewater
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-19 time 09:32 2
U(init) 295 mV MET Ipol *******
smpl size 100 ml
EP1 6.047 ml 363 mV
H2O2 5.14 mg/L
stop V reached
============
'pa
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-19 time 09:32 2
MET Ipol ********
parameters
V step 0.05 ml
equilibr.time 26 s
start V: abs.
start V 4 ml
pause 20 s
I(pol) 1 A
electrode test: OFF
temperature 25.0 C
>stop conditions
stop V: abs.
stop V 8 ml
stop U OFF mV
stop EP 9
>statistics
status: OFF
>evaluation
EPC 30 mV
EP recognition: all
fix-EP1 at U OFF mV
>preselections
req.ident: OFF
req.smpl size: OFF
activate pulse: OFF
============
- Ti Application Note no. T-25 Hydrogen peroxide in aqueous solutions
Complexing capacity
General remarks and relevant literature
It is common knowledge that the complexing of metal ions by organic ligands influ-
ences the bioavailability as well as the toxicity towards aquatic organisms of metal
species. Investigations have shown that generally the bulk, i.e. up to 90%, of the
trace metals in surface waters (rivers, lakes, sea) is complexed by organic ligands.
These results are important for understanding the biological cycles of water
systems.
Metal speciation is the subject of a large number of publications. Many of these de-
scribe a type of voltammetric titration during which increments of the free metal
ion are added to the water sample. After an equilibration time an ASV or CSV run is
carried out (ASV = Anodic Stripping Voltammetry, CSV = Cyclic Stripping Voltam-
metry). The normally V- or L-shaped titration curves allow to calculate the stability
constants and complexing capacity. As the formation of metal complexes is strongly
pH-dependent, the measurements must be carried out at a defined pH to be compa-
rable with each other.
The procedure is similar to that described above for the Bi complexing index, albeit
with different metal ions, e.g. Cu, Zn, and at natural pH values, so that weaker
complexing agents can also be detected. Some publications contain extensive
reports concerning the determination of complex formation constants. These latter
allow to get further information on the bonding type of the corresponding species.
This monograph does not allow an in-depth treatment of this highly interesting
subject. The small literature selection appearing below is meant for readers who
wish to get additional information.
- Chau,Y.K., Gchter,R., Lum-Shue-Chan,K. Determination of the apparent com-
plexing capacity of lake waters. J.Fish.Res. Board Can. 31, (1974) 1515-1519
- Ruzic,I. Theoretical aspects of the direct titration of natural waters and its
information yield for trace metal speciation. Anal.Chim.Acta 140, (1982) 99-113
- van den Berg,C.M.G. Determination of copper in sea water by cathodic stripping
voltammetry of complexes with catechol. Anal.Chim.Acta 164, (1984) 195-207
- Apte,S.C., Gardner,M.J., Ravencroft,J.E. An evaluation of voltammetric titration
procedures for the determination of trace metal complexation in natural waters
by use of computer simulation. Anal.Chim.Acta 212, (1988) 1-21
- Campos,L.A., van den Berg,C.M.G. Determination of copper complexation in
sea water by cathodic stripping voltammetry and ligand competition with salicyl-
aldoxime. Anal.Chim.Acta 284, (1994) 481-496
- Xue,H.B., Sigg,L. Zinc speciation in lake waters and its determination by ligand
exchange with EDTA and differential pulse anodic stripping voltammetry.
Anal.Chim.Acta 284, (1994) 505-515
- Van den Berg,C.M.G. Evidence for organic complexation of iron in seawater.
Marine Chemistry 50, (1995) 139-157
Complexing capacity
- Einax,J., Kunze,C. Complexation capacity of aquatic systems in dependance of
different ligands and heavy metals electroanalytical investigations and statisti-
cal evaluation. Fresenius,J.Anal.Chem. 354, (1996) 895-899
- Nolting,R.F., Gerringa,L.J.A., Swagerman,M.J.W., Timmermans,K.R., de
Baar,H.J.W. Fe(III) speciation in the high nutrient, low chlorophyll Pacific region
of the Southern Ocean. Marine Chemistry 62, (1998) 335-352
- Xue,H.B., Sigg,L. Cadmium speciation and complexation by natural organic
ligands in fresh water. Anal.Chim.Acta 363, (1998) 249-259
- Ellwood,M.J., van den Berg,C.M.G. Zinc speciation in the Northeastern Atlantic
Ocean Marine Chemistry 68, (2000) 295-306
- Jin,L., Gogan,N.J. Copper complexing capacities of freshwaters by adsorptive
cathodic stripping voltammetry. Anal.Chim.Acta 412, (2000) 77-88
- Ellwood,M.J., van den Berg,C.M.G. Determination of organic complexation of
cobalt in seawater by cathodic stripping voltammetry. Marine Chemistry 75,
(2001) 33-47
- Xue,H.B., Sigg,L. A review of competitive ligand-exchange-voltammetric
methods for speciation of trace metals in freshwater
In: Taillefert,M., Rozan,T.F. (eds.) Environmental Electrochemistry Analysis
of Trace Element Biogeochemistry. ACS, Washington (2002) ISBN 0-8412-
3774-3, Chapter 18
- Gardner,M., van Veen,E. Comparability of copper complexation capacity
determination by absorption by chelating resin column and cathodic stripping
voltammetry. Anal.Chim.Acta 501, (2004) 113-117
- Meylan,S., Odzak,N., Behra,R., Sigg,L. Speciation of copper and zinc in natural
freshwater: comparison of voltammetric measurements, diffusive gradients in
thin films (DGT) and chemical equilibrium models. Anal.Chim.Acta 510, (2004)
91-100
- Guthrie,J.W., Hassan,N.M. et al. Complexation of Ni, Zn, and Cd by DOC in
some metal-impacted freshwater lakes: a comparison of approaches using
electrochemical determination of free-metal-ion and labile complexes and a
computer speciation model, WHAM V and VI. Anal.Chim.Acta 528, (2005) 205-
218
C Gaseous water constituents
Free and total chlorine
General remarks
Free chlorine or residual chlorine is the chlorine that is present as hypochloric
acid, hypochlorite ion or as elementary chlorine.
Bound chlorine is the portion of total chlorine that is present as chloroamines
5
or
organic chloroamines.
Total chlorine is the chlorine that is present in free and/or bound form.
All the species described release, when potassium iodide is added to them, a
corresponding amount of elementary iodine, which in turn can be titrated with
phenylarsine oxide or thiosulfate. If the titration is carried out at pH = 4.0, the total
chlorine is determined. At pH = 10.0, only the free (residual) chlorine is deter-
mined. Thiosulfate can only be used as the titrant under acidic conditions.
- Magnetic stirrer
- 6.0451.100 combined Pt-ring electrode or 6.0309.100 double Pt-sheet electrode
with 6.2104.020 electrode cable
Reagents
- Titrant 1: c(Na
2
S
2
O
3
) = 0.01 mol/L
Prepare fresh titrant daily from c(Na
2
S
2
O
3
) = 0.1 mol/L
6
by diluting with O
2
-free
dist. H
2
O.
- Titrant 2: c(phenylarsine oxide) = 0.00282 mol/L (0.00564 N)
Weigh 0.49 g C
6
H
5
AsO into a 1000-mL volumetric flask and dissolve in a small
volume of dist. H
2
O and 1 mL c(NaOH) = 1 mol/L. Make up to the mark with O
2
-
free dist. H
2
O and mix.
- Acetate buffer pH = 4.0:
Dissolve 146 g anhydrous sodium acetate (or 243 g sodium acetate trihydrate)
in approx. 400 mL dist. H
2
O. Add 480 mL w(acetic acid) = 98%, make up to 1 L
with dist. H
2
O and mix.

5
Derivatives of ammonia; monochloramine (NH
2
Cl), dichloramine (NHCl
2
) and nitrogen
trichloride (NCl
3,
also known as trichloramine).
6
Free and total chlorine
Dissolve 40 g NaOH under stirring in approx. 800 mL dist. H
2
O. Leave to cool
down, then make up to 1 L with dist. H
2
O and mix.
- Potassium iodide solution:
Dissolve 5 g potassium iodide in dist. H
2
O and make up to 100 mL with dist.
H
2
O. Store the solution in a dark glass bottle. Reject the solution as soon as it
becomes yellowish.
- Potassium iodate stock solution: c(1/6 KIO
3
) = 0.1 mol/L
Weigh 3.5667 g KIO
3
into a 1000-mL volumetric flask, dissolve in dist. H
2
O, fill
up to the mark with dist. H
2
O and mix.
- Potassium iodate solution for immediate use: c(1/6 KIO
3
) = 0.005 mol/L
Make up 5.00 mL stock solution to 100 mL with dist. H
2
O and mix. Prepare
fresh solution daily.
- Sulfuric acid 1:4:
Cautiously and under stirring add 200 mL w(H
2
SO
4
) = 98% to 800 mL dist. H
2
O.
Titer determination
Transfer 1...2 g potassium iodide into a beaker and dissolve in 100 mL dist. H
2
O.
Add 10 mL sulfuric acid and 5.00...10.00 mL potassium iodate solution c(1/6 KIO
3
)
= 0.005 mol/L and place the mixture in a dark place for 10 min. After this, add
100 mL dist. H
2
O and titrate the released iodine immediately with the
corresponding titrant.
The titer should be determined daily. The mean value of the titer is stored as a
Common Variable (e.g. C30) in the titrator.
Analysis
Determination of free chlorine
Add 1 mL each KI solution and c(NaOH) = 1 mol/L to 200 mL sample in the titra-
tion beaker and titrate immediately. If the free chlorine content is >5 mg/L, reduce
the sample volume accordingly and make up to 200 mL with dist. H
2
O.
Determination of total chlorine
Add 1 mL each KI solution and buffer solution pH = 4.0 to 200 mL sample in the
titration beaker and titrate immediately. If the total chlorine content is >5 mg/L,
reduce the sample volume accordingly and make up to 200 mL with dist. H
2
O.
Calculations
1 mL c(Na
2
S
2
O
3
) = 0.01 mol/L corresponds to 0.3545 mg chlorine
1 mL c(phenylarsine oxide) = 0.00282 mol/L corresponds to 0.20 mg chlorine
mg/L chlorine = EP1 x C01 x C02 x C30 / C00
EP1 = mL titrant consumed to reach the endpoint
C01 = 0.3545 or 0.2
C02 = 1000 (for 1 L)
C30 = titer of titrant
Remarks
- The endpoint of the titration can be indicated potentiometrically (combined Pt
electrode) or bivoltametrically (I
pol
= 1 A, double Pt electrode).
- Free chlorine can only be determined with thiosulfate if bivoltametric indication
is applied potentiometric indication does not yield any useful titration curves.
Example: Free and total chlorine in tap water
Dissolved oxygen
- Application Bulletin no. 249 Titrimetric determination of total and residual
chlorine in drinking and process water
Dissolved oxygen
General remarks
Iodometric titration according to Winkler is an elegant method for determining the
oxygen content of water samples.
Manganese(II) chloride and NaOH are added to the water sample. The oxygen
reacts to form manganese(III) hydroxide, which is then dissolved in acid and re-
duced to Mn(II) by iodide. This latter reaction releases an amount of iodine that is
equivalent to the oxygen and can be titrated with thiosulfate. The following reaction
equations give an overview:
Fixation in the alkaline solution:
MnCl
2
+ 2 NaOH = Mn(OH)
2
+ 2 NaCl
2 Mn(OH)
2
+ O
2
= 2 Mn(OH)
3
+ 2 H
+
(2 H
+
+ 2 OH
(excess) = 2 H
2
O)
After acidification:
2 Mn(OH)
3
+ 6 HCl = 2 MnCl
3
+ 6 H
2
O
2 MnCl
3
+ 2 KI = 2 MnCl
2
+ 2 KCl + I
2
During the titration:
2 Na
2
S
2
O
3
+ I
2
= Na
2
S
4
O
6
+ 2 NaI
- Magnetic stirrer
- 6.0309.100 double Pt-sheet electrode with 6.2104.020 electrode cable
- Winkler bottles with wide-neck ground-joint openings plus stoppers
Reagents
- Titrant: c(Na
2
S
2
O
3
) = 0.05 mol/L
- Winkler solution I
Dissolve 400 g MnCl
2
x 4 H
2
O in dist. H
2
O and make up to 1 L with dist. H
2
O.
- Winkler solution II
Dissolve 500 g NaOH, 1 g sodium azide (NaN
3
) and 150 g potassium iodide in
dist. H
2
O. Leave to cool down, then make up to 1 L with dist. H
2
O and mix
(NaN
3
prevents interferences by nitrite ions).
- Acid mixture:
Mix 350 mL each of w(H
3
PO
4
) = 85% and w(HCl) = 36% and make up to 1 L
with dist. H
2
O (the H
3
PO
4
prevents interferences by Fe(III) ions).
Sample preparation
Fill the water sample into the sample bottle until it flows over. Make sure no bub-
bles are trapped and seal the bottle. Remove the stopper and immediately add,
below the water surface, 2 mL each of Winkler solution I and II, reseal immediately
and mix. If the sample contains no O
2
, the precipitate formed is white. The more
O
2
the sample contains, the darker brown the precipitate is.
When the precipate has settled, i.e. after several hours, carefully aspirate approx.
1/3 of the supernatant liquid, add 10 mL acid mixture to the bottle contents, seal
the bottle and mix.
Dissolved oxygen
Analysis
If wide-neck bottles are used, add a stirrer bar. Otherwise, transfer the solution
quantitatively into a titration beaker with dist. H
2
O and titrate immediately with
c(Na
2
S
2
O
3
) = 0.05 mol/L in the SET mode (I
pol
= 1 A) to the predefined endpoint.
Calculation
1 mL c(Na
2
S
2
O
3
) = 0.05 mol/L corresponds to 0.40 mg O
2
g/L O
2
= EP1 x C01 x C02 / (C00 C03)
EP1 = mL thiosulfate solution consumed to reach the endpoint
C00 = volume of sample bottle in mL
C01 = 0.4
C02 = 1000 (for 1 L)
C03 = 4 (2 mL each of Winkler solution I and II)
Remarks
The oxygen-uptake capacity of waters depends on three parameters:
- Temperature increasing temperature reduces the uptake capacity.
- Pressure increasing pressure increases the uptake capacity.
- Salt content increasing salt content reduces the uptake capacity. The de-
crease amounts to approx. 0.554% per g/L salt.
To calculate the oxygen saturation of a water sample, one has to take into account
the air pressure, temperature and salt content of the sample. The following tables
give an overview:
Air pressure as a function height above sea level
101.325 kPa = 1 atm = 760 mm Hg
H/m = height above sea level in meters
kPa = average air pressure in kilopascal
H/m kPa H/m kPa
0 101.3 900 90.5
100 100.1 1000 89.4
200 98.8 1100 88.3
300 97.6 1200 87.2
400 96.4 1300 86.1
500 95.2 1400 85.0
600 94.0 1500 84.0
700 92.8 1600 82.9
800 91.7 1700 81.9
Solubility of oxygen (saturation) as a function of temperature and air pressure
Temperature in C, air pressure in kPa, oxygen saturation in mg/L O
2
Temp. 111.5 kPa 101.3 kPa 91.2 kPa 81.1 kPa 70.9 kPa
0.0 16.09 14.62 13.14 11.69 10.21
5.0 14.06 12.77 11.48 10.20 8.91
10.0 12.43 11.29 10.15 9.00 7.86
15.0 11.10 10.08 9.05 8.03 7.01
20.0 10.02 9.09 8.14 7.23 6.30
25.0 9.12 8.62 7.40 6.56 5.70
30.0 8.35 7.56 6.76 5.99 5.19
35.0 7.69 6.95 6.22 5.47 4.75
Dissolved oxygen
Example: Oxygen content of a river water
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-20 time 11:46 15
U(init) 1 mV SET Ipol *******
smpl size 118.18 g
EP1 3.287 ml 33 mV
O2 11.52 mg/L
============
'pa
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-20 time 11:46 15
SET Ipol ********
parameters
>SET1
EP at U 30 mV
dynamics 2 mV
max.rate 2 ml/min
min.rate 10 l/min
stop crit: time
stop time 10 s
>SET2
EP at U OFF mV
titr.direction: auto
pause 1 0 s
start V: OFF
pause 2 0 s
extr.time 0 s
I(pol) 1 A
electrode test: OFF
temperature 25.0 C
time interval 2 s
>stop conditions
stop V: abs.
stop V 10 ml
>statistics
status: OFF
>preselections
conditioning: OFF
req.ident: OFF
req.smpl size: OFF
limit smpl size OFF
activate pulse: OFF
============
Ozone
General remarks
The iodometric method is suitable for determining higher ozone levels in
drinking water and swimming-pool water. Any oxidants present in the water, e.g.
chlorine, chlorine dioxide, hydrogen peroxide, interfere with the determination.
Ozone oxidizes iodide to elementary iodine, which latter can be titrated with
thiosulfate. To prevent loss of ozone by degassing or decomposition, the water
sample is added to a potassium iodide solution.
- Magnetic stirrer
- 6.0309.100 double Pt-sheet electrode with 6.2104.020 electrode cable
Reagents
- Titrant: c(Na
2
S
2
O
3
) = 0.01 mol/L
- Neutral potassium iodide solution:
Dissolve 20 g KI, 7.3 g Na
2
HPO
4
x 2 H
2
O and 3.5 g KH
2
PO
4
in dist. H
2
O, make
up to 1 L with dist. H
2
O and mix.
- Dilute sulfuric acid: w(H
2
SO
4
) = approx. 25%
Cautiously and under cooling add 25 mL w(H
2
SO
4
) = 98% to 75 mL dist. H
2
O
and mix.
Sampling
Transfer 100 mL neutral potassium iodide solution into a 500-mL volumetric flask.
Make up to the mark with the water sample and mix.
Analysis
Transfer 250 mL of the pretreated sample (corresponding to 200 mL original
sample) into a titration beaker, add 10 mL dilute sulfuric acid and titrate imme-
diately with c(Na
2
S
2
O
3
) = 0.01 mol/L past the first endpoint.
Ozone
Calculation
1 mL c(Na
2
S
2
O
3
) = 0.01 mol/L corresponds to 0.24 mg O
3
mg/L O
3
= EP1 x C01 x C02 / C00
EP1 = mL thiosulfate solution consumed to reach the endpoint
C01 = 0.24
C02 = 1000 (for 1 L)
The ozone mass concentration is rounded to 0.1 mg/L.
Example: Freshly prepared swimming-pool water
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-18 time 15:48 6
U(init) 0 mV MET Ipol ******
smpl size 200 ml
EP1 2.050 ml 225
mV
ozone 2.46 mg/L
stop V reached
============
'pa
785 DMP Titrino 02287 785.0011
user cst
date 2004-10-18 time 15:48 6
MET Ipol ********
parameters
V step 0.05 ml
equilibr.time 26 s
start V: OFF
pause 0 s
I(pol) 1 A
electrode test: OFF
temperature 25.0 C
>stop conditions
stop V: abs.
stop V 3 ml
stop U OFF mV
stop EP 9
>statistics
status: OFF
>evaluation
EPC 30 mV
EP recognition: all
fix-EP1 at U OFF mV
>preselections
req.ident: OFF
req.smpl size: OFF
activate pulse: OFF
============
D1 Titration: Chloride
D Anions
General remarks
Chloride ions occur in most waters, even in rain water. Their concentrations range
from a few mg/L (ground and drinking water) to g/L (brackish, sea and waste-
water).
The titrimetric determination of chloride ions is carried out with silver nitrate. Inter-
ferences occur with any anions forming precipitates with AgNO
3
that are less solu-
ble than AgCl. These anions are mainly sulfide, cyanide, iodide and bromide. The
precipitation and titration sequence can be predicted from the solubility product K
L
.
The least soluble precipitate is always titrated first. The table gives an overview:
Ag salt
K
L
mol
2
/ L
2
AgBr 7.7 x 10
13
Ag
2
CO
3
6.15 x 10
12
AgCl 1.56 x 10
10
AgCN 2.2 x 10
12
AgCNS 1.16 x 10
12
AgI 1.5 x 10
16
Ag
2
S 1.6 x 10
49
Interferences by sulfide can be eliminated by adding H
2
O
2
, which oxidizes sulfide
to sulfate. Interferences by carbonate are overcome by titrating in acidic solution
(pH value <4).
- Magnetic stirrer
- 6.0430.100S Ag Titrode with Ag
2
S coating; 6.2104.020 electrode cable
Reagents
- Titrant 1: c(AgNO
3
) = 0.1 mol/L
For chloride contents >300 mg/L. This titrant is available ready-for-use from the
reagent manufacturers.
D Anions
- Titrant 2: c(AgNO
3
) = 0.01 mol/L
For chloride contents <300 mg/L. Add 1 mL w(HNO
3
) = 65% to 100 mL
c(AgNO
3
) = 0.1 mol/L, make up to 1 L with dist. H
2
O and mix. Store in a dark
bottle.
- Nitric acid: c(HNO
3
) = approx. 2 mol/L
Mix 20 mL w(HNO
3
) = 65% with 80 mL dist. H
2
O.
Analysis
Transfer 100 mL water sample into a beaker, add 5 mL c(HNO
3
) = 2 mol/L and
titrate with c(AgNO
3
) = 0.01 mol/L or 0.1 mol/L. At higher chloride contents, add 5
mL c(HNO
3
) = 2 mol/L to 1 to 50 mL water sample and make up to approx. 100 mL
with dist. H
2
O.
Calculations
1 mL c(AgNO
3
) = 0.01 mol/L corresponds to 0.3545 mg chloride
1 mL c(AgNO
3
) = 0.10 mol/L corresponds to 3.545 mg chloride
mg/L chloride = EP1 x C01 x C02 / C00
EP1 = mL AgNO
3
solution consumed to reach the endpoint
C01 = 0.3545 or 3.545
C02 = 1000 (for 1 L)
The result is given with three significant digits.
- Application Bulletin no. 130 Chloride titrations with potentiometric indication
Example: Chloride in tap water (Herisau)
D Anions
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-21 time 11:01 2
U(init) 115 mV DET U chloride
smpl size 100 ml
EP1 2.296 ml 48 mV
chloride 8.14 mg/L
stop V reached
============
'pa
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-21 time 11:01 2
DET U chloride
parameters
meas.pt.density 4
min. incr. 10.0 l
equilibr.time 32 s
start V: OFF
pause 0 s
meas.input: 1
temperature 25.0 C
>stop conditions
stop V: abs.
stop V 5 ml
stop U OFF mV
stop EP 9
>statistics
status: OFF
>evaluation
EPC 10
fix-EP1 at U OFF mV
pK/HNP: OFF
>preselections
req.ident: OFF
req.smpl size: OFF
activate pulse: OFF
============
D1 Titration: Cyanide
General remarks
The determination of cyanide in seepage water and electroplating wastewater
before and after decontamination is highly important. Concentrations as low as
0.05 mg/L of cyanide can be lethal for fish species.
One has to distinguish between easily released cyanides, e.g. from KCN, and the
total cyanide content, which comprises also the CN complexes of heavy metals.
The decomposition and separation occurs according to DIN 38405 D13/D14. We
will use the potentiometric titration with silver nitrate, which is described by the
following reactions:
2 CN
-
+ Ag
+
|Ag(CN)
2
|
-
EP 1 (large potential jump)
|Ag(CN
2
)
-
+ Ag
+
2 AgCN ! EP 2 (small potential jump)
EP 1 is used for the titration. If c(AgNO
3
) = 0.0002 mol/L is used as the titrant,
concentrations as low as 0.01 mg/L CN
can be determined. HCN, as shown by its

pK
A
of 9.4, is a very weak acid. To prevent losses, the titration is always carried
out in strongly alkaline solution (pH = >12).
- Magnetic stirrer
2
Reagents
- Titrant stock solution: c(AgNO
3
) = 0.1 mol/L
- Titrant solutions: c(AgNO
3
) = 0.01, 0.002 or 0.0002 mol/L
These solutions are prepared by diluting the stock solution with c(HNO
3
) =
0.001 mol/L and have to be stored in dark bottles.
In a beaker dissolve under stirring 40 g NaOH in approx. 500 mL dist. H
2
O.
Leave to cool down and make up to 1 L with dist. H
2
O.
- Decomposition chemicals:
These can be found in Application Bulletin no. 46.
Analysis
The easily released cyanides (e.g. from KCN) are determined by driving off HCN
at room temperature and a pH value of approx. 4 by means of an air stream and
absorbed in c(NaOH) = 1 mol/L.
D Anions
The determination of the total cyanide content, which also comprises the complex
heavy metal cyanides, is carried out by driving off the HCN under boiling in the
presence of Cu(I) ions and HCl and absorbing the HCN in c(NaOH) = 1 mol/L.
Normally, 100 mL water sample is used. If the water contains less than 0.1 mg/L
cyanide, the sample volume is increased to 200 mL.
Rinse the contents of the absorption vessel into a beaker using dist. H
2
O. At
cyanide concentrations of 0.2...10 mg/L, titrate with c(AgNO
3
) = 0.002 mol/L, at
cyanide concentrations of 0.01...0.5 mg/L with c(AgNO
3
) = 0.0002 mol/L. Higher
cyanide concentrations e.g. in electroplating wastewaters can be titrated at pH
= >12 directly with c(AgNO
3
) = 0.01 mol/L.
Calculations
1 mL c(AgNO
3
) = 0.0002 mol/L corresponds to 0.0104 mg CN
-
1 mL c(AgNO
3
-
1 mL c(AgNO
3
-
mg/L CN
-
= EP1 x C01 x C02 / C00
EP1 = titrant consumption in mL
C00 = sample volume in mL (100...200)
C01 = 0.52 or 0.104 or 0.0104
C02 = 1000 (for 1 L)
Remarks
- Condition the electrode before the first analysis for 20 min in a solution of 0.3
mg/L CN
in c(NaOH) = 0.4 mol/L.

- The detailed procedure is described in Application Bulletin no. 46 Potentio-
metric determination of cyanide.
Example: Cyanide in an electroplating wastewater
(direct titration)
D Anions
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-23 time 14:26 9
U(init) -98 mV DET U M14
smpl size 100 ml
EP1 5.637 ml -207 mV
CN- 29.33 mg/l
stop V reached
============
'pa
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-23 time 14:26 9
DET U M14
parameters
meas.pt.density 2
min. incr. 10.0 l
equilibr.time 32 s
start V: OFF
pause 0 s
meas.input: 1
temperature 25.0 C
>stop conditions
stop V: abs.
stop V 10 ml
stop U OFF mV
stop EP 9
>statistics
status: OFF
>evaluation
EPC 5
fix-EP1 at U OFF mV
pK/HNP: OFF
>preselections
req.ident: OFF
req.smpl size: OFF
activate pulse: OFF
============
- Application Bulletin no. 46 Potentiometric determination of cyanide
D1 Titration: Sulfate
General remarks
The method allows the interference-free determination of sulfate in the presence of
Ca, Mg and Cl ions. An excess of Ba ions is added to the sample. This causes the
sulfate to be precipitated as BaSO
4
. The portion of the Ba not precipitated with the
sulfate is determined by back-titration with EGTA. This titration yields two end-
points, EP1 corresponding to the Ca and the difference EP2EP1 to the excess
Ba. Mg does not interfere as it is not complexed by EGTA.
The determination limit is approx. 10 mg/L sulfate.
- Magnetic stirrer
- 6.0508.110 Ca ISE with 6.2104.020 electrode cable
Reagents
- Titrant: c(EGTA) = 0.05 mol/L
Weight 19.4 g ethyleneglycol-bis-(2-aminoethyl)-tetraacetic acid (98%) into a
beaker and suspend under stirring in approx. 200 mL dist. H
2
O. Add c(NaOH) =
10 mol/L until the substance is completely dissolved. Leave to cool down and
transfer with dist. H
2
O quantitatively into a 1-L volumetric flask, make up to the
mark with dist. H
2
O and mix.
- Barium chloride solution: c(BaCl
2
) = 0.05 mol/L
Weigh 12.34 g BaCl
2
x 2 H
2
O (99%) into a 1-L volumetric flask, dissolve in
c(HCl) = 0.01 mol/L, fill up to the mark with this latter and mix.
Weigh 9 g NH
4
Cl into a 1-L volumetric flask and dissolve in approx. 800 mL dist.
H
2
O. Add 60 mL w(NH
3
) = 25%, make up to the mark with dist. H
2
O and mix.
- Hydrochloric acid: c(HCl) = approx. 2 mol/L
Dilute conc. HCl with dist. H
2
O 1:5.
Blank value determination
Transfer approx. 30 mL dist. H
2
O and 5.00 mL c(BaCl
2
) = 0.05 mol/L into the
titration beaker. Add 5 mL buffer solution pH = 10, leave to react for 3 min under
stirring, then titrate with c(EGTA) = 0.05 mol/L. Store the titrant consumption as a
Common Variable (e.g. C31 in the Titrinos).
D Anions
Analysis
A water sample containing not more than 20 mg sulfate is pipetted into the titration
beaker and brought to a pH value of <4 by the dropwise addition of HCl. Add 5.00
mL c(BaCl
2
) = 0.05 mol/L and leave to react for 3 min under stirring. Add 5 mL
buffer solution pH = 10 and leave to react for another 3 min under stirring. Titrate
with c(EGTA) = 0.05 mol/L past the second endpoint. EP1 corresponds to the Ca
and the difference EP2EP1 to the Ba excess.
Calculations
1 mL c(EGTA) = 0.05 mol/L corresponds to 4.803 mg sulfate or 2.004 mg Ca
RS1; EP2 EP1 (mL)
RS2; mg/L sulfate = (C31 RS1) x C01 x C02 / C00
RS3; mg/L calcium = EP1 x C03 x C02 / C00
EP1 = mL EGTA consumed to reach the first endpoint
EP2 = mL EGTA consumed to reach the second endpoint
C01 = 4.803
C02 = 1000 (for 1 L)
C03 = 2.004
C31 = mL EGTA consumend in blank determination (Common Variable)
Remarks
- The water samples must be acified with HCl to prevent the precipitation of
BaCO
3
.
- Waters that do not contain Ca must be spiked, e.g. with 2 mg Ca standard.
- The total water hardness cannot be determined with this method as Mg is not
taken into account.
Example: Titration curves for blank consumption and sulfate in a
ground-water sample
D Anions
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-21 time 17:02 10
U(init) 25 mV DET U sulfate
smpl size 100 ml
EP1 3.859 ml -26
mV
EP2 5.765 ml -91
mV
Sulfat 30.26 mg/L
Ca 77.33 mg/L
stop V reached
============
'pa
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-21 time 15:01 8
DET U sulfate
parameters
meas.pt.density 4
min. incr. 10.0 l
equilibr.time 32 s
start V: OFF
pause 0 s
meas.input: 1
temperature 25.0 C
>stop conditions
stop V: abs.
stop V 10 ml
stop U OFF mV
stop EP 9
>statistics
status: OFF
>evaluation
EPC 5
EP recognition: all
fix-EP1 at U OFF mV
pK/HNP: OFF
>preselections
req.ident: OFF
req.smpl size: OFF
activate pulse: OFF
============
- Application Bulletin no. 140 Titrimetric determination of sulfate
D1 Titration: Sulfides and hydrogen sulfide
General remarks
Sulfides and/or H
2
S can be present in reductive ground water, in seepage water
and at the bottom of surface waters (under anaerobic conditions). The addition of
silver nitrate produces insoluble precipitates (K
L
= 1.6 x 10
49
).
Sulfides are volatile and easily oxidized by atmospheric oxygen. They are
determined by titration with AgNO
3
in strongly alkaline solution and under nitrogen
sparging.
The determination limit is approx. 0.05 mg/L sulfide.
- Magnetic stirrer
2
Reagents
- Titrant: c(AgNO
3
) = 0.001 mol/L
Add 0.1 mL w(HNO
3
) = 65% to 10.0 mL c(AgNO
3
) = 0.1 mol/L (commercially
available), make up to 1 L with dist. H
2
O in a volumetric flask and mix. Store in
a dark bottle.
- Sodium hydroxide solution: w(NaOH) = 30%
- Nitrogen: O
2
-free from a pressure cylinder or from the lab's gas supply system
Analysis
Transfer 1 mL NaOH into the titration beaker. Add 100 mL water sample, sparge
with nitrogen and titrate with c(AgNO
3
) = 0.001 mol/L past the first endpoint.
Calculations
1 mL c(AgNO
3
) = 0.001 mol/L corresponds to 0.016 mg S
2
or 0.017 mg H
2
S
mg/L sulfide = EP1 x C01 x C02 / C00
EP1 = mL AgNO
3
consumed to reach the first endpoint
C01 = 0.016 or 0.017
C02 = 1000 (for 1 L)
D Anions
Remarks
- Sulfides and hydrogen sulfide are very volatile compounds. We therefore
recommend to make the samples alkaline immediately after sampling.
- The Ag
2
S coating on the Ag Titrode ensures the fast response and stable
adjustment of this electrode.
Example: Sulfide in a wastewater sample
'fr
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-23 time 10:27 7
U(init) -300 mV DET U
smpl size 100 ml
EP1 5.268 ml -402 mV
H2S 0.90 mg/l
S2- 0.84 mg/l
stop V reached
============
'pa
785 DMP Titrino 02287 785.0011
user cst
date 2004-09-23 time 08:52 5
DET U M14
parameters
meas.pt.density 2
min. incr. 10.0 l
equilibr.time 32 s
start V: OFF
pause 0 s
meas.input: 2
temperature 25.0 C
>stop conditions
stop V: abs.
stop V 10 ml
stop U OFF mV
stop EP 9
>statistics
status: OFF
>evaluation
EPC 3
fix-EP1 at U OFF mV
pK/HNP: OFF
>preselections
req.ident: OFF
req.smpl size: OFF
activate pulse: OFF
============
- Ti Application Note no. T-32 Hydrogen sulfide or sulfide in water
D Anions
D2 Ion chromatography: Introduction
Ion chromatography (IC) is the method of choice for water analysis. It almost
seems to have been invented especially for this field. Its advantages are obvious:
- Multispecies analysis several species (e.g. anions, cations) can be deter-
mined simultaneously in one run.
- High selectivity optimized columns and eluents improve separations
perfectly separated peaks.
- Low detection limits; preconcentration allows to reach the ng/L (ppt) range.
- High precision and accuracy thanks to software programs for linear and non-
linear calibration curves.
- High degree of automation allows large sample series and monitoring.
As a support to its customers Metrohm publishes a wide range of monographs.
Please consult the list of monographs on our website and order those that interest
you free of charge from your Metrohm distributor.
Of course one has to consider which ions have to be determined at which concen-
tration in which type of water (wastewater, ground water, drinking water, lake, river
or sea water, cooling or rain water). These questions are treated in a large number
of publications in scientific journals. A small selection of these is given below.
For reasons of space the practical examples that follow after the publications
present only a small number of analytical methods.
Publications in scientific journals
- Magnuson,M.L., Urbansky,E.T., Kelty,C.A. Determination of perchlorate at trace
levels in drinking water by ion-pair extraction with electrospray ionisation mass
spectrometry. Anal.Chem. 72, (2000) 25-29
- Olesky-Frenzel,J., Wischnak,S., Jekel,M. Application of ion-chromatography for
the determination of the organic-group parameters AOCl, AOBr and AOI in
water. Fresenius, J.Anal.Chem. 366, (2000) 89-94
- Ko,Y.W., Gremm,T.J., Abbt-Braun,G., Frimmel,F.H. Chiang,P.Ch.
Determination of dichloroacetic acid and trichloroacetic acid by liquid-liquid
extraction and ion chromatography. Fresenius, J.Anal.Chem. 366, (2000) 244-
248
- Huang,Y., Mou,S., Riviello,J.M. Determination of ammonium in seawater by
column-switching ion chromatography. J. Chromatogr. 868, (2000) 209-216
- Li,H.B., Chen,F. Determination of silicate in water by ion exclusion chromato-
graphy with conductivity detection. J.Chromatogr. 874, (2000) 143-147
- Jackson,P.E., Gokhale,S., Streib,T., Rohrer,J.S., Pohl,C.A. Improved method
for the determination of trace perchlorate in ground and drinking waters by ion
chromatography. J.Chromatogr. 888, (2000) 151-158
D2 Ion chromatography: Introduction
- Schminke,G., Seubert,A. Simultaneous determination of inorganic disinfection
by-products and the seven standard anions by ion chromatography.
J.Chromatogr. 890, (2000) 295-301
- De Borba,M., Rowe,D.E. Determination of trace-level perchlorate according to
US EPA method 314.0 using a polyvinyl alcohol gel resin. American Laboratory
News 33, (2001) 22-24
- Stefanovic,S.C., Bolanca,T., Curkovic,L. Simultaneous determination of six
inorganic anions in drinking water by non-suppressed ion chromatography.
J.Chromatogr. 918, (2001) 325-334
- De Borba,B.M., Brewer,J.M., Camarda,J. On-line dialysis as a sample
preparation technique for ion chromatography. J.Chromatogr. 919, (2001) 59-65
- Nickus,U., Thies,H. Ion chromatographic determination of lithium at trace level
concentrations. Application to a tracer experiment in a high-mountain lake.
J.Chromatogr. 920, (2001) 201-204
- Hautman,D.P., Munch,D.J., Frebisw,Ch., Wagner,H.P., Pepich,B.V. Review of
the methods of the US Environment Protection Acency for bromate
determination and validation of method 317.0 for disinfection by-product anions
and low level bromate. J.Chromatogr. 920, (2001) 221-229
- Prenzel,H. Development of ion chromatography in power plant chemistry.
Powerplant Chemistry 3, (2001) 93-97
- Fischer,K. Environmental analysis of aliphatic carboxylic acids by ion-exclusion
chromatography. Anal.Chim.Acta 465, (2002) 157-173
- De Borba,B.M., Laikhtman,M., Rohrer,J.S. Determination of sodium at low ng/L
concentrations in simulated power plant waters by ion chromatography.
J.Chromatogr. 995, (2003) 143-152
- Liu,Y., Mou,S. Determination of trace levels of haloacetic acids and perchlorate
in drinking water by ion chromatography with direct injection. J.Chromatogr.
997, (2003) 225-235
- Lubli,M., Proost,R., Seifert,N., Unger,S., Wille,A. Bromate in drinking water
Which method to use in ion chromatography ? LC/GC Europe (Appl.Book) Sept.
(2003) 6-7
- Giuriati,C., Cavalli,S., Gorni,A., Badocco,D., Pastore,P. Ion chromatographic
determination of sulfide and cyanide in real matrices by using pulsed
amperometric detection on a silver electrode. J.Chromatogr. 1023, (2004) 105-
112
- Wang,F., Dicinoski,G.W., Zhu,Y., Haddad,P.R. Simultaneous determination of
monofluoroacetate, difluoroacetate and trifluoroacetate in environmental
samples by ion chromatography. J.Chromatogr. 1032, (2004) 31-35
- Gandhi,J., Johnson,M., Hedrick,J. Determination of trace level perchlorate by
ion chromatography mass spectrometry. LC/GC North America (Suppl.) Febr.
(2004) 36
D Anions
- Zwiener,Ch., Frimmel,F.H. LC-MS analysis in the aquatic environment and in
water treatment a critical review. Part I: Instrumentation and general aspects
of analysis and detection. Anal.Bioanal.Chem. 378, (2004) 851-861
- Kano,I., Castillo,E., Darbouret,D., Mabic,S. Using ultrapure water in ion chroma-
tography to run at the ng/L level. J.Chromatogr. 1039, (2004) 27-31
- McDowell,M.M. et al. Detection of hypophosphite, phosphite, and orthophos-
phate in natural geothermal water by ion chromatography. J.Chromatogr. 1039,
(2004) 105-111
- Mori,M., Tanaka,K., Xu,Q., Ikedo,M., Taoda,H., Hu,W. Highly sensitive determi-
nation of hydrazine ion by ion-exclusion chromatography with ion-exchange en-
hancement of conductivity detection. J.Chromatogr. 1039, (2004) 135-139
- Paull,B., Barron,L. Using ion chromatography to monitor haloacetic acids in
drinking water: a review of current technologies. J.Chromatogr. 1046, (2004)
1-9
- Rohrer,J.S., Kaiser,E., Newton,B., Srinivasan,K., Lin,D., Riley,E. Ion chromato-
graphy for anion analysis of borated waters. Power Plant Chemistry 6, (2004)
605-609
D2 Anion determination with IC
General remarks
The determination of fluoride, chloride, nitrite, bromide, nitrate, phosphate and
sulfate is of great importance for assessing the quality of drinking or mineral water,
for example. The ion chromatographic determination of these anions is therefore
the subject of various standards.
- 861 Advanced Compact IC or MIC-2 Advanced IC system
- Anion exchange column, e.g. Metrosep Anion Dual 3 (6.1006.120) plus Metro-
sep RP Guard (6.1011.020), Metrosep A Supp 4 250 (6.1006.430), Metrosep
A Supp 5 150 (6.1006.520) plus Metrosep A Supp 4/5 Guard (6.1006.500)
Reagents
- Exclusively use reagents of highest purity and ultrapure water with a specific
resistance of >18 MOhm cm.
- The eluent contains Na
2
CO
3
and NaHCO
3
, the concentrations depend on the
column used and the application.
- Suppressor regenerant solution: c(H
2
SO
4
) = 50 mmol/L.
- Suppressor rinsing solution: ultrapure water with a specific resistance
>18 MOhm cm).
- Stock solutions containing 1 g/L fluoride, chloride, nitrite, bromide, nitrate,
phosphate and sulfate for ion chromatography can be obtained from different
manufacturers; after dilution they are used for calibrating.
- PRIMUS standards, the only primary multi-ion standards for ion chromato-
graphy, have a shelf life of three years.
Sample preparation methods
The samples have to be filtered, for example using Minisart (Sartorius) or dispos-
able filter supports (Whatman, formerly Schleicher & Schuell) with a pore size of
0.45 m or less. Even seemingly clear solutions can contain very fine particles that
damage the column.
The samples can be filtered automatically applying ultrafiltration.
At higher concentrations it may be necessary to dilute the samples.
For water samples containing a high proportion of organic substances we recom-
mend to apply dialysis as a sample preparation step that can be completely
automated.
Metrohm offers fully automated IC systems that carry out inline ultrafiltration, inline
dialysis (patented) and also inline dilution. The MISP systems (Metrohm Inline
Sample Preparation) simplify and improve sample preparation significantly.
Analysis
When working in the concentration range 10 ppb to 100 ppm, one normally injects
20...100 L sample, which is separated on the anion exchanger column and
undergoes chemical and possibly CO
2
suppression followed by conductometric
detection.
If lower detection limits are to be achieved, the sample volume must be increased
markedly. Consider, however, that larger sample volumes mean a larger water
peak, which affects the evaluation of the early-eluting peaks.
Sample preconcentration is a simple method for lowering the detection limit by
several orders of magnitude. The sample loop is replaced by a preconcentration
column. An increased sample volume, e.g. 10 mL, is passed over the
preconcentration column, which contains essentially the same material as the
separation column. This ensures that all anions contained in the sample solution to
be analyzed (e.g. ultrapure water) are kept back on the column and are
D Anions
preconcentrated. The preconcentrated analyte ions are then brought to the
separation column by the eluent flowing counter-current.
Quantitation is performed by means of an external calibration in the concentration
range concerned. A five-point calibration is recommended for the determination of
anions with chemical suppression.
Examples
Anions in drinking water with chemical suppression
0 1 2 3 4 5 6 7 8 9 min
16
18
20
22
24
26
28
30
32
uS/cm
Cond
1
2
3
4
5
Peak no. Component Retention time [min] Concentration [mg/L]
1 Fluoride 2.24 0.045
2 Chloride 3.35 9.03
3 System peak 4.62 -
4 Nitrate 5.72 10.92
5 Sulfate 8.22 5.30
Instrument 861 Advanced Compact IC (2.861.0020)
Full Scale 50 S/cm
Polarity +
Column Metrosep A Supp 5 100 (6.1006.510) plus Metrosep A Supp 4/5
Guard (6.1006.500)
Eluent 3.2 mmol/L Na
2
CO
3
/ 1.0 mmol/L NaHCO
3
Flow 0.7 mL/min
Loop 20 L
Anions in drinking water with sequential suppression
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 min
2
4
6
8
10
12
14
16
uS/cm
Cond
1
2
3
4
1 Fluoride 4.31 0.037
3 Nitrate 9.70 8.59
4 Sulfate 15.1 5.38
D Anions
Instrument 861 Advanced Compact IC (2.861.0040) with 853 CO
2
Suppressor
Full Scale 50 S/cm
Polarity +
Column Metrosep A Supp 4 250 (6.1006.430) plus Metrosep A Supp 4/5
Guard (6.1006.500)
2
CO
3
/ 1.7 mmol/L NaHCO
3
Flow 1.0 mL/min
Loop 20 L
- IC Application Note S 33 Five anions in surface water (nitrite with ELCD)
- IC Application Note S 38 Anions in wastewater with a high organic load using
dialysis for sample preparation
- IC Application Note S 52 Anions in rain water
- IC Application Note S 76 Six anions in wastewater
- IC Application Note S 187 Iodide besides standard anions in mineral water
- Metrohm Monograph Practical ion chromatography
Additional literature
- US EPA Method 300.1 Determination of inorganic anions in drinking water by
ion chromatography
- EN ISO 10304-1 Water quality Determination of dissolved anions by ion
chromatography. Determination of fluoride, chloride, nitrite, orthophosphate,
bromide, nitrate and sulfate. Part 1: Method for water with low contamination
- EN ISO 10304-2 Water quality Determination of dissolved anions by ion
chromatography. Part 2: Determination of bromide, chloride, nitrate, nitrite,
orthophosphate and sulfate in waste water
D2 Oxyhalides with IC: Chlorate, chlorite, bromate
General remarks
Chlorate, chlorite and bromate are disinfection by-products that have to be moni-
tored in water types such as drinking water and mineral water. The determination
of bromate is especially important as bromate affects the thyroid gland and is a
suspected carcinogen. Bromate is formed by the oxidation of bromide, whose
determination is therefore also very important.
The US EPA Method 300.1 part A and B is a standard method for determining inor-
ganic anions including oxyhalides in water. If this method is used, dichloroacetate
(DCA) must be added to test the method. The IC column Metrosep A Supp 7 250
fulfills the method's requirements.
- 861 Advanced Compact IC or MIC-2 Advanced IC system
- Metrosep A Supp 5 250 (6.1006.530) plus Metrosep A Supp 1 Guard
(6.1005.340)
- Metrosep A Supp 7 250 (6.1006.630)
Reagents
- Use only reagents of highest purity and ultrapure water having a specific resis-
tance >18 MOhm cm.
- Eluent: 3.2 mmol/L Na
2
CO
3
/1.0 mmol/L NaHCO
3
for Metrosep A Supp 5 250
plus Metrosep A Supp 1 Guard
2
CO
3
for Metrosep A Supp 7 250
2
SO
4
) = 50 mmol/L
- Suppressor rinsing solution: ultrapure water (specific resistance >18 Mohm cm)
- Chlorite standard: |(chlorite) = 1 g/L
Weigh 0.1676 g sodium chlorite (80%) into a 100-mL volumetric flask and
dissolve in ultrapure water. Make up to 100 mL with ultrapure water and mix.
If stored in the dark and at 4 C, the stock solution has a shelf life of approx.
2 weeks.
- Chlorate standard: |(chlorate) = 1 g/L
Weigh 0.1275 g sodium chlorate into a 100-mL volumetric flask and dissolve in
ultrapure water. Make up to 100 mL with ultrapure water and mix.
- Bromate standard: |(bromate) = 1 g/L
Weigh 0.1180 g sodium bromate into a 100-mL volumetric flask and dissolve in
D Anions
- Bromide standard: |(bromide) = 1 g/L; commercially available
- DCA solution: |(DCA) = 0.5 g/L
Weigh 0.065 g potassium dichloroacetate into a 100-mL volumetric flask and
dissolve in ultrapure water. Make up to 100 mL with ultrapure water and mix.
All water samples should be filtered through a filter with 0.45 m pore size.
Analysis
The determination needs an external multipoint calibration in the concentration
range concerned. The required concentrations are obtained by diluting the above-
mentioned standards with ultrapure water.
Examples
Anions in drinking water
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 min
0
10
20
30
40
50
60
70
mV
ch1
1
2
3
4
Peak no. Component Retention time [min] Concentration [g/L]
1 Chlorite 9.31 3.22
2 Bromate 10.0 2.81
3 Chlorate 17.5 111.5
4 Bromide 18.3 9.78
Instrument MIC-2 Advanced IC system
Range 100 S/cm
Full Scale 5.0 S/cm
Polarity +
Column Metrosep A Supp 5 250 (6.1006.530) plus Metrosep A Supp 1
Guard (6.1005.340)
2
CO
3
/ 1.0 mmol/L NaHCO
3
Flow 0.7 mL/min
Loop 100 L
D Anions
Anions in drinking water (Houston) spiked with chlorite, bromate and chlorate
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 min
1
2
3
4
5
6
7
8
mV
ch1
1
2
3
4
5
6
7
8
9
10
11
12
13
1 Fluoride 6.09 0.64
2 not identified 7.72
3 Chlorite 8.94 0.013
4 Bromate 9.56 0.006
6 N as nitrite 13.5 0.079
8 Bromide 17.68 0.050
9 Chlorate 18.41 0.045
10 DCA 19.41 0.873
11 N as nitrate 21.13 0.264
12 P as phosphate 25.12 0.171
13 Sulfate 27.85 23.4
D2 Bromate with IC
Range 100 S/cm
Full Scale 100 S/cm
Polarity +
Column Metrosep A Supp 7 250 (6.1006.630)
2
CO
3
Flow 0.8 mL/min
Loop 20 L
Column temp. 45 C
- IC Application Note S 161 Detection limits of bromate in drinking water
- IC Application Note S 170 Oxyhalides in drinking water
- IC Application Note S 235 Determination of anions and oxyhalides by US EPA
method 300.1 A and B in a single analysis (standard solution)
- IC Application Note S 236 Determination of anions and oxyhalides by US EPA
method 300.1 A and B in a single analysis (sample)
ion chromatography
D2 Bromate with IC
General remarks
Bromate affects the thyroid gland and is a potential carcinogen. It is formed by
oxidation of bromide traces during the disinfection of water, for example by
ozonization.
The limiting values prescribed by the pertinent laws differ from one country to the
other. The German Drinking Water Regulation
7
prescribes a provisional limit of
25 g/L that will be reduced to 10 g/L in 2008. For mineral water a limiting value
of 3 g/L has been in force in Germany since 2004.

7
Deutsche Trinkwasserverordnung (TrinkwV 2001).
D Anions
The internationally accepted standards stipulate different methods for determining
bromate. Four of these will be described below:
- Bromate determination after separation on an anion-exchange column (see D2
Oxyhalides) using conductivity detection after chemical suppression. The
universally applicable conductivity detection can be used to determine
additional anions in the same run (US EPA 300.1).
- Bromate determination by means of post-column derivatization with o-danis-
idine followed by VIS detection. The separation occurs on an anion-exchange
column. The post-column reaction with o-danisidine, which is highly selective for
bromate, can be inserted after the conductivity measurement. This allows to
determine additional anionic constituents (US EPA 317).
- Bromate determination by means of post-column derivatization with potassium
iodide (triiodide method) followed by UV detection. The separation occurs on
an anion-exchange column (US EPA 326, but without acidification by the
suppressor).
- Bromate determination using an anion-exchange column followed by MS
detection. The coupling of ion chromatic separation and MS detection opens
up another possibility to increase the selectivity and sensitivity of bromate
determination.
The following limits of detection LoD (according to DIN 32 645) can be reached:

8
Drinking water matrix: 100 mg/L each of chloride, carbonate, sulfate.
Method
Injected
volume
L
LoD in
ultrapure
water
g/L
LoD in
drinking water
matrix
8
g/L
Determination using conductivity
detection after chemical suppression
100 0.13 0.39
(o-dianisidine) and VIS detection 100 0.21 0.64
Determination by means of post-
column derivatization with KI
(triiodide method) and UV detection
1000 0.032 0.066
Determination using MS detection 100 0.0064 0.0067
D2 Bromate with IC
a) for bromate determination using post-column derivatization with o-dianisidine
and VIS detection
- MIC-2 Advanced IC system with column heater, Lambda 1010 UV/VIS detector,
833 Advanced IC Liquid Handling Pump Unit and 6.2836.000 post-column
reactor
- 844 UV/VIS Compact IC (2.844.0120)
- Metrosep A Supp 5 250 (6.1006.530) plus Metrosep A Supp 4/5 Guard
(6.1006.500)
b) for bromate determination using post-column derivatization with potassium
iodide (triiodide method) and UV detection
- MIC-1 Advanced IC system plus Lambda 1010 UV/VIS detector, 833 Advanced
IC Liquid Handling Pump Unit and 6.2836.000 post-column reactor
- 844 UV/VIS Compact IC (2.844.0120)
- Bromate separation column
c) for bromate determination using IC-MS
- MIC-2 Advanced IC system plus Agilent MS detector
- Metrosep A Supp 5 250 (6.1006.530) plus Metrosep A Supp 1 Guard
(6.1005.430)
Reagents
Use only reagents of highest purity and ultrapure water having a specific resis-
tance >18 MOhm cm.
- Bromate standard: |(bromate) = 1 g/L
Weigh 0.1180 g sodium bromate into a 100-mL volumetric flask and dissolve in
a) for bromate determination using post-column derivatization with o-dianisidine
and VIS detection
2
CO
3
/1.0 mmol/L NaHCO
3
2
SO
4
) = 50 mmol/L
- Suppressor rinsing solution: ultrapure water (specific resistance >18 MOhm cm)
- Post-column derivatization reagent: transfer 300 mL ultrapure water into a 500-
mL volumetric flask and add 40 mL 70% nitric acid and 2.5 g KBr.
In a separate vessel dissolve 0.250 g o-dianisidine dihydrochloride in 100 mL
methanol. Add this solution to the KBr-nitric acid solution and make up to the
mark with ultrapure water. The reagent initially has a yellow color that fades with
time. We recommend to leave the solution standing overnight before use.
D Anions
b) for bromate determination using post-column derivatization with potassium
iodide (triiodide method) and UV detection
- Eluent: 100 mmol/L H
2
SO
4
/0.045 mmol/L ammonium molybdate
((NH
4
)
6
Mo
7
O
24
x
4 H
2
O)Post-column derivatization reagent: 0.26 mol/L KI in
ultrapure water; the reagent should be degassed before use.
c) for bromate determination using IC-MS
2
CO
3
/1.0 mmol/L NaHCO
3
2
SO
4
) = 50 mmol/L
Analysis
The determination needs an external multipoint calibration in the concentration
range concerned. The required concentrations are obtained by diluting the above-
mentioned standard with ultrapure water.
Chromatographic conditions plus example chromatogram
a) Bromate determination using post-column derivatization with o-dianisidine and
VIS detection
Instrument MIC-2 Advanced IC system with column heater, Lambda
1010 UV/VIS detector, 833 Advanced IC Liquid Handling
Pump Unit and 6.2836.000 post-column reactor
Lamp Tungsten
Wavelength 450 nm
Column Metrosep A Supp 5 250 (6.1006.530) plus Metrosep A
Supp 4/5 Guard (6.1006.500)
2
CO
3
/1.0 mmol/L NaHCO
3
Eluent flow 0.7 mL/min
Reagent flow 0.5 mL/min
Temperature for post-
column derivatization
75 C
Loop 100 L
D2 Bromate with IC
Drinking water, spiked with 8 ppb of bromate
1 Bromate 8.52 8.6
b) Bromate determination using post-column derivatization with potassium iodide
(triiodide method) and UV detection
Instrument MIC-1 Advanced IC system plus Lambda 1010 UV/VIS detector,
833 Advanced IC Liquid Handling Pump Unit and 6.2836.000
post-column reactor
Lamp Deuterium
Wavelength 352 nm
Eluent 100 mmol/L H
2
SO
4
/0.045 mmol/L ammonium molybdate
((NH
4
)
6
Mo
7
O
24
x
4 H
2
O)
Reagent flow 0.24 mL/min
Loop 1000 L
D Anions
Drinking water
0 1 2 3 4 5 6 7 8 9 min
-3.5
-3.4
-3.3
-3.2
-3.1
-3.0
-2.9
mV
ch2
1
1 Bromate 7.76 0.13
c) Bromate determination using IC-MS
Instrument MIC-2 Advanced IC system plus Agilent MS detector
m/z a) 127 + 129; b) 127; c) 129
SIM negative
Fragmentor
voltage
70 V
2
CO
3
/ 1.0 mmol/L NaHCO
3
Loop 100 L
D2 Bromate with IC
Drinking water
1 Bromate 9.5 0.32
- IC Application Note S 169 Bromate determination using post column reaction
(o-dianisidine method)
- IC Application Note N 47 Bromate determination using post-column reaction
(triiodide method)
- Poster CIA 2005, Bromate determination in water samples comparison of IC
and IC/MS methods
D Anions
ion chromatography
- US EPA Method 317 Determination of inorganic oxyhalide disinfection by-
products in drinking water using Ion Chromatography with the addition of a post-
column reagent for trace bromate analysis
- US EPA Method 326 Determination of inorganic oxyhalide disinfection by-
products in drinking water using Ion Chromatography incorporating the addition
of a suppressor-acidified post-column reagent for trace bromate analysis
D2 Perchlorate with IC
General remarks
Perchlorate salts are used as oxidants in rocket propellants, in explosives and in
the electroplating industry. Investigations have shown that perchlorate accumu-
lates in water. Accordingly, perchlorate contamination is found in surface waters in
regions adjacent to former or actual rocket testing sites in California, Nevada and
Arizona, for example.
The effects of perchlorate on humans are still not sufficiently known. One knows
for sure, however, that perchlorate slows down the uptake of iodine into the thyroid
gland. The determination of perchlorate in different types of water (drinking water,
ground water, surface water, wastewater) is therefore of paramount importance.
The determination of perchlorate is the subject of various international methods.
An example is US EPA Method 332, which describes the determination of perchlo-
rate using IC-MS coupling.The detection limits are given as 0.02 ppb. The IC-MS
coupling has the advantage of significantly reducing matrix effects.
US EPA Method 314 describes perchlorate determination using a system based
entirely on ion chromatography.
Both methods will be dealt with in the following:
- Perchlorate determination in the ppb range (US EPA 314) after separation on a
high-capacity anion-exchange column using conductivity detection after chemi-
cal suppression.
With increasing matrix concentrations of chloride, carbonate and sulfate, the
determination of perchlorate using conductivity detection becomes increasingly
difficult in the range 1 to 5 ppb. With the high-capacity anion-exchange column
used here, however, even 0.5 ppb perchlorate can be determined in a matrix
containing 1000 mg/L each of chloride, carbonate and sulfate.
- Perchlorate determination using conductivity detection after chemical suppres-
sion followed by mass detection. Also here, the separation is carried out on an
anion-exchange column. This method allows to determine perchlorate reliably in
the ppt range. The IC-MS coupling reduces matrix effects significantly (US EPA
332).
a) for perchlorate determination using conductivity detection after chemical
suppression
- MIC-2 Advanced IC system
- Metrosep Dual 4 50 (6.1016.020) plus Metrosep Dual 4 precolumn
(6.1016.500); Metrosep RP Trap 1 column (6.1014.100)
b) for perchlorate determination using conductivity detection after chemical
suppression followed by mass detection
- MIC-2 Advanced IC system plus Agilent MS detector
- Metrosep A Supp 5 100 (6.1006.510) plus Metrosep A Supp 4/5 Guard
(6.1006.500)
Reagents
tance >18 MOhm cm.
- Perchlorate standard: |(perchlorate) = 1 g/L
Weigh 0.123 g sodium perchlorate into a 100-mL volumetric flask, dissolve in
ultrapure water, make up to 100 mL with ultrapure water and mix.
suppression
- Eluent: 5.0 mmol/L LiOH/12.0 mmol/L p-cyanophenol
- Suppressor regenerant solution: c(HNO
3
) = 100 mmol/L plus 1% acetonitrile
plus 1% acetonitrile
- Eluent: 30 mmol/L NaOH / 30% methanol
- Suppressor regenerant solution: c(HNO
3
) = 60 mmol/L plus 10% methanol
plus 10% methanol
D Anions
Analysis
Quantitation is carried out by means of an external multipoint calibration covering
the concentration range concerned. To obtain the required concentrations, the
above-mentioned standard is diluted with ultrapure water.
Chromatographic conditions plus example chromatograms
suppression
Range 100 S/cm
Full Scale 10 S/cm
Polarity +
Column Metrosep Dual 4 50 (6.1016.020) plus Metrosep Dual 4
precolumn (6.1016.500); Metrosep RP Trap 1 column (6.1014.100)
Eluent 5.0 mmol/L LiOH / 12.0 mmol/L p-cyanophenol
Flow 1.75 mL/min
Loop 750 L
Matrix with 1000 ppm each of chloride, carbonate, sulfate plus addition of
perchlorate
0 1 2 3 4 5 6 7 8 9 10 11 min
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
mV
ch1
1
1 Perchlorate 10.5 0.55
Instrument MIC-2 Advanced IC system plus Agilent MS detector
m/z 99
SIM negative
Fragmentor
voltage
150 V
Eluent 30 mmol/L NaOH / 30% methanol
Loop 100 L
D Anions
Groundwater Houston (a)
and groundwater Houston spiked with 1 ppb perchlorate (b)
Peak
no.
Component Retention time
[min]
Concentration
chromatogram a
[g/L]
Concentration
chromatogram b
[g/L]
1 Perchlorate 13.5 0.35 1.35
- IC Application Note S 217 Ultratrace-level perchlorate in reagent water, ground
water, surface water and water containing 3000 ppm of total dissolved solids
(US EPA method 314.0)
- IC Application Note M 2 Chlorite, chlorate and perchlorate in explosion residue
applying IC/MS coupling
- Reprint LC-GC, The Applications Book, September 2004, p. 14; Determination
of trace level perchlorate in different vegetable extracts by Ion Chromatography-
Mass Spectrometry, Jay Gandhi, Joe Hedrick
- Reprint LC-GC, The Application Notebook, 2005, September. p. 1; Simulta-
neous Determination of Bromide and Perchlorate in Vegetables by Ion Chro-
matography-Mass Spectrometry, Jay Gandhi, Joe Hedrick
D2 Chromate Cr(VI) with IC
- Agilent Application Note 5989-0816EN The Analysis of Perchlorate by Ion
Chromatography/Mass Spectrometry
- US EPA Method 314.0 Determination of Perchlorate in Drinking water using
Ion Chromatography
- US EPA Method 332.0 Determination of Perchlorate in Drinking water by Ion
chromatography with suppressed conductivity and Electrospray Ionization Mass
Spectrometry
General remarks
Chromium is considered as an essential trace element. Only the compounds of
hexavalent chromium are toxic because of their oxidative effect on cell constitu-
ents. Cr(VI) has mutagenic and carcinogenic properties and can cause skin
allergies. It is therefore important to know the chromium content of the different
types of water.
The chromium content of surface waters ranges from 0.2 to 20 g/L. The require-
ments for drinking water depend on local legislation, the limiting values ranging
from <1 g/L Cr(VI) to 50 g/L total chromium.
We are going to describe two methods for the determination of Cr(VI):
- Separation on an anion exchange column followed by chemical suppression
and conductivity detection. The generally applicable conductivity detection can
be taken advantage of to determine additional anions in the same run.
- Separation on an anion exchange column, post-column derivatization with
diphenyl carbazide and VIS detection (US EPA 218.6).
The post-column derivatization with diphenyl carbazide, which is highly selec-
tive for chromate, can be carried out after the conductivity measurement. This
allows to determine further ionic species besides chromate.
a) for chromate determination using conductivity detection after chemical
suppression
- MIC-2 Advanced IC system or 861 Advanced Compact IC
- Anion exchange column, e.g. Metrosep A Supp 5 100 (6.1006.510) plus
Metrosep A Supp 4/5 Guard (6.1006.500), Metrosep Anion Dual 3 (6.1006.120)
plus Metrosep RP Guard (6.1011.020), Metrosep A Supp 4 250 (6.1006.430)
plus Metrosep A Supp 4/5 Guard (6.1006.500), Phenomenex Star Ion A300
(6.1005.100)
D Anions
b) for chromate determination using post-column derivatization with diphenyl
carbazide and VIS detection
- MIC-2 or MIC-1 Advanced IC system plus Lambda 1010 UV/VIS detector, 833
Advanced IC Liquid Handling Pump Unit and 6.2836.000 post-column reactor
- 844 UV/VIS Compact IC (2.844.0120)
Metrosep A Supp 4/5 Guard (6.1006.500), Metrosep Anion Dual 3 (6.1006.120)
plus Metrosep RP Guard (6.1011.020), Metrosep A Supp 4 250 (6.1006.430)
plus Metrosep A Supp 4/5 Guard (6.1006.500), Phenomenex Star Ion A300
(6.1005.100)
Reagents
tance >18 MOhm cm.
- Chromate standard: |(chromate) = 1 g/L
Weigh 0.167 g potassium chloride into a 100-mL volumetric flask, dissolve in
ultrapure water, make up to 100 mL with ultrapure water and mix.
suppression
- Eluent containing Na
2
CO
3
and NaHCO
3
, concentrations depend on the column
used
2
SO
4
) = 50 mmol/L
2
CO
3
and NaHCO
3
used
- Reagent for post-column derivatization: dissolve 0.5 g 1,5-diphenyl carbazide in
100 mL methanol (HPLC grade). Transfer approx. 600 mL ultrapure water into a
1-L volumetric flask, then add 28 mL 98% sulfuric acid. Add the diphenyl carba-
zide solution and make up to the mark with ultrapure water. This solution has a
shelf life of 5 days.
Analysis
Chromatographic conditions plus example chromatograms
suppression
Instrument 861 Advanced Compact IC
Full Scale 250 S/cm or 50 S/cm
Polarity +
Column Metrosep A Supp 5 100 (6.1006.510) plus Metrosep ASupp 4/5
Guard (6.1006.500)
2
CO
3
, 1.0 mmol/L NaHCO
3
Flow 0.7 mL/min
Loop 20 L
Wastewater
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 min
20
40
60
80
100
120
140
160
180
uS/cm
Cond
1
2
3
4
5 6
13 14 15 16 17 18 19 min
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
uS/cm
Cond
5
6
D Anions
2 Nitrite 4.98 105
3 Nitrate 7.46 3652
4 Sulfate 9.61 53.0
6 Chromate 17.12 0.11
Instrument
MIC-2 Advanced IC system plus Lambda 1010 UV/VIS detector, 833
Advanced IC Liquid Handling Pump Unit and 6.2836.000 post-
column reactor
Lamp Tungsten
Wavelength 540 nm
Column Phenomenex Star Ion A300 (6.1005.100)
2
CO
3
, 1.7 mmol/L NaHCO
3
Reagent
flow
0.5 mL/min
Loop 20 L
Wastewater
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 min
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
mV
ch2
1
1 Chromate 11.77 0.05
- IC Application Note N 45 Chromate using post-column reaction
- IC Application Note S 93 Nitrate, phosphate, sulfate and chromate in a
cataphoretic paint bath
- IC Application Note S 175 Chromate in wastewater using conductivity and
subsequent UV/VIS detection after post-column reaction with diphenyl carba-
zide
- US EPA Method 218.6 Determination of dissolved hexavalent chromium in
drinking water, groundwater and industrial wastewater effluents by ion chro-
matography
D Anions
D2 Silicate dissolved silicic acid with IC
General remarks
Silicates are salts of silicic acid and form a large group of minerals. The earth's
crust cosists to more than 90%, the earth's mantle almost completely of silicates.
The silicates occur in dissolved form in virtually all types of water and their
determination, for example in drinking water, is of considerable interest.
The silicate ion is also an indicator of the quality of ultrapure water as it is one of
the first ions that appear in the purified water when the ion exchangers used for
water purification becomes exhausted. The determination at very low levels of
concentration is therefore very important, for example in thermal power plants.
As silicates are salts of a very weak acid they dissociate only in the alkaline region
and there can be detected by conductivity without chemical suppression.
For the determination of silicate in the low ppb range the preconcentration tech-
nique is used.
- MIC-1 Advanced IC system
- Anion exchange column, e.g. Hamilton PRP-X 100 (6.1005.000) plus Hamilton
PRP-X 100 precolumn cartridge (6.1005.020), Phenomenex Star Ion A300
(6.1005.100)
- Preconcentration column, e.g. Hamilton PRP-X 100 precolumn cartridge
(6.1005.020), Metrosep A PCC 1 anion preconcentration column (6.1006.300)
Reagents
tance >18 MOhm cm.
- Silicate standard: |(silicate) = 1 g/L
Weigh 0.100 g pure silicate (SiO
2
) into a 100-mL volumetric flask, dissolve in
0.2% NaOH, make up to 100 mL with 0.2% NaOH and mix.
2
CO
3
and NaHCO
3
used
D2 Silicate dissolved silicic acid with IC
Analysis
If one works in the low ppb range using preconcentration, it is recommended to
apply inline calibration.
Examples
Silicate in drinking water
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 min
200
400
600
800
1000
1200
1400
1600
1800
2000
2200
mV
ch1
1
2
2 Silicate 4.18 5.32
D Anions
Range 1 mS/cm
Full Scale 5 S/cm
Polarity
Column Hamilton PRP-X 100 (6.1005.000) plus Hamilton PRP-X 100
precolumn cartridge (6.1005.020)
Eluent 3.2 mmol/L NaOH / 0.5 mmol/L Na
2
CO
3
Flow 1.0 mL/min
Loop 100 L
Silicate in boiler feed water (ultrapure water)
0 1 2 3 4 5 6 7 8 9 10 min
20
40
60
80
100
120
140
mV ch1
1
1 Silicate 3.71 0.89
D2 Sulfite, sulfate and thiosulfate with IC
Range 1 mS/cm
Full Scale 10 S/cm
Polarity
Column Hamilton PRP-X 100 (6.1005.000) plus Hamilton PRP-X 100
precolumn cartridge (6.1005.020)
Preconcentration
column
IC anion preconcentration column Metrosep A PCC 1
(6.1006.300)
Preconcentration
volume
10 mL
Eluent 3.2 mmol/L NaOH / 0.5 mmol/L Na
2
CO
3
Flow 1.0 mL/min
Metrohm literature concerning silicate determination with IC
- IC Application Note N 44 Silicate in tap water
- IC Application Note N 54 Borate and silicate in ultrapure water
- IC Application Note N 56 Silicate besides fluoride in tap water
- IC Application Note N 60 and Q 1 Online monitoring of trace levels of silicate in
boiler feed water
General remarks
With ion chromatography the determination of the sulfur species sulfite, sulfate
and thiosulfate can be carried out in one run. This determination is of high interest
in the analysis of wastewaters, especially in the paper industry, where sulfate- and
sulfite-containing solutions are used for paper production.
Metrosep RP Guard (6.1011.020), Metrosep Anion Dual 3 (6.1006.120) plus
Metrosep RP Guard (6.1011.020), Metrosep A Supp 4 250 (6.1006.430),
Metrosep A Supp 5 150 (6.1006.520) plus Metrosep A Supp 4/5 Guard
(6.1006.500)
D Anions
Reagents
tance >18 MOhm cm.
- Sulfite standard: |(sulfite) = 1 g/L
Stabilizing the sulfite requires addition of formaldehyde or 2-propanol (isopro-
panol). Accordingly, there are two possibilities of preparing the standard:
a) Weigh 0.157 g sodium sulfite into a 100-mLvolumetric flask and dissolve in
0.2 mmol/L NaOH and 0.037% formaldehyde. Make up to 100 mL with this
mixture and mix.
b) Weigh 0.157 g sodium sulfite into a 100-mLvolumetric flask and dissolve in
ultrapure water. Add 10 mL 2-propanol, make up to the mark with ultrapure
water and mix.
- Sulfate standard: |(sulfate) = 1 g/L; commercially available.
- Thiosulfate standard: |(thiosulfate) = 1 g/L
Weigh 0.222 g sodium thiosulfate pentahydrate into a 100-mLvolumetric flask,
dissolve in ultrapure water, make up to 100 mL with ultrapure water and mix.
2
CO
3
and NaHCO
3
; possibly also acetone; concentrations
depend on the column used
2
SO
4
) = 50 mmol/L
As wastewaters can contain considerable amounts of organic substances, an
additional sample preparation using an RP cartridge (6.1012.000) is recom-
mended.
Analysis
above-mentioned standards are diluted with ultrapure water. To stabilize the di-
luted sulfite standards, formaldehyde (0.0037%) or 2-propanol (1%) must be
added to them.
Examples
Sulfite, sulfate and thiosulfate in wastewater
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 min
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
uS/cm
Cond
1
2
3
4
5
6
7
8
2 System peak 5.80
3 Bromide 6.75 0.34
4 Nitrate 7.88 not quantified
5 Sulfite 10.4 1.54
6 Sulfate 13.61 146
7 Oxalate 16.49 2.02
8 Thiosulfate 25.87 12.7
D Anions
Full Scale 50 S/cm
Polarity +
Column Metrosep Anion Dual 3 (6.1006.120) plus Metrosep RP Guard
(6.1011.020)
2
CO
3
/ 2.0 mmol/L NaHCO
3
/ 15% acetone
Flow 0.8 mL/min
Loop 20 L
- IC Application Note S 144 Heat stable salts in scrubber solutions
- IC Application Note S 155 Sulfite, oxalate and thiosulfate besides standard
anions in process water of paper industry
D2 Organic acids with IC
General remarks
The determination of weak organic acids such as acetic acid or propionic acid is
carried out using ion exclusion chromatography. The completely dissociated acids
are not retained on the stationary phase by Donnan exclusion and therefore elute
within the dead time.
The determination of short-chain organic acids is applied in wastewater analysis.
Compared to gas chromatography, which is also used for this but requires a
sample derivatization step, ion exclusion chromatography has the advantage of
requiring significantly less sample preparation effort.
The determination of the organic acids after their separation on an ion exclusion
column can be done with direct conductivity measurment or after inverse
suppression with lithium.
- Ion exclusion column, e.g. Metrosep Organic Acids 250 (6.1005.200) plus
Metrosep Organic Acids Guard (6.1005.250)
Reagents
tance >18 MOhm cm.
- Organic acid standards 1 g/L
In a 100-mL volumetric flask dissolve the corresponding amounts of the salts of
the organic acids or the acids themselves in ultrapure water. Make up to 100
mL with ultrapure water and mix.
- Eluent containing a dilute acid, such as sulfuric or perchloric acid, possibly also
acetone; concentrations depend on the application and the column used
- Suppressor regenerant solution: c(LiCl) = 10 mmol/L
It is recommended to pass the samples through a H
+
cartridge (6.1012.010) to
neutralize them and to eliminate the divalent cations.
Analysis
above-mentioned standards are diluted with ultrapure water.
D Anions
Examples
Organic acids in process water with inverse suppression
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 min
46
48
50
52
54
56
58
60
62
64
uS/cm
Cond
1
2
3
4
5 6
7
8
9
2 Glycolic acid 11.44 3.30
3 Formic acid 12.45 0.97
4 Glutaric acid 14.23 0.93
5 Acetic acid 15.41 724
6 Propionic acid 18.14 530
7 Carbonate 20.04 not quantified
8 Butyric acid 22.32 24.2
9 Sulfide 25.73 not quantified
Full Scale 250 S/cm
Polarity +
Column Metrosep Organic Acids 250 (6.1005.200) plus Metrosep Organic
Acids Guard (6.1005.250)
Eluent 0.5 mmol/L HClO
4
Flow 0.5 mL/min
Loop 20 L
Suppressor 10 mmol/L LiCl as regenerant solution; ultrapure water for rinsing
- IC Application Note O 21 Six organic acids in a process water of the paper
industry
- IC Application Note O 34 Aliphatic monocarboxylic acids in produced water
using IC/MS coupling
D Anions
D3 Chromate/dichromate Cr(VI) with VA
General remarks
Chromium is considered as an essential trace element. Only the compounds of
hexavalent chromium are toxic because of their oxidative effect on cell constitu-
ents. Cr(VI) has mutagenic and carcinogenic properties and can cause skin
allergies. It is therefore important to know the chromium content of the different
types of water.
The chromium content of surface waters ranges from 0.2 to 20 g/L. The require-
ments for drinking water depend on local legislation, the limiting values ranging
from <1 g/L Cr(VI) to 50 g/L total chromium.
We are going to describe two methods:
- DP polarography for chromium contents >10 g/L and
- catalytic DP stripping voltammetry for contents ranging from 0.02 to 1.5 g/L.
- 797 VA Computrace with Dosino
- 705 UV Digester
Reagents
tance >18 MOhm cm.
a) for the polarographic method:
- Cr(VI) standard: |(Cr
6+
) = 100 mg/L
Pipet 10.0 mL |(Cr
6+
) = 1 g/L (commercially available) into a 100-mL volumetric
flask, make up to the mark with ultrapure water and mix.
- Potassium hydroxide solution: w(KOH) = 45%
- Ammonia: w(NH
3
) = 5%
- Acetic acid: w(CH
3
COOH) = 98%
- Ethylene diamine: puriss p.a. (CAS 107-15-3)
b) for the stripping-voltammetric method:
6+
) = 100 mg/L
Pipet 10.0 mL |(Cr
6+
) = 1 g/L (commercially available) into a 100-mL volumetric
flask, make up to the mark with ultrapure water and mix.
6+
) = 0.02 mg/L
Pipet 2.0 mL |(Cr
6+
) = 100 mg/L into a 100-mL volumetric flask, make up to the
mark with ultrapure water and mix. In a second 100-mL volumetric flask make
up to the mark 1.0 mL of this solution with ultrapure water and mix. Prepare
fresh solutions daily (both intermediate and 0.02 mg/L solution).
- Base electrolyte:
Dissolve 1.64 g sodium acetate, 1.96 g disodium diethylenetriamine pentaace-
tate (DTPA, CAS 67-43-6) and 21.3 g sodium nitrate in ultrapure water, make
up to 100 mL with ultrapure water and mix.
Waters moderately loaded with organic substances:
Adjust the sample to a pH value of 5...7. Transfer 10 mL of the resulting mixture
into a quartz reaction vessel, add 10 L w(H
2
O
2
) = 30% and digest in the UV Di-
gester for 1 h at 90 C. Add another 10 L H
2
O
2
and digest for another 30 min.
Wastewater heavily loaded with organic substances:
This type of wastewater requires wet digestion (e.g. with H
2
SO
4
/ H
2
O
2
). After the
digested solution has cooled down, add 10 mL ultrapure water and 2 drops of
c(KMnO
4
) = 0.02 mol/L and heat to boiling. Dropwise add permanganate solution
until the pink color remains. Keep the solution boiling for approx. 5 min while main-
taining the total volume constant by adding small amounts of ultrapure water. Be-
fore it has cooled down, adjust the solution to pH = 5...9 with KOH solution. Rinse
the solution into the polarographic vessel with ultrapure water.
Polarographic analysis
Preneutralize the sample or the digested solution with KOH solution to pH = 7...8.
To 10 mL sample or digested solution in the polarographic vessel add 20 L
ethylenediamine, 150 L acetic acid, 300 L KOH and 200 L ammonia. If
necessary adjust the pH value to approx. 9.5 by adding KOH solution or acetic
acid, deaerate with nitrogen and record the DP polarogram applying the following
conditions:
Working electrode DME Start potential 80 mV
Stirrer 2000 rpm End potential 400 mV
Mode DP Potential step 6 mV
Deaeration time 600 s Time 0.4 s
Pulse amplitude 50 mV Potential gradient 10 mV/s
Equilibration time 3 s Peak potential
Cr(VI)
approx. 250
mV
D Anions
The Cr(VI) content is obtained by means of the standard addition method (in the
present example: three times 100 L Cr standard, | = 100 mg/L).
Stripping voltammetric analysis
Transfer 10 mL sample or digested solution (or an aliquot) into the polarographic
vessel and add 5 mL base electrolyte. Adjust the pH value of the mixture to 6.2
0.1 with NaOH solution and record the DP stripping voltammogram applying the
following conditions:
Working electrode HMDE
Stirrer 2000 rpm
Mode DP
Deaeration time 300 s
Pulse amplitude 50 mV
Electrolysis under stirring 60 s
Electrolysis without
stirring
5 s
Preconcentration
potential
1.0 V
Start potential 1.0 V
End potential 1.45 V
Potential step 10 mV
Time 0.3 s
Potential gradient 33.3 mV/s
Peak potential Cr approx. 1.25 V
The Cr content of the sample was determined by twice adding 100 L |(Cr
6+
) =
0.02 mg/L. The blank value was also determined.
Examples: Cr content of a wastewater (polarographic) and a surface water
(voltammetric)
- Application Bulletin no. 116 Polarographic/voltammetric determination of
chromium in small quantities
D Anions
D3 Cyanide with VA
General remarks
The determination of cyanides in waters (e.g. seepage water, electroplating
wastewater before and after detoxification) is highly important. Cyanide
concentrations as low as 50 g/L can be lethal for fish. Depending on the
legislation for drinking water, the maximum allowable cyanide concentrations vary
between 50 and 100 g/L.
The following methods will be described:
- DP polarography for cyanide contents of 0.1...10 mg/L and
- DP stripping voltammetry for cyanide contents 10...100 g/L.
Reagents
Use only reagents of the highest purity and ultrapure water.
- Cyanide standard: |(CN
-
) = 100 mg/L
Dissolve first 0.6 g KOH and then 0.2503 g KCN in ultrapure water, make up to
1 L with ultrapure water and mix.
- Cyanide standard: |(CN
-
) = 10 mg/L
Transfer 0.6 g KOH into a 100-mL volumetric flask and dissolve in approx. 50
mL ultrapure water. Add 10.0 mL |(CN
) = 100 mg/L, make up to the mark with

ultrapure water and mix. Fresh solution has to be prepared daily.
- Ground electrolyte:
Dissolve 100 g KOH and 123 g H
3
BO
3
in approx. 750 mL ultrapure water.
Leave to cool down, make up to 1 L with ultrapure water and mix.
If only the free cyanide is of interest, the samples can be used directly.
Otherwise one has to distinguish between easily released cyanides (e.g. from
KCN) and the total cyanide content, which also comprises the CN complexes of
heavy metals. Digestion and separation occur according to DIN 38405 D13/D14
and are described in detail in Application Bulletin no. 46 Potentiometric
determination of cyanide.
For the voltammetric analyses, the ground electrolyte is used instead of the NaOH
absorption solution.
D3 Cyanide with VA
Polarographic analysis
Transfer 10...20 mL absorption solution or 1...10 mL sample solution plus 10 mL
ground electrolyte into the polarographic vessel and deaerate with nitrogen. Re-
cord the DP polarogram applying the following conditions:
Pulse amplitude 50 mV Potential gradient 6.6 mV/s
Pulse time 0.04 s
Equilibration time 5 s
Peak potential CN
approx.
0.22 V
The cyanide content is determined by means of standard additions.
Stripping-voltammetric analysis
Transfer 10...20 mL absorption solution or 1...10 mL sample solution plus 10 mL
ground electrolyte into the polarographic vessel and deaerate with nitrogen. Re-
cord the DP stripping voltammogram applying the following conditions:
Working electrode HMDE Preconcentration
potential
80 mV
Stirrer 2000 rpm Start potential 80 mV
Mode DP End potential 400 mV
Deaeration time 300 s Potential step 4 mV
Pulse amplitude 50 mV Time 0.4 s
Electrolysis under
stirring
60 s Potential gradient 10 mV/s
Electrolysis without
stirring
3 s Peak potential CN
approx.
0.20 V
The cyanide content is determined by means of standard additions.
D Anions
Examples: CN content in an artificial wastewater and in drinking water
- Application Bulletin no. 110 Polarographic determination of free cyanide
D3 Sulfides and hydrogen sulfide with VA
D3 Sulfides and hydrogen sulfide with VA
General remarks
Sulfides and/or H
2
S can be present in reductive ground water, in seepage water
and, under anaerobic conditions, at the bottom of surface waters. Sulfides are
volatile and easily oxidized by atmospheric oxygen. Care has therefore to be taken
during sampling: the samples must be made alkaline with NaOH and be well
sealed for transport.
Sulfides can be easily determined with stripping-voltammetric methods.
The method is suitable for contents ranging from 0.3 to 20 g/L.
Reagents
Dissolve 80 g NaOH under stirring in approx. 100 mL dist. H
2
O. Leave to cool
down, make up to 200 mL with dist. H
2
O and mix.
- Sodium hydroxide solution: c(NaOH) = 0.1 mol/L
Transfer 10 mL c(NaOH) = 10 mol/L into a 1000-mL volumetric flask containing
approx. 800 mL dist. H
2
O. Make up to the mark with dist. H
2
O and mix.
- Sulfide standard: |(S
2-
) = 1 g/L
Mix 1 mL c(NaOH) = 10 mol/L with 98 mL dist. H
2
O and deaerate with nitrogen
for 5 min. Dissolve 700 mg sodium sulfide hydrate (approx. 35% Na
2
S) in this
solution and store the resulting solution in a sealed dark bottle in the refrigera-
tor. The solution has a storage life of approx. 1 week. To determine its exact
content, 1 mL of this solution is added to 40 mL c(NaOH) = 0.1 mol/L (O
2
-free);
nitrogen is passed over the solution while it is titrated with c(AgNO
3
) = 0.01
mol/L using the Ag Titrode coated with Ag
2
S. 1 mL c(AgNO
3
) = 0.01 mol/L
corresponds to 0.16 mg S
2-
(see also chapter D1).
2-
) = approx. 100 mg/L
Deaerate approx. 150 mL dist. H
2
O plus 2 mL c(NaOH) = 10 mol/L in a 200-mL
volumetric flask with nitrogen. Add 20.0 mL |(S
2-
) = approx. 1 g/L, make up to
the mark with O
2
-free dist. H
2
O and mix. Prepare fresh solution daily.
2-
) = approx. 5 mg/L
Add 1 mL c(NaOH) = 10 mol/L to 5.0 mL |(S
2-
) = approx. 100 mg/L, make up to
100 mL with O
2
-free ultrapure water and mix. Prepare fresh solution daily.
D Anions
Analysis
Stripping-voltammetric method
In the polarographic vessel deaerate 10 mL c(NaOH) = 0.1 mol/L during 5 min with
nitrogen. Depending on the sulfide content, add 1...10 mL sample and mix by
sparging with nitrogen, then record the DP stripping voltammogram applying the
following conditions:
Working electrode HMDE Electrolysis under stirring 30 s
Stirrer 2000 rpm Electrolysis without stirring 10 s
Mode DP Preconcentration potential 450 mV
Deaeration time 300 s Potential gradient 450 mV to
1000 mV
Pulse time 0.04 s
Peak potential sulfide approx.
730 mV
The content is determined by means of two standard additions. This method is
suitable for sulfide contents of 0.3...20 g/L.
Example: Sulfide in ground water (with added sulfide)
- Application Bulletin no. 199 Polarographic determination of sulfide and sulfite
D3 Sulfite with VA
- He,Y., Zheng,Y., Locke,D.C. Differential pulse cathodic stripping voltammetric
determination of nanomolar levels of dissolved sulfide applicable to field
analysis of groundwater. Anal.Chim.Acta 459, (2002) 209-217
D3 Sulfite with VA
General remarks
Sulfite only occurs in wastewaters, for example of the photo and the paper
industries it is not found in industrial water, ground water and surface water.
Ambient oxygen rapidly oxidizes sulfite to sulfate, especially in alkaline solution.
This has to be taken into account during sampling and sample treatment.
The method described here allows to determine, in a simple manner, sulfite
concentrations ranging from 1 mg/L to approx. 10 mg/L by means of DP
polarography.
Reagents
- Acetate buffer: c(NaOH) = 0.2 mol/L plus c(CH
3
COOH) = 0.4 mol/L
In a glass beaker dissolve under stirring 4 g NaOH in approx. 400 mL dist. H
2
O.
Under stirring then add 12 mL w(CH
3
COOH) = 98%. Leave to cool down, make
up to 500 mL with dist. H
2
O and mix.
- Sulfite standard: |(sulfite) = 1 g/L
Weigh 161 mg Na
2
SO
3
(98%) into a 100-mL volumetric flask and dissolve in
approx. 90 mL O
2
-free dist. H
2
O, make up with dist. H
2
O to 100 mL and mix. If
stored in a dark bottle and covered with N
2
, this solution has a shelf life of
approx. 1 week.
- Sulfite standard: |(sulfite) = 200 mg/L
Pipet 20.0 mL |(sulfite) = 1 g/L into a 100-mL volumetric flask, make up to the
mark with O
2
-free dist. H
2
O and mix. Prepare fresh solution daily.
D Anions
Analysis
In the polarographic vessel deaerate 10 mL acetate buffer for 5 min with nitrogen.
Depending on the sulfite content, add 1...10 mL sample and mix manually (do not
sparge with nitrogen). Record the DP polarogram applying the following
conditions:
Working electrode SMDE
Stirrer 2000 rpm
Mode DP
Pulse time 40 ms
Start potential 400 mV
End potential 850 mV
Potential step 6 mV
Time 0.8 s
Potential gradient 5 mV/s
Peak potential sulfite approx. 610 mV
The content is determined by means of two standard additions (mix manually, do
not sparge with nitrogen).
Remarks
- In the presence of sulfide there is a peak at approx. 0.45 V.
- In the presence of thiosulfate there are two overlapping peaks between 0.14 V
and 0.28 V.
D3 Sulfite with VA
Example: Sulfite in wastewater
- Application Bulletin no. 199 Polarographic determination of sulfide and sulfite
E Cations
E Cations
E1 Titration: Calcium and magnesium
Please find the detailed procedures for these determinations in the chapter Water
hardness on page 22.
E2 Cation determination with IC
General remarks
The determination of lithium, sodium, ammonium, potassium, calcium, magne-
sium, barium und strontium in different water types (drinking water, mineral water,
etc.) is of paramount importance for the assessment of water quality. The determi-
nation of these cations by means of ion chromatography is therefore the subject of
various standards.
- Cation exchange column, e.g. Metrosep Cation 1-2 (6.1010.100), Metrosep C 2
100 (6.1010.210), Metrosep C 2 150 (6.1010.220), Metrosep C 2 250
(6.1010.230) plus Metrosep C 2 Guard (6.1010.200)
Reagents
tance >18 MOhm cm.
- Eluent containing tartaric acid and dipicolinic acid (2,6-pyridine dicarbonic acid)
or nitric acid; concentrations depend on the column used and the application.
- 1-g/L stock solutions of lithium, sodium, ammonium, potassium, calcium,
magnesium, barium, strontium can be obtained especially for ion chromato-
graphy from different reagent manufacturers; after appropriate dilution, these
solutions are used for calibration. The standard solutions are prepared in 2
mmol/L nitric acid (pH value 2.5).
- PRIMUS standards, the only primary multiion standards for ion chromato-
graphy.
damage the column.
The samples can be filtered automatically applying ultrafiltration.
automated.
The pH value of the samples should be adjusted to pH 2.5 by means of nitric acid.
Analysis
When working in the concentration range 10 ppb to 100 ppm, one normally injects
10...100 L sample, which is separated on the cation exchanger column followed
by indirect conductometric detection.
If lower detection limits are to be achieved, the sample volume must be increased
markedly. Consider, however, that larger sample volumes mean a larger water
peak, which affects the evaluation of the early-eluting peaks.
Sample preconcentration is a simple method for lowering the detection limit by
several orders of magnitude. The sample loop is replaced by a preconcentration
column. An increased sample volume, e.g. 10 mL, is passed over the preconcen-
tration column, which contains essentially the same material as the separation
column. This ensures that all cations contained in the sample solution to be ana-
lyzed (e.g. ultrapure water) are kept back on the column and are preconcentrated.
The preconcentrated analyte ions are then brought to the separation column by
the eluent flowing counter-current.
range concerned. A three-point calibration is recommended for the determination
of cations.
E Cations
Examples
Cations in wastewater
0 1 2 3 4 5 6 7 8 9 10 11 min
100
200
300
400
500
600
700
800
mV
ch1
1
2
3
4
5
1 Sodium 3.08 7126
2 Ammonium 3.35 450
3 Potassium 4.09 158
4 Calcium 6.24 3049
5 Magnesium 9.87 80
Range 1.0 mS/cm
Full Scale 50 S/cm
Polarity
Column Metrosep Cation 1-2 (6.1010.100) plus Metrosep C 2 Guard
(6.1010.200)
Eluent 4 mmol/L tartaric acid, 1 mmol/L dipicolinic acid (2,6-pyridine
dicarbonic acid)
Flow 1.2 mL/min
Loop 10 L
Cations in drinking water
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 min
1
2
3
4
5
6
7
uS/cm
Cond
1
2
3
4
1 Sodium 4.42 10.1
2 Potassium 7.96 5.61
3 Calcium 9.99 18.3
4 Magnesium 12.7 9.03
E Cations
Full Scale 1000 S/cm
Polarity
Column Metrosep Cation 1-2 (6.1010.100) plus Metrosep C 2 Guard
(6.1010.200)
Eluent 4 mmol/L tartaric acid, 0.75 mmol/L dipicolinic acid (2,6-pyridine
dicarbonic acid)
Flow 1.0 mL/min
Loop 10 L
Cations in mineral water
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 min
10
20
30
40
50
60
70
mV
ch3
1
2
3
4
1 Sodium 5.03 1.96
3 Calcium 14.28 86
Range 1.0 mS/cm
Full Scale 50 S/cm
Polarity
Column Metrosep C 2 150 (6.1010.220) plus Metrosep C 2 Guard
(6.1010.200)
dicarbonic acid)
Flow 1.0 mL/min
Loop 10 L
Cations in a boiler feed water
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 min
10
20
30
40
50
60
70
80
mV
ch3
1
2
3
4
5
6
E Cations
1 Sodium 4.00 0.70
2 Ammonium 4.51 0.12
4 not identified 8.23 -
6 Calcium 15.53 0.83
Range 1.0 mS/cm
Full Scale 10 S/cm
Polarity
(6.1010.200)
Eluent 2.5 mmol/L nitric acid
Flow 1.0 mL/min
Preconcentra-
tion colunm
Metrosep C 2 S-Guard (6.1010.240)
Preconcentra-
tion volume
10 mL
Barium, strontium and magnesium in process water (oil production)
Has a very high sodium content (sea water)
0 1 2 3 4 5 6 7 8 9 10 11 12 13 min
1
2
3
4
5
6
7
uS/cm
Cond
1
2
3
1 Strontium 6.04 34
2 Barium 8.64 54
3 Magnesium 10.32 29
Polarity
Column Nucleosil 5 SA (6.1007.000) plus Metrosep RP Guard (6.1011.020)
Eluent 4 mmol/L tartaric acid, 0.5 mmol/L dipicolinic acid, 3 mmol/L
ethylenediamine, 5% acetone
Flow 1.5 mL/min
Loop 20 L
E Cations
- Application Note C 1 Sodium, potassium, calcium and magnesium in drinking
water
- Application Note C 2 Sodium, potassium, calcium and magnesium in cooling
water
- Application Note C 12 Determination of alkali and alkaline earth metal cations
- Application Note C 14 Sodium, ammonium, potassium, calcium and
magnesium in wastewater
- Application Note C 19 Five cations in rain water
- Application Note C 33 Four cations in sea water
- Application Note C 39 Five cations in offshore water
- Application Note C 44 Five cations in tap water
- Application Note C 60 Magnesium, strontium and barium in produced water
- Application Note C 83 On-line monitoring of trace levels of cations in boiler
feed water
- Monograph Practical ion chromatography
- DIN EN ISO 14911 Determination of dissolved Li
+
, Na
+
, NH
4
+
, K
+
, Mn
2+
, Ca
2+
,
Mg
2+
, Sr
2+
and Ba
2+
using ion chromatography
E2 Amines, for example methylamine, ethanolamine
with IC
General remarks
The determination of amines such as ethanolamine, diethanolamine, methylamine,
dimethylamine, guanidine, etc., can be carried out by means of ion chromatogra-
phy. The amines are separated on a cation exchange column and determined
using indirect conductivity detection.
- MIC-1 Advanced or 861 Advanced Compact IC
- Cation exchange column, e.g. Metrosep C 2 150 (6.1010.220), Metrosep C 2
250 (6.1010.230) plus Metrosep C 2 Guard (6.1010.200)
E2 Amines, for example methylamine, ethanolamine with IC
Reagents
tance >18 MOhm cm.
- Eluent containing tartaric acid and dipicolinic acid (2,6-pyridine dicarbonic acid)
or nitric acid; organic solvents such as acetone are added if required. The
eluent concentrations depend on the column used and the application.
- 1-g/L stock solutions of the different amines are prepared by dissolving the
compounds in ultrapure water.
Dialysis or C18 sample preparation cartridges (6.1012.200) can be used for the
preparation of samples with high organic loads.
Analysis
of cations.
Examples
N-Methyldiethanolamine (MDEA), Na, NH
4
, K, Ca and Mg in wastewater
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 min
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
uS/cm
Cond
1
2
3
4
5
6
E Cations
1 Sodium 8.38 680
2 Ammonium 9.59 33
3 Potassium 13.80 12
4 MDEA 14.90 21
5 Calcium 17.18 88
6 Magnesium 26.37 16
Polarity
(6.1010.200)
dicarbonic acid) / 10% acetone
Flow 1.0 mL/min
Loop 10 L
Methylamine, guanidine, aminoguanidine, Na
+
and NH
4
+
in wastewater
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 min
50
100
150
200
250
300
350
400
450
500
550
600
650
mV
ch1
1
2
3
4
5
6
7
E2 Amines, for example methylamine, ethanolamine with IC
1 Sodium 4.77 883
2 Ammonium 5.39 465
3 Methylamine 6.63 1.21
4 Guanidine 9.79 99.6
5 Calcium 11.02 not quantified
6 Magnesium 16.08 not quantified
7 Aminoguanidine 20.02 2.16
Range 1.0 mS/cm
Full Scale 10 S/cm
Polarity
(6.1010.200)
dicarbonic acid), 5% acetone
Flow 1.0 mL/min
Loop 10 L
- Application Note C 23 Sodium, ammonium, diethanolamine, diglycolamine and
potassium in wastewater
- Application Note C 52 Determination of cations and ethanolamine
- Application Note C 56 Sodium, ammonium, methylamine, guanidine and
aminoguanidine in wastewater
- Application Note C 58 N-Methyldiethanolamine (MDEA) in the presence of
standard cations in wastewater
- Application Note C 78 Ethanolamines besides alkali and alkaline earth metal
cations
E Cations
E2 Transition metals zinc, manganese etc. with IC
General remarks
The determination of transition metals such as zinc, manganese, nickel, etc., can
be carried out by separation on a cation exchange column followed by indirect
conductivity detection. This method has the advantage that alkali and alkaline-
earth metals can be determined simultaneously.
There is also the possibility of determining the transition metals by means of
UV/VIS detection after post-column derivatization with PAR. The metals form
colored complexes with the PAR reagent, these can be detected at 520 nm. As
this method is very selective for the transition metals, these can be determined
without interferences also in samples with very high alkali-metal concentrations.
Both methods will be described briefly.
a) for the determination of transition metals using indirect conductivity detection
- MIC-1 Advanced or 861 Advanced Compact IC
- Cation exchange column, e.g. Metrosep Cation 1-2 (6.1010.100), Metrosep C 2
100 (6.1010.210), Metrosep C 2 150 (6.1010.220), Metrosep C 2 250
(6.1010.230) plus Metrosep C 2 Guard (6.1010.200)
b) for the determination of transition metals using post-column derivatization with
PAR and UV/VIS detection
- MIC-1 Advanced IC system plus Lambda 1010 UV/VIS detector, 833 Advanced
IC Liquid Handling Pump Unit and 6.2836.000 post-column reactor
- 844 UV/VIS Compact IC (2.844.0120)
- Cation exchange column, e.g. Metrosep C 2 150 (6.1010.220), Metrosep C 2
250 (6.1010.230) plus Metrosep C 2 Guard (6.1010.200), Nucleosil 5 SA
(6.1007.000) plus Nucleosil 5SA precolumn cartridge (6.1007.010)
Reagents
tance >18 MOhm cm.
- Eluent containing tartaric acid and dipicolinic acid (2,6-pyridine dicarbonic acid),
oxalic acid, etc. The eluent concentrations depend on the column used and the
application.
- 1-g/L stock solutions are prepared by weighing the corresponding amounts of
the salts and dissolving them in ultrapure water.
- 1000-mg/L stock solutions of manganese, zinc, cobalt, copper, nickel, lead,
cadmium, etc., can be obtained especially for ion chromatography from different
reagent manufacturers; after appropriate dilution, these solutions are used for
calibration. The standard solutions are prepared in 2 mmol/L nitric acid (pH
value 2.5).
b) for the determination of transition metals using post-column derivatization with
PAR and UV/VIS detection
Derivatization reagent: 0.15 mmol/L 4-(2-pyridylazo)-resorcinol (PAR), 0.4 mol/L
NH
3
, 80 mmol/L HNO
3
(pH 10).
damage the column.
The samples can be filtered automatically applying ultrafiltration. At higher concen-
trations it may be necessary to dilute the samples.
automated.
In addition, the pH value of the samples should be adjusted to pH 2.5 with nitric
acid.
Analysis
Depending on the concentration range, 10...1000 L sample are introduced.
of cations.
E Cations
Examples for the determination of transition metals with indirect
conductivity detection:
Zinc, manganese in the presence of sodium, ammonium, calcium and magnesium
in an industrial wastewater
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 min
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
uS/cm
Cond
1
2
3
4
1 Zinc 4.44 2484
2 Sodium 8.98 107
3 Ammonium 10.27 108
4 Manganese 29.75 5688
Polarity
(6.1010.200)
Eluent 5 mmol/L tartaric acid, 0.11 mmol/L dipicolinic acid (2,6-
pyridine dicarbonic acid)
Flow 1.0 mL/min
Loop 10 L
Dilution Sample was diluted 1:500 in 2 mmol/L nitric acid
Transition metals in boiler feed water, spiked
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 min
5
10
15
20
25
30
35
mV
ch1
1
2
3
4
5
6
7
8
1 Lithium 7.13 24.4
2 Sodium 8.65 19.3
3 Ammonium 9.72 31.0
5 Zinc 13.64 2.53
6 Iron(II) 24.49 14.6
8 Calcium 46.21 6.08
E Cations
Range 1.0 mS/cm
Full Scale 50 S/cm
Polarity
(6.1010.200)
Eluent 1.75 mmol/L oxalic acid, 1.75 mmol/L ascorbic acid
Flow 1.0 mL/min
Loop 200 L
Example for the determination of transition metals by means of post-column
derivatization with PAR and UV/VIS detection:
Zinc, manganese, copper in a wastewater
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17min
20
40
60
80
100
120
140
160
180
mAU
Abs.1
1
2
3 4
1 Copper 3.34 84
2 Zinc 5.55 370
4 Manganese 14.57 64
Instrument 844 UV/VIS Compact IC (2.844.0120)
Wavelength 510 nm
Polarity
Column Nucleosil 5 SA (6.1007.000) plus Nucleosil 5SA precolumn
cartridge (6.1007.010)
Eluent 70 mmol/L tartaric acid pH 3.3 (adjusted with NH
4
+
)
Flow 1.0 mL/min
Loop 100 L
Derivatization
reagent
0.15 mmol/L PAR, 0.4 mol/L NH
3
, 80 mmol/L HNO
3
Flow of
derivatization
reagent
0.4 mL/min
- Application Note C 49 Trace cations in power plant feed water stabilized with
7 ppm monoethanolamine (MEA)
- Application Note C 55 Determination of lead, zinc, indium, cadmium, cobalt,
ammonium, potassium, manganese, magnesium and calcium
- Poster CIA 2005, UV/VIS Compact IC: Determination of transition metals
E Cations
E3 VA methods: Introduction
Metrohm has been concerned with voltammetric water analysis for many years.
Progress has been remarkable since the introduction of the Polarecord E 261 in
1957. This is true for instrument technology as well as for keeping pace with
general trends: lower detection limits, higher precision, validation, etc. Today,
metal traces down to the ppt level can be determined using voltammetric methods.
Further advantages of voltammetric methods are species analyses and last not
least the relatively modest acquisition and running costs.
The important parameters are the type of metal ions, their concentration and the
type of water to be analyzed (wastewater, ground, drinking, lake, river, sea or rain
water). Concentrations ranging from ppt to ppm can be determined. When
analyzing surface waters, species analyses are very important to answer the
question: Are the metals present as free ions or as metal complexes?
Voltammetry is an elegant, specific, economic and quite modern tool that allows to
answer this question. The examples given here cannot show the whole spectrum
of voltammetric applications but restrict themselves to analysis methods for
determining the total metal content at the trace level.
Voltammetric methods also allow to determine other species that occur in water at
trace levels such as nitrophenols, TNT, iodide/iodate, iodoform, NTA, EDTA, thio-
sulfate, organo-tin compounds, etc.
Before we start let's consider a list of recent literature references. This list is by no
means complete. It is rather meant to demonstrate the broad application spectrum
of voltammetric methods in water analysis:
- Riesenhofer,E., Adami,G., Favretto,A. Heavy metals and nutrients in costal,
surface seawaters (Gulf of Trieste, Nothern Adriatic Sea): an environmental
study by factor analysis. (Zn, Cd, Pb, Cu in seawater). Fresenius,J.Anal.Chem.
354, (1996) 729-734
- Colombo,C., van den Berg,C.M.G. Simultaneous determination of several trace
metals in sea water using cathodic stripping voltammetry with mixed ligands.
(Cu, Cd, Pb, Ni, Co, Zn in seawater). Anal.Chim.Acta 337, (1997) 29-40
- Sander,S. Simultaneous adsorptive stripping voltammetric determination of
molybdenum(VI), uranium(VI), vanadium(V), and antimony(III) (Mo, U, V, Sb in
potable water, seawater, slag). Anal.Chim.Acta 394, (1999) 81-89
- Morales,M.M., Marti,P., Llopis,A., Campos,L., Sagrado,S. An environmental
study by factor analysis of surface seawaters in the Gulf of Valencia (Western
Mediterranean).(Zn, Cd, Pb, Ni, Cr in seawater). Anal.Chim.Acta 394, (1999)
109-117
(continued on page 2136)
This page lists a selection of Application Bulletins that you can obtain free of
charge from you Metrohm distributor.
AB no. 36 Polarographic analysis half-wave potentials of inorganic substances
AB no. 74 Polarographic and stripping voltammetric analysis methods for
thallium, antimony, bismuth and iron (copper, vanadium) (Tl, Sb, Bi,
Fe, Cu, V)
AB no. 96 Determination of mercury by stripping voltammetry (Hg)
AB no. 113 Determination of lead, cadmium and copper in foodstuffs, wastewater
and sewage sludge by anodic stripping voltammetry after digestion
(Cd, Pb, Cu)
AB no. 114 Polarographic determination of five metals (copper, cobalt, nickel, zinc
and iron) in a single operation (Cu, Co, Ni, Zn, Fe)
AB no. 116 Polarographic/voltammetric determination of chromium in small
quantities (Cr)
AB no. 117 Determination of selenium by stripping voltammetry (Se)
AB no. 123 Voltammetric determination of iron and manganese in water samples
(Fe, Mn)
AB no. 131 Voltammetric determination of aluminum (Al)
AB no. 146 Direct polarographic determination of trace amounts of molybdenum in
water (Mo)
AB no. 176 Simultaneous determination of lead and tin by anodic stripping
voltammetry (Sn, Pb)
AB no. 186 Determination of aluminum in water samples by adsorptive
voltammetry (Al)
AB no. 207 Stripping voltammetric determination of silver (Ag)
AB no. 220 Voltammetric determination of platinum and rhodium in the ultratrace
range (Pt. Rh)
AB no. 231 Voltammetric determination of zinc, cadmium, lead, copper, thallium,
nickel and cobalt in water samples according to DIN 38406 Part 16
(Zn, Cd, Cu, Tl, Ni, Co)
AB no. 241 Determination of cadmium and lead at the Ultra Trace graphite
electrode by anodic stripping voltammetry (Cd. Pb)
AB no. 242 Determination of tungsten at the Ultra Trace graphite electrode by
anodic stripping voltammetry (W)
AB no. 243 Determination of chromium at the Ultra Trace graphite electrode by
cathodic stripping voltammetry (Cr)
AB no. 254 Determination of zinc, cadmium, lead and copper by anodic stripping
voltammetry using carbon electrodes (Zn, Cd, Pb, Cu)
AB no. 276 Validation of Metrohm VA instruments using Standard Operating
Procedures (SOP)
E Cations
(continued from page 3H134)
- Achterberg,E.P., Braungardt,Ch. Stripping voltammetry for the determination of
trace metal speciation and in-situ measurements of trace metal distributions in
marine waters. (Al, As, Co, Cr, Cu, Fe, Mo, Ni, Pt, Sb, Se, Sn, Ti, U, V, Zn in
seawater, speciation). Anal.Chim.Acta 400, (1999) 381-397
- Bazzi,A. et al. Chemical speciation of dissolved copper in Saginaw bay, lake
Huron, with square wave anodic stripping voltammetry (Cu in lake water,
speciation). J.Great Lakes Res. 28, (2002) 466-478
- Liu,J. et al. Speciation analysis of aluminium(III) in natural waters and biological
fluids by complexing with various catechols followed by differential pulse
voltammetric detection. (Al in river and lake water, speciation). Analyst 127,
(2002) 1657-1665
- Bowie,A.R. et al. Shipboard analytical intercomparison of dissolved iron in
surface waters along a north-south transect of the Atlantic Ocean. (Fe in
seawater). Marine Chemistry 84, (2003) 19-34
- Mylon,S.E., Twining,B.S., Fisher,N.S., Benoit,G. Relating the speciation of Cd,
Cu, and Pb in two Connecticut rivers with their uptake in algae. (Cd, Cu, Pb in
river water, speciation). Environ.Sci. & Technol. 37, (2003) 1261-1267
- Sander,S., Koschinsky,A., Halbach,P. Redox speciation of chromium in the
oceanic water column of the lesser Antilles and offshore Otago Peninsula, New
Zealand. (Cr in seawater, speciation). Marine & Freshwater Research 54,
(2003) 745-754
- Cobelo-Garcia,A., Prego,R., Nieto,O. Chemical speciation of dissolved lead in
polluted environments. A case of study: the Pontevedra Ria (NW Spain). (Pb in
river water, speciation). Ciencias Marinas 29, (2003) 377-388
- Perez-Lopez,M. Lead and cadmium levels in seawater and limpet (Patella
vulgata L.) from the Vigo estuary. (Cd, Pb in seawater estuary water). Revista
de Toxicologia (Alicante, Spain) 20, (2003) 19-22
- Farghali,O.A. Direct and simultaneous voltammetric analysis of heavy metals in
tap water samples at Assuit City: an approach to improve the analysis time for
nickel and cobalt determination at a mercury film electrode. (Ni, Co in tap
water). Microchem.J. 75, (2003) 119-131
- Scoullos,M.J., Pavlidou,A.S. Determination of the lability characteristics of lead,
cadmium and zinc in a polluted Mediterranean brackish-marine interface
system. (Pb, Cd, Zn in estuary water, speciation). Water, Air, and Soil Pollution
147, (2003) 203-227
- Huang,Sh., Wang,Z. Application of anodic stripping voltammetry to predict the
bioavailable/toxic concentration of Cu in natural water. (Cu in surface waters,
speciation). Applied Geochem. 18, (2003) 1215-1223
- El Makhfouk,M., Souissi,A., El Meray,M. Speciation of heavy metals dissolved
in the marine environment along the coast of the town of Safi (Marocco). (Cd,
Zn, Pb, Cu in seawater, speciation). Bull.Electrochem. 19, (2003) 271-278
- Vargas Camara,M. et al. Simultaneous determination of chromium(VI) and
aluminium(III) by adsorptive stripping voltammetry with pyrocatechol violet. (Cr,
Al in river water). Helv.Chim.Acta 86, (2003) 2434-2440
- Pozzi,A. et al. Ultra trace determination of Pt and Rh in wastewater and gullypot
sediments from a low pollution area. (Pt, Rh in wastewater and sediments)
Annali di Chimica (Rome) 93, (2003) 181-186
- Herzl,V.M.C. et al. Species of dissolved Cu and Ni and their adsorption kinetics
in turbid river water. (Cu, Ni in river water, speciation). Estuarine, Coastal and
Shelf Science 56, (2003) 43-52
- Lim,P.E., Mak,K.Y., Mohamed,N., Noor,A.M. Removal and speciation of heavy
metals along the treatment path of wastewater in subsurface-flow constructed
wetlands. (Zn, Cd, Pb, Cu in groundwater). Water Sci. Technol. 48, (2003) 307-
313
- Linnik,P.N. Complexation as the most important factor in the fate and transport
of heavy metals in the Dnieper water bodies. (Cd, Pb, Zn in river water or
groundwater, speciation). Anal.Bioanal.Chem. 376, (2003) 405-412
- Grabarczyk,M., Korolczuk,M. Modification of catalytic adsorptive stripping
voltammetric method for hexavalent chromium determination in the presence of
DTPA and nitrate. (Cr in river and tap water, speciation). Anal.Bioanal.Chem.
376, (2003) 1115-1118
- van Elteren,J.T., Woroniecka,U.D. Investigation into sorption process in the
anodic stripping voltammetric speciation of Cu in natural waters. (Cu in river
water, speciation). Anal.Chim.Acta 476, (2003) 33-42
- Soko,L., Chimuka,L., Cukrowska,E. Pole,S. Extraction and preconcentration of
manganese(II) from biological fluids (water, milk , blood serum) using supported
liquid membrane and membrane probe methods. (Mn traces in water samples).
Anal.Chim.Acta 485, (2003) 25-35
- Jurado-Gonzalez,J.A., Galindo-Riano,M.D., Garcia-Vargas,M. Experimental
designs in the development of a new method for the sensitive determination of
cadmium in seawater by adsorptive cathodic stripping voltammetry. (Cd in
seawater). Anal.Chim.Acta 487, (2003) 229-241
- Riso,R.D., Waeles,M., Garbarino,S., Le Corre,P. Measurement of total selenium
and selenium(IV) in seawater by stripping chronopotentiometry. (Se in
seawater, speciation). Anal.Bioanal.Chem. 379, (2004) 1113-1119
- Korolczuk,M., Moroziewicz,A., Grabarczyk,M., Kutyla,R. Adsorptive stripping
voltammetric determination of cobalt in the presence of dimethylglyoxime and
cetyltrimethylammonium bromide. (Co in river water). Anal.Bioanal.Chem. 380,
(2004) 141-145
- Taher,M.A., Rezaeipour,E., Afzali,D. Anodic stripping voltammetric
determination of bismuth after solid-phase extraction using Amberlite XAD-2
resin modified with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol. (Bi in river
water). Talanta 63, (2004) 797-801
E Cations
- Bobrowski,A. et al. Chromium speciation study in polluted waters using catalytic
adsorptive stripping voltammetry and tangential flow filtration. (Cr in wastewater
and river water, speciation). Talanta 63, (2004) 1003-1012
- Kiptoo,J.K., Ngila,J.C., Sawula,G.M. Speciation studies of nickel and chromium
in wastewater from an electroplating plant ( Ni, Cr in wastewater, speciation).
Talanta 64, (2004) 54-59
- Mlakar,M. Determination of titanium in water solutions. (Ti in seawater).
Electroanalysis 16, (2004) 217-223
- Desimoni,E., Brunetti,B. Cattaneo,R. Validation of some procedures for
quantifying platinum sub-g/L level in some real matrices by catalytic adsorptive
stripping voltammetry. (Pt in tap water). Electroanalysis 16, (2004) 304-310
- Grabarczyk,M., Kaczmarek,L., Korolzuk,M. Determination of Cr(VI) by catalytic
adsorptive stripping voltammetry with application of nitrilotriacetic acid as a
masking agent. (Cr in surface waters, speciation). Electroanalysis 16, (2004)
1503-1507
- Prego,R., Cobelo-Garcia,A. Cadmium, copper and lead contamination of the
seawater column on the Prestige shipwreck (NE Atlantic Ocean). (Cd, Cu, Pb in
seawater). Anal.Chim.Acta 524, (2004) 23-26
- Ensafi,A.A., Khayamian,T., Khaloo,S.S. Application of adsorptive cathodic
differential pulse stripping method for simultaneous determination of copper and
molybdenum using pyrogallol red. (Cu, Mo in river and tap water).
Anal.Chim.Acta 502, (2004) 201-207
- Meylan,S., Odzak,N., Behra,R., Sigg,L. Speciation of copper and zinc in natural
freshwater: comparison of voltammetric measurements, diffusive gradients in
thin films (DGT) and chemical equilibrium models. (Cu, Zn in river water,
speciation). Anal.Chim.Acta 510, (2004) 91-100
- He,Y., Zheng,Y., Ramnaraine,M., Locke,D.C. Differential pulse cathodic
stripping voltammetric speciation of trace level inorganic arsenic compounds in
natural water samples. (As in groundwater, speciation). Anal.Chim.Acta 511,
(2004) 55-61
- Paolicchi,I. et al. Application of an optimization procedure in adsorptive stripping
voltammetry for the determination of trace contaminant metals in aqueous
medium (In in waters). Anal.Chim.Acta 511, (2004) 223-229
- Cobelo-Garcia,A., Prego,R. Chemical speciation of dissolved copper, lead and
zinc in a ria costal system: the role of resuspended sediments. (Cu, Pb, Zn in
seawater and sediments, speciation). Anal.Chim.Acta 524, (2004) 109-114
E3 Determination of Cu, Cd, Pb, Zn with VA
- 705 UV Digester
Reagents
Use only reagents of highest purity and ultrapure water.
- Background electrolyte I: ammonium acetate buffer
Add 59 mL w(CH
3
COOH) = 96% and 75 mL w(NH
3
) = 25% to approx. 300 mL
ultrapure water. Leave to cool down, make up to 500 mL with ultrapure water
and mix. This solution is to be used for samples with a very low chloride
content.
- Background electrolyte II: KCl-sodium acetate buffer
Dissolve 55.9 g KCl and 14.5 g NaOH x H
2
O in approx. 300 mL ultrapure water.
Add 14.7 mL w(CH
3
COOH) = 96%, leave to cool down, make up to 500 mL with
ultrapure water and mix. This solution is used for samples with higher chloride
contents.
- Standard solutions: |(Me) = 1 g/L (Me = Zn, Cd, Pb, Cu)
These are commercially available.
- Standard solutions: |(Me) = 10 mg/L or |(Me) = 1 mg/L
Prepare these solutions by diluting the standard solutions |(Me) = 1 g/L with
ultrapure water. Acidify the resulting solutions by adding 0.1 mL w(HNO
3
) =
65% per 100 mL solution. Ideally the first standard addition should increase
the sample peak height by 50 to 100%. In our example we used a combined
standard solution with the following analyte concentrations |(Me): Zn = 5
mg/L, Cd = 0.02 mg/L, Pb = 0.05 mg/L and Cu = 0.5 mg/L.
Sample preparation
After sampling, immediately filter the water samples through a microfilter (0.45 m)
and acidify by adding 1 mL w(HNO
3
) = 65% per 1 L.
Add 100 L w(H
2
O
2
) = 30% to 10 mL sample and digest in the UV Digester for
60 min at 90 C.
E Cations
Analysis
In the polarographic vessel add 5 mL ultrapure water and 1 mL background
electrolyte to 10 mL digested sample solution and deaerate for 5 min with
nitrogen. After this, record the ASV voltammogram applying the following
conditions:
Stirrer 2000 rpm
Mode DP
Pulse time 0.04 s
Preconcentration potential 1150 mV
Potential gradient 1150 mV to 20 mV
Peak potential Zn approx. 960 mV
Peak potential Cd approx. 560 mV
Peak potential Pb approx. 60 mV
Peak potential Cu approx. 100 mV
The content is determined by means of two standard additions.
Remarks
Tap water that has been at rest in the piping for a longer time can contain up to
2 mg/L Zn. Under these circumstances, zinc is determined by polarography.
The blank values of the chemicals used (including those used for digestion) must
be determined and taken into account when calculating contents.
Example: Zn, Cd, Pb and Cu in river water
E Cations
--------------------------------------------------------------------------------
Method parameters
--------------------------------------------------------------------------------
Method : Co, Ni.mth
Title : Co, Ni
Remark1 :
Remark2 :
Calibration : Standard addition
Technique : Batch
Addition : Manual
Sample ID : river water
Sample amount (mL): 10.000
Cell volume (mL): 10.600
Voltammetric parameters
--------------------------------------------------------------------------------
Mode : DP - Differential Pulse
Highest current range : 10 mA
Lowest current range : 100 nA
Electrode : HMDE
Drop size (1..9) : 4
Stirrer speed (rpm) : 2000
Initial electr. conditioning : No
No. of additions : 2
No. of replications : 2
Measure blank : No
Addition purge time (s) : 10
Initial purge time (s) : 300
Conditioning cycles
Start potential (V) : 0.000
End potential (V) : 0.000
No. of cycles : 0
Hydrodynamic (measurement) : No
Cleaning potential (V) : -0.700
Cleaning time (s) : 10.000
Deposition potential (V) : -0.700
Deposition time (s) : 30.000
Start potential (V) : -0.700
End potential (V) : -1.300
Voltage step (V) : 0.006
Voltage step time (s) : 0.400
Sweep rate (V/s) : 0.015
Pulse amplitude (V) : 0.050
Pulse time (s) : 0.040
Cell off after measurement : Yes
--------------------------------------------------------------------------------
Peak evaluation
Regression technique : Linear regression
Peak evaluation : Height
Minimum peak width (V.steps) : 5
Minimum peak height (A) : 1.000e-010
Reverse peaks : No
Smooth factor : 4
Eliminate spikes : Yes
Substances
--------------------------------------------------------------------------------
Co : -1.050 V +/- 0.050 V
Standard solution : 1 5.000 g/L
Addition volume (mL) : 0.100
default : Final result (Co) =
Conc * (10.6 / 10) * (1e+006 / 1) + 0 - 0
Ni : -0.970 V +/- 0.050 V
Standard solution : 1 100.000 g/L
Addition volume (mL) : 0.100
default : Final result (Ni) =
Conc * (10.6 / 10) * (1e+006 / 1) + 0 - 0
Solutions
--------------------------------------------------------------------------------
No. Content Predose (mL)
--- ------------------------------------------------ ------------
E Cations
- Application Bulletin no. 231 Voltammetric determination of zinc, cadmium,
lead, copper, thallium, nickel and cobalt in water samples according to DIN
38406 Part 16
E3 Determination of Co and Ni with VA
- 705 UV Digester
Reagents
- Background electrolyte: NH
3
-NH
4
Cl buffer
Under stirring add 53 mL w(HCl) = 30% and 112.5 mL w(NH
3
) = 25% to approx.
300 mL ultrapure water. Leave to cool down, make up to 500 mL with ultrapure
water and mix.
- DMG, Na salt (CAS 75006-64-3) in ultrapure water: c(DMG-Na) = 0.1 mol/L.
Prepare fresh solution every second day.
- Standard solutions: |(Me) = 1 g/L (Me = Co and Ni)
These solutions are commercially available.
- Standard solutions: |(Me) = 1 mg/L
Prepare these solutions by diluting the standard solutions |(Me) = 1 g/L with
ultrapure water. Acidify the resulting solutions by adding 0.1 mL w(HNO
3
) =
65% per 100 mL solution. Ideally the first standard addition should increase the
sample peak height by 50 to 100%. In our example we used a combined
standard solution with the following analyte concentrations |(Me): Ni = 0.1
mg/L, Co = 5 g/L.
Sample preparation
After sampling, immediately filter the water samples through a microfilter (0.45 m)
and acidify by adding 1 mL w(HNO
3
) = 65% per 1 L.
Add 100 L w(H
2
O
2
) = 30% to 10 mL sample and digest in the UV Digester for
60 min at 90 C.
E3 Determination of Co and Ni with VA
Analysis
In the polarographic vessel add 0.5 mL background electrolyte and 100 L
DMG solution to 10 mL digested sample solution (the pH value of the
measuring solution should be between 8.5 and 9) and deaerate for 5 min with
nitrogen. After this, record the CSV voltammogram applying the following
conditions:
Stirrer 2000 rpm
Mode DP
Pulse time 0.04 s
Peak potential Ni approx. 950 mV
Peak potential Co approx. 1070 mV
Remarks
- The blank values of the chemicals used (including those used for digestion)
must be determined and taken into account when calculating contents.
- According to this method Co and Ni can be determined in the range 20 ng/L to
10 g/L. If higher concentrations have to be determined, the samples must be
diluted with ultrapure water.
E Cations
Example: Co and Ni in river water
- Application Bulletin no. 231 Voltammetric determination of zinc, cadmium,
lead, copper, thallium, nickel and cobalt in water samples according to DIN
38406 Part 16
E3 Determination of Fe with VA
General remarks
The method to be described is very sensitive for iron. It is especially useful for
investigating ground, drinking, surface and cooling waters, where iron concentra-
tion is important. The DPCSV method is applied to the triethanolamine complex
formed. The determination limit lies at |(Fe) = 5 g/L.
The constituents normally occurring in these water types do not interfere with the
determination of iron.
- 705 UV Digester
E3 Determination of Fe with VA
Sample preparation
Add 50 L w(HCl) = 30% and 100 L w(H
2
O
2
) = 30% to 10 mL water sample and
digest for 60 min at 90 C in the UV Digester.
Reagents
- Background electrolyte:
Dissolve 10 g KBrO
3
and 5 g triethanolamine (CAS 102-71-6) in approx.
300 mL ultrapure water, make up with ultrapure water to 500 mL and mix.
Standard solution: |(Fe) = 1 g/L
This standard solution is commercially available.
- Standard solution: |(Fe) = 10 mg/L
Add 50 L w(HCl) = 30% to 1.00 mL |(Fe) = 1 g/L, make up to 100 mL with
ultrapure water and mix. Ideally the first standard addition should increase the
sample peak height by 50 to 100%.
Analysis
In the polarographic vessel deaerate 10 mL digested water sample during 5 min
with nitrogen and add 1 mL background electrolyte. Record the DPCSV voltam-
mogram applying the following conditions:
Stirrer 2000 rpm
Mode DP
Pulse time 0.04 s
Peak potential Fe approx. 1000 mV
E Cations
Example: Fe in river water
- Application Bulletin no. 123 Voltammetric determination of iron and manga-
nese in water samples
E3 Determination of Mo with VA
General remarks
Natural waters contain only traces of Mo. The determination limit of the present
method lies at |(Mo) = 50 ng/L.
The method is based on the fact that the molybdate ion MoO
4
2
forms a complex
with 8-hydroxy-7-iodo-5-quinolinesulfonic acid (H
2
L). This complex, which can be
written as MoO
2
L
2
2
, is adsorbed at the Hg electrode and electrochemically
reduced to the Mo(V) complex. The protons present in the solution oxidize the
Mo(V) immediately to the Mo(VI) complex, which is then again available for elec-
trochemical reduction. This catalytic reaction is the reason for the high sensitivity
of the method.
- 705 UV Digester
E3 Determination of Mo with VA
Sample preparation
2
O
2
Reagents
- Reagent solution:
Dissolve 70 mg 8-hydroxy-7-iodo-5-quinolinesulfonic acid (CAS 547-91-1) in
approx. 900 mL c(H
2
SO
4
) = 0.1 mol/L. In this solution dissolve under stirring
52.2 g KCl, make up to 1 liter with c(H
2
SO
4
) = 0.1 mol/L and mix.
- Standard solution: |(Mo) = 1 g/L
- Standard solution: |(Mo) = 1 mg/L
Make up 100 L |(Mo) = 1 g/L to 100 mL with c(H
2
SO
4
Ideally the first standard addition should increase the sample peak height by 50
to 100%.
Analysis
In the polarographic vessel add 2 mL reagent solution to 10 mL digested water
sample and deaerate for 5 min with nitrogen. Record the DP polarogram applying
the following conditions:
Pulse amplitude 50 mV Potential gradient 10 mV/s
Equilibration time 3 s Peak potential Mo approx. 990
mV
Remark
For accurate concentration determinations, the blank value of the chemicals used
has to be taken into account. The blank value is obtained by determining the Mo
concentration of 10 mL ultrapure water plus 2 mL reagent solution.
E Cations
Example: Mo in lake water
Mo
water
-0.80 -0.90 -1.00 -1.10
U (V)
5.00u
2.50u
0
-2.50u
-5.00u
-7.50u
-10.0u
I

(
A
)
Mo
-5.00e-7 0 5.00e-7 1.00e-6 1.50e-6
c (g/L)
0
-2.00u
-4.00u
-6.00u
-8.00u
-10.0u
-12.0u
I

(
A
)
-4.7e-007
Mo
c = 0.568 g/L
+/- 0.013 g/L (2.32%)
- Application Bulletin no. 146 Direct polarographic determination of trace
amounts of molybdenum in water
E3 Determination of U with VA
General remarks
The unranium content of natural waters generally lies in the lower g/L range.
Depending on the degree of contamination or on the geology of the catchment
area, river waters have an uranium content between 30 ng/L und 20 g/L while
sea and brackish waters normally contain 2 to 5 g/L U.
The method described here is based on the adsorption voltammetric determination
of the uranyl-chloranilic acid complex. It is fairly specific and allows the
determination of uranium concentrations in the range 24 ng/L to 40 g/L. More
details concerning the method can be found in the following references:
- Sander,S., Henze,G. Adsorption voltammetric techniques for the determination
of uranium(VI) with 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone as complex
forming reagent. Fresenius,J.Anal.Chem. 349, (1994)654-658
- Sander,S., Wagner,W., Henze,G. Direct determination of uranium traces by
adsorptive stripping voltammetry. Anal.Chim.Acta 305, (1995)154-158
E3 Determination of U with VA
- 705 UV Digester
Sample preparation
2
O
2
Reagents
- Chloranilic acid: c = 5 mmol/L (EC no. 201-780-7)
Dissolve 261 mg 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone in ultrapure
water, make up to 250 mL with ultrapure water and mix. This solution has a
shelf life of approx. 1 week.
- Sodium hydroxide solution: c(NaOH) = 0.1 mol/L
- Hydrochloric acid: c(HCl) = 0.1 mol/L
- Standard solution: |(U) = 1 g/L
Dissolve 1.78 g (CH
3
COO)
2
UO
2
x 2 H
2
O in approx. 900 mL ultrapure water.
Add 1 mL w(HNO
3
) = 65%, make up to 1 liter with ultrapure water and mix.
- Standard solution: |(U) = 1 mg/L
Transfer 100 L of each |(U) = 1 g/L and w(HNO
3
) = 65% into a 100-mL volu-
metric flask, make up to mark with ultrapure water and mix. Ideally the first
standard addition should increase the sample peak height by 50 to 100%.
Analysis
Transfer 10 mL of the digested water sample into the polarographic vessel, add
100 L chloranilic acid and adjust the pH value to 2.5 0.05 by adding NaOH or
HCl solution. Deaerate for 5 min with nitrogen and record the AdSV voltammo-
gram applying the following conditions:
E Cations
Stirrer 2000 rpm
Mode DP
Pulse time 0.04 s
Preconcentration
potential
0 mV
Peak potential U approx. 40 mV
Example: U in river water
E3 Determination of Ti with VA
E3 Determination of Ti with VA
General remarks
Natural waters contain only traces of titanium 20 to 70 ng/L Ti have been found
in sea water. Clearly, once again a sensitive analysis method is required to deter-
mine such low contents.
The present method is based on the adsorptive voltammetric determination of the
Ti-mandelic acid complex. To increase sensitivity, chlorate ions are added to the
solution; these act as catalysts by reoxydizing the Ti(III) ions formed, thus boosting
the analytical signal. Find more information in the following publication:
- Yokoi,K., van den Berg,C.M.G. Determination of titanium in sea water using
catalytic cathodic stripping voltammetry. Anal.Chim.Acta 245, (1991)167-176
- 705 VA Digester
Sample preparation
2
O
2
) = 30% to 10 mL water sample (sea
water: 2 mL sample plus 8 mL ultrapure water) and digest for 60 min at 90 C in
the UV Digester.
Reagents
- Mandelic acid:
Dissolve 6.7 g mandelic acid (CAS 611-72-3) in ultrapure water, make up to 100
mL with ultrapure water and mix.
- Potassium chlorate solution:
Dissolve 6.1 g KClO
3
in ultrapure water, make up to 100 mL with ultrapure
water and mix.
- Ammonia solution: w(NH
3
) = 8.75%
Add 35 mL w(NH
3
) = 25% to approx. 50 mL ultrapure water. Make up to 100 mL
with ultrapure water and mix.
- Standard solution: |(Ti) = 1 g/L
E Cations
- Standard solution: |(Ti) = 1 mg/L
Transfer 100 L |(Ti) = 1 g/L and 2.5 mL w(HCl) = 30% into a 100-mL volu-
metric flask. Make up to the mark with ultrapure water and mix. Ideally the first
standard addition should increase the sample peak height by 50 to 100%. In our
example we used a standard solution with |(Ti) = 100 g/L.
Analysis
Transfer 10 mL digested water sample into the polarographic vessel and add 1 mL
KClO
3
solution, 100 L mandelic acid and 20 L NH
3
solution. The pH value
should be in the range 3.0 to 3.3; adjust with NH
3
solution if necessary. Deaerate
for 5 min with nitrogen and record the AdSV voltammogram applying the following
conditions:
Stirrer 2000 rpm
Mode DP
Pulse time 0.04 s
Purification potential / time8F
9
750 mV / 10 s
Peak potential Ti approx. 780 mV
Remarks
- The blank value of the chemicals used has to be determined and taken into
account.
- The concentration of the standard solution should be chosen such that approx.
10 L can be added with each addition. The peak potential of Ti moves to more
negative values if the pH value decreases (this effect occurs if the standard
solution is too acidic).

9
To prevent interferences by Mo.
E3 Determination of Sb with VA
Example: Ti in sea water
Ti
sea water
-0.60 -0.70 -0.80 -0.90 -1.00
U (V)
-5.00n
-10.0n
-15.0n
-20.0n
-25.0n
I

(
A
)
Ti
-1.00e-7 -5.00e-8 0 5.00e-8 1.00e-7 1.50e-7 2.00e-7
c (g/L)
0
-5.00n
-10.0n
-15.0n
I

(
A
)
-8.1e-008
Ti
c = 460.037 ng/L
+/- 5.022 ng/L (1.09%)
E3 Determination of Sb with VA
General remarks
In natural waters and other environmental water samples such as snow or rain
water, antimony occurs only at the trace level. The ranges of total Sb found are as
follows: sea water 3 to 12 g/L, lake water 0.1 to 0.5 g/L, rain water 0.4 to 0.9
g/L and molten snow 0.2 to 0.4 g/L.
The voltammetric method (ASV) to be described determines the total Sb content.
The determination is carried out in strongly acidic solution to prevent interferences
bei Cu(II) ions, which are present in most cases.
If Sb(III) and Sb(V) have to be determined, please consult the following reference:
- Metzger,M., Braun,H. Stripping voltammetry of traces of antimony(III) and
antimony(V) in natural waters after selective extraction. Anal.Chim.Acta 198,
(1986) 263-275 (in German)
- 705 UV Digester
E Cations
Sample preparation
2
O
2
Reagents
- Hydrochloric acid: w(HCl) = 30%
- Standard solution: |(Sb) = 1 g/L
This solution is commercially available.
- Standard solution: |(Sb) = 1 mg/L
Pipet 100 L |(Sb) = 1 g/L into a 100-mL volumetric flask and add 0.5 mL
w(HCl) = 30%. Fill up to the mark with ultrapure water and mix. Prepare fresh
solution weekly. Ideally the first standard addition should increase the sample
peak height by 50 to 100%. In our example we used a standard solution with
|(Sb) = 0.5 mg/L.
Analysis
Pipet 10 mL digested water sample into the polarography vessel with 5 mL w(HCl)
= 30% and deaerate for 5 min with nitrogen. Record the anodic stripping voltam-
mogram applying the following conditions:
Stirrer 2000 rpm
Mode DP
Pulse time 0.04 s
Electrolysis time 180 s
Peak potential Sb(V) approx. 130 mV
E3 Determination of Se with VA
Example: Total Sb in river water
- Application Bulletin no. 74 Polarographic and stripping voltammetric analysis
methods for thallium, antimony, bismuth and iron (copper, vanadium)
General remarks
On the one hand, selenium is an esssential element for living organisms but on
the other, its toxicity levels are dangerously low. Legal requirements concerning
the highest allowable concentrations in drinking water specify highly varying
values such as <1 g/L (Switzerland), 10 g/L (European Union) and 50 g/L
(US EPA). If extreme cases are included, selenium concentrations in surface
waters range from a few ng/L to 80 g/L.
The CSV methode presented here allows to determine Se with a determination
limit of approx. 0.2 g/L.
As only Se(IV) is electrochemically active, organo-Se compounds, Se(II) or Se(VI)
must be converted to this valency during the digestion step. The following refer-
ence gives additional information:
E Cations
- Lange,B., van den Berg,C.M.G. Determination of selenium by catalytic cathodic
stripping voltammetry. Anal.Chim.Acta 418, (2000)33-42
- 705 VA Digester
Sample preparation
Filter the water sample through a microfilter (0.45 m). Add 1 mL c(NaHCO
3
) = 0.2
mol/L (1700 mg in 100 mL ultrapure water) to 10 mL filtrated sample. The pH
value of the mixture should be 8.3, otherwise adjust with NaHCO
3
. Digest the
mixture for 2 h at 90 C in the UV Digester.
Reagents
- Ammonium sulfate: (NH
4
)
2
SO
4
- Na
2
EDTA solution: c(Na
2
EDTA) = 0.1 mol/L
Dissolve 3.7 g Na
2
EDTA x 2 H
2
O in ultrapure water, make up to 100 mL with
ultrapure water and mix.
- Sulfuric acid: c(H
2
SO
4
) = 0.01 mol/L
- Cu solution: |(Cu) = 0.1 g/L
Pipet 10.0 mL |(Cu) = 1 g/L (commercially available) into a 100-mL volumetric
flask, make up to the mark with c(H
2
SO
4
- Standard solution: |(Se) = 1 g/L
- Standard solution: |(Se) = 1 mg/L
Pipet 100 L |(Se) = 1 g/L into a 100-mL volumetric flask and add 10 mL
c(H
2
SO
4
) = 0.01 mol/L. Make up to the mark with ultrapure water and mix.
Ideally the first standard addition should increase the sample peak height by 50
to 100%.
Analysis
Transfer the digested water sample, 0.2 g ammonium sulfate, 2 mL Na
2
EDTA
solution and 0.5 mL Cu solution into the polarographic vessel. Using c(H
2
SO
4
) = 1
mol/L, adjust the pH value of the mixture under stirring to 2.2. Deaerate for 5 min
with nitrogen and record the stripping voltammogram applying the following
conditions:
Stirrer 2000 rpm
Mode DP
Pulse time 0.04 s
Peak potential Se(IV) approx. 630 mV
Example: Se in lake water
Se
water
-0.50 -0.55 -0.60 -0.65 -0.70 -0.75
U (V)
0
-2.00n
-4.00n
-6.00n
-8.00n
-10.0n
-12.0n
I

(
A
)
Se
-5.00e-7 0 5.00e-7 1.00e-6 1.50e-6
c (g/L)
0
-1.00n
-2.00n
-3.00n
-4.00n
-5.00n
-6.00n
I

(
A
)
-4.8e-007
Se
c = 0.650 g/L
+/- 0.026 g/L (3.95%)
- Application Bulletin no. 117 Determination of selenium by stripping
voltammetry
E Cations
E3 Determination of Pt and Rh with VA
General remarks
The determination of platinum and rhodium traces has gained strongly in interest
since the 1990s. The emission of these metals by the exhaust catalysts has in-
creased their occurrence, especially near highly frequented roads. The contents
normally range in the lower ng/L.
We are going to describe two extremely sensitive catalytic-voltammetric determi-
nation procedures that allow to determine 0.1 ng/L Pt or 0.5 ng/L Rh. Both meth-
ods are extremely sensitive towards interferences by organic water constituents.
All water samples, including drinking water, must therefore be digested.
- 705 UV Digester
Sample preparation
Acidify 10 mL water sample with 10 L w(HCl) = 30% (pH = approx. 2), add 50 L
w(H
2
O
2
) = 30% and digest for 90 min in the UV Digester. After this digestion step
the water samples can be used directly for the voltammetric determination.
Determination of platinum
Reagents
- Hydrazine sulfate (CAS 10034-93-2): c(N
2
H
6
SO
4
) = 0.1 mol/L
Dissolve 0.13 g hydrazine sulfate in 10 mL ultrapure water. Prepare fresh
solution every week.
- Formaldehyde solution: w(HCHO) = 37%
- Background electrolyte:
Mix approx. 15 mL ultrapure water with 0.8 mL w(H
2
SO
4
) = 96% in a 20-mL
volumetric flask. Leave to cool to room temperature (very important!), add 10 L
w(HCHO) = 37% and 0.6 mL hydrazine sulfate solution, make up to the mark
with ultrapure water and mix. Prepare fresh solution daily.
- Standard solution: |(Pt) = 1 g/L
- Standard solution: |(Pt) = 1 g/L
Prepare this solution daily by stepwise dilution of |(Pt) = 1 g/L with c(HCl) =
0.1 mol/L.
Analysis
Transfer 10 mL digested water sample into the polarographic vessel, add 1.5 mL
background electrolyte and deaerate for 5 min with nitrogen. Record the cathodic
stripping voltammogram (CSV) applying the following conditions:
Stirrer 2000 rpm
Mode DP
Pulse time 0.04 s
Peak potential Pt(IV) approx. 880 mV
Remarks
- It is mandatory to use a Glassy Carbon (GC) electrode as the auxiliairy elec-
trode (6.1241.020 + 6.1247.000).
- It is strongly recommended to use all electrodes and vessels exclusively for Pt
and Rh determination.
- With a preconcentation time of 60 s the linear range extends to 200 ng/L Pt. For
samples with higher contents the sample volume is reduced and made up to 10
mL with ultrapure water.
- At high nitrate contents the Pt peak disappears in the ascending base line. At
10 g/L NO
3
the recovery rate for 5 ng/L Pt is approx. 50%.

- Determine the blank value of the chemicals with ultrapure water and take it into
account when calculating the result. In our case the blank value was approx.
1 ng/L Pt.
E Cations
Determination of rhodium
Reagents
- Hydrochloric acid: w(HCl) = 30%
- Formaldehyde solution: w(HCHO) = 37%
- Standard solution: |(Rh) = 1 g/L
- Standard solution: |(Rh) = 1 g/L
Prepare this solution daily by stepwise dilution of |(Rh) = 1 g/L with c(HCl) =
0.1 mol/L.
Analysis
Transfer 10 mL digested water sample into the polarographic vessel, add 100 L
w(HCl) = 30% and 10 L w(HCHO) = 37% and deaerate for 5 min with nitrogen.
Record the cathodic stripping voltammogram (CSV) applying the following
conditions:
Working electrode HMDE Potential step 4 mV
Stirrer 2000 rpm Electrolysis under
stirring
60 s
Mode DP Equilibration time 10 s
Deaeration time 300 s Preconcentration
potential
700 mV
Pulse amplitude 50 mV Potential gradient 1000 mV to
1200 mV
Pulse time 0.04 s Peak potential
Rh(III)
approx. 1150 mV
The content is determined by means of two standard additions, select Front end
baseline parameter.
Remarks
- With a preconcentation time of 60 s the linear range extends to 500 ng/L Rh.
For samples with higher contents the sample volume is reduced and made up
to 10 mL with ultrapure water.
- As the Rh peak lies in the area where hydrogen evolution starts, it is recom-
mended to evaluate only the front half of the peak.
- Determine the blank value of the chemicals with ultrapure water and take it into
account when calculating the result. In our case the blank value was approx.
1 ng/L Rh.
Examples: Pt and Rh in snow water
Pt
Snow
-0.60 -0.70 -0.80 -0.90 -1.00 -1.10
U (V)
-10.0n
-20.0n
-30.0n
-40.0n
-50.0n
I

(
A
)
Unk Unk
Pt
Unk
Unk
-1.00e-9 -5.00e-10 0 5.00e-10 1.00e-9 1.50e-9
c (g/L)
0
-5.00n
-10.0n
-15.0n
-20.0n
-25.0n
-30.0n
I

(
A
)
-8e-010
Pt
c = 0.918 ng/L
+/- 0.013 ng/L (1.45%)
Rh
Snow
-1.00 -1.05 -1.10 -1.15 -1.20
U (V)
-100n
-200n
-300n
-400n
-500n
-600n
I
(A)
Rh
-4.00e-9 -2.00e-9 0 2.00e-9 4.00e-9 6.00e-9
c (g/L)
0
-100n
-200n
-300n
-400n
I

(
A
)
-3.5e-009
Rh
c = 3.564 ng/L
+/- 0.012 ng/L (0.33%)
- Application Bulletin no. 220 Voltammetric determination of platinum and
rhodium in the ultratrace range
F Specific water constituents
F1 Ion chromatography: NTA, EDTA and DTPA
General remarks
The procedure described below allows the determination of the dissolved
complexing agents nitrilotriacetic acid (NTA), ethylenedinitrilotetraacetic acid
(EDTA) and diethylenetrinitrilopentaacetic acid (DTPA) by means of liquid
chromatography (DIN 38413-8).
NTA, EDTA und DTPA are complexed by iron(III) ions; this is followed by
separation on a reversed-phase column by means of ion-pair chromatography.
The eluent contains nitric acid, tetrabutylammonium hydrogensulfate (TBA-HSO
4
),
tetrabutylammonium hydroxide (TBA-OH) and methanol. The detection of the
complexing agents is carried out by UV/VIS detection. Before the detection, a
suppressor removes the excess free iron(III).
- MIC-2 Advanced IC system plus Lambda 1010 UV/VIS detector or 844 UV/VIS
Compact IC plus 833 IC Liquid Handling Suppressor Unit
- Reversed-phase column, e.g. Prontosil 120-5-C18 AQ, 250 mm
Reagents
tance >18 MOhm cm.
- NTA: |(NTA) = 1 g/L
Weigh 0.100 g NTA into a 100-mL volumetric flask, dissolve in 1 mL NaOH
(1 mol/L) and make up to the mark with ultrapure water.
- EDTA: |(EDTA) = 1 g/L
Weigh 0.100 g EDTA into a 100-mL volumetric flask, dissolve in 1 mL NaOH
- DTPA: |(DTPA) = 1 g/L
Weigh 0.100 g DTPA into a 100-mL volumetric flask, dissolve in 1 mL NaOH
Instead of the acids the corresponding sodium salts can be used. In this case no
addition of NaOH is required.
F1 Ion chromatography: NTA, EDTA and DTPA
- Eluent: 0.5 mmol/L nitric acid, 2.5 mmol/L TBA-OH, 7.5 mmol/L TBA-HSO
4
,
5% methanol
Transfer 0.25 mL HNO
3
(2 mol/L), 1.6 mL TBA-OH solution (40%), 2.55 g TBA-
HSO
4
and 50 mL methanol into a 1000-mL volumetric flask, make up to the
mark with ultrapure water and mix.
- Suppressor regenerant solution: 200 mmol/L H
2
SO
4
, 50 mmol/L oxalic acid,
10% acetone in ultrapure water
- Suppressor rinsing solution: 50 mmol/L MgSO
4
in ultrapure water
- Derivatization solution: 37 mmol/L iron(III) nitrate, 130 mmol/L TBA-HSO
4
in
ultrapure water
Weigh 1.5 g iron(III) nitrate nonahydrate (37 mmol/L Fe(III)(NO
3
)
3
x 9 H
2
O) and
4.4 g into a 1000-mL volumetric flask and make up to the mark with ultrapure
water.
The samples have to be derivatized before the analysis. This is done as follows:
add 1 part derivatization solution (e.g. 1 mL) to 20 parts sample (e.g. 20 mL), seal
and keep at 60 C for 20 minutes.
Analysis
above-mentioned standards are diluted with ultrapure water.
Like the samples the standard solutions have to be derivatized before injection.
This is done as follows: add 1 part derivatization solution (e.g. 1 mL) to 20 parts
standard (e.g. 20 mL), seal and keep at 60 C for 20 minutes.
Examples
NTA, EDTA and DTPA in water
0 1 2 3 4 5 6 7 8 9 10 11 min
2
4
6
8
10
12
14
16
18
20
22
24
mV
ch1
1
2
3
1 NTA 4.51 0.48
2 EDTA 5.07 0.50
3 DTPA 7.8 0.98
Instrument MIC-2 Advanced system plus Lambda 1010 UV/VIS detector
Wavelength 206 nm
Column Prontosil 120-5-C18 AQ, 250 mm
Eluent 0.5 mmol/L nitric acid / 2.5 mmol/L TBA-OH / 7.5 mmol/L TBA-
HSO
4
/ 5% methanol
Flow 1.0 mL/min
Loop 100 L
F2 VA method: NTA and EDTA in wastewater
- IC Application Note S 36 The use of the MSM in the determination of NTA,
EDTA and DTPA in water samples
- DIN 38413-8 Determination of nitrilotriacetic acid (NTA), ethylenedinitrilotetra-
acetic acid (EDTA) and diethylenetrinitrilopentaacetic acid (DTPA) by liquid
chromatography
General remarks
The procedure described below allows the determination of NTA and EDTA at
mass concentrations of |(NTA/EDTA) = 0.05 to 25 mg/L in loaded water and
wastewater samples.
In a first step, NTA and EDTA are converted into their Bi complexes by adding Bi
3+
ions at pH 2.0. These complexes have different peak potentials and can therefore
be separated from each other by DP polarography.
The interfering anions nitrite, sulfite and sulfide are removed by making the
solution acidic and gas sparging. Interfering cations are removed by cation
exchange heavy-metal complexes of NTA or EDTA present in the sample are
decomposed by this step. To remove interfering organic constituents (e.g.
surfactants), the sample solution is percolated through a column filled with an
nonpolar adsorber resin.
Reagents
tance >18 MOhm cm.
- Nitric acid: w(HNO
3
) = 65% and c(HNO
3
) = 2 mol/L
- Basic Bi(III) nitrate: Bi(OH)
2
NO
3
(CAS 1304-85-4)
- Potassium nitrate: KNO
3
- Methanol: CH
3
OH
- Ascorbic acid: vitamin C (CAS 50-81-7)
- NTA: nitrilotriacetic acid (CAS 139-13-9
- EDTA: ethylenediaminetetraacetic acid disodium salt dihydrate, Na
2
EDTA x
2 H
2
O (CAS 6381-96-6)
- Sodium hydroxide solution: c(NaOH) = 0.1 mol/L and c(NaOH) = 2 mol/L
- Hydrochloric acid: c(HCl) = 0.1 mol/L
- Strongly acidic cation exchanger in Na
+
form: 3001000 m (2050 mesh),
e.g. Amberlite IR 120
- Nonpolar adsorber resin: on a polystyrene base, for analytical purposes;
300...1000 m (20...50 mesh), e.g. XAD 2
- Bi(III) nitrate solution: |(Bi
3+
) = 2000 mg/L
Dissolve 2.8 g Bi(OH)
2
NO
3
in 25 mL w(HNO
3
) = 65% and make up to 1 liter with
ultrapure water. You can also use a commercially available Bi standard with
|(Bi
3+
) = 1000 mg/L. In this case the standard addition volumes have to be
doubled.
- Bi/NTA stock solution: |(NTA) = 1000 mg/L
a) Dissolve 4.5 g Bi(OH)
2
NO
3
in 30 mL w(HNO
3
) = 65% and make up to approx.
400 mL with ultrapure water.
b) Dissolve 1000 mg NTA in 20 mL c(NaOH) = 2 mol/L and make up to approx.
Mix the two solutions, leave to cool down and make up to 1 liter with ultra-
pure water. This stock solution has a shelf life of approx. 1 month.
- Bi/NTA standard solution: |(NTA) = 100 mg/L
Transfer 10.0 mL Bi/NTA stock solution into a 100-mL volumetric flask, add 50
mL ultrapure water and 15 mL c(HNO
3
) = 2 mol/L, fill up to the mark with ultra-
pure water and mix. This standard solution has a shelf life of approx. 1 week.
- Bi/EDTA stock solution: |(EDTA) = 1000 mg/L
a) Dissolve 3.1 g Bi(OH)
2
NO
3
in 30 mL w(HNO
3
) = 65% and make up to approx.
b) Dissolve 1274 mg Na
2
EDTA x 2 H
2
O in 20 mL c(NaOH) = 2 mol/L and make
up to approx. 400 mL with ultrapure water.
Mix the two solutions, leave to cool down and make up to 1 liter with ultra-
pure water. This stock solution has a shelf life of approx. 1 month.
- Bi/EDTA standard solution: |(EDTA) = 100 mg/L
Transfer 10.0 mL Bi/EDTA stock solution into a 100-mL volumetric flask, add
50 mL ultrapure water and 15 mL c(HNO
3
) = 2 mol/L, make up to the mark with
ultrapure water and mix. This standard solution has a shelf life of approx. 1
week.
Preparation of the columns for solid-phase extraction
The columns used are glass colums with an inner diameter of 8 mm and a one-
way cock (2.5 mm bore), e.g. according to DIN Analysis EHB 3 NS.
Cation exchanger resin
Add c(HCl) = 0.1 mol/L to the cation exchanger, the volume of the solution being
five times the volume of the cation exchanger resin. Stir the suspension for at least
2 h. Wash with ultrapure water until acid-free, decant the excess water and add
c(NaOH) = 0.1 mol/L to the resin, again using the five-fold volume. Stir for 2 h to
convert the resin into the Na
+
form. Wash the treated resin with ultrapure water
until the wash water is neutral.
Plug the column with glass wool. Suspend 5 mL cation exchanger resin in ultra-
pure water, fill the suspension into the column without generating air bubbles and
rinse with 20 mL ultrapure water (filling height approx. 100 mm). Do not let the
water level above the packing descend to less than 2 to 3 mm and discard the
cation exchanger resin after use.
Nonpolar adsorber resin
Plug the column with glass wool. Suspend 5 mL adsorber resin in methanol and fill
the suspension into the column without generating air bubbles. Rinse the absorber
resin with 10 mL methanol and then with 20 mL ultrapure water. Do not let the
water level above the packing descend to less than 2 to 3 mm and discard the
adsorber resin after use.
Sampling and sample preparation
Acidify the water sample to pH = 2 by adding w(HNO
3
) = 65% (1 mL/L). Solid
constituents are removed from the sample by filtration through a membrane filter
with a pore size of 0.45 m. The sample is now stabilized and can be kept in the
refrigerator at 4 C for approx. 1 week.
Dissolve 20 g KNO
3
in 100 mL pretreated water sample and percolate the solution
through the adsorber resin at a rate of 5 mL/min. Discard the first 20 mL and per-
colate the remaining 80 mL through the cation exchanger at a rate of 5 mL/min.
Again discard the first 20 mL, which means that 60 mL sample are available for
the polarographic analysis.
Analysis
Pipet 10 mL sample solution into the polarographic vessel, add approx. 400 mg
ascorbic acid and deaerate for 5 min with nitrogen. Record the DP polarogram
between +0.1 V and 0.6 V. There must be no peaks at the potentials corre-
sponding to Bi-NTA (approx. 0.23 V) and Bi-EDTA (approx. 0.44 V).
Add now 25 L Bi(III) nitrate solution (at higher contents correspondingly more)
and under stirring deaerate for 5 min with nitrogen. Record another DP polarogram
applying the same conditions as above. The Bi peak appearing at approx. +0.02 V
should be about twice as high as the peaks of the corresponding Bi complexes. If
this is not the case, add more Bi(III) nitrate solution.
The NTA and/or EDTA concentrations are obtained by means of standard
additions with the corresponding stock or standard solutions.
Working electrode DME
Stirrer 2000 rpm
Mode DP
Start potential 100 mV
End potential 600 mV
Potential step 6 mV
Time 0.6 s
Potential gradient 10 mV/s
Peak potential, Bi-NTA 0.22 V
Peak potential, Bi-EDTA 0.44 V
Remarks
To eliminate errors in sample preparation, the recovery rate R has to be deter-
mined for each measuring series. This is done by subjecting 100 mL NTA or EDTA
standard solution to the complete analysis procedure (including the resins). The
recovery rate must be >90% and has to be taken into account when calculating the
content. If the recovery rate is <90%, the quality of the cation exchanger has to be
checked.
The following formulas apply:
Recovery rate R in % = A x 100 / B
A = mg/L NTA or EDTA found
B = mg/L NTA or EDTA added
Content calculation taking R into account:
D = C x 100 / R
C = mg/L NTA or EDTA found
D = mg/L NTA or EDTA corrected
Example: NTA and EDTA contents of an industrial wastewater
Final results +/-St. dev. RSD % Comments
NTA: = 0.513 mg/L 0.005 1.025
EDTA: = 0.574 mg/L 0.014 2.362
- Application Bulletin no. 76 Polarographic determination of nitrilotriacetic acid
(NTA) and ethylenediaminetetraacetic acid (EDTA) according to DIN 38413 part
5
Potentiometric/titrimetric analyses
Automation examples
MATi 1: Fully automated water analysis system for series of
up to 59 samples
1. Design Qualification
Fully automated and PC-controlled water analysis system based on the 836
Titrando and the 815 Robotic USB Sample Processor XL.
In particular it contains the new quick aliquoting device 6.9958.007, an overflow
buret allowing quick and precise dosing of a 100 mL sample after conductivity
measurement, necessary for alkalinity determination and the water hardness
titration. MATi 1 has all it takes to perform 59 water determinations fully automati-
cally and includes all necessary accessories and sensors. It is a ready-to-use PC-
controlled system that measures conductivity and pH, determines p and m values
as well as water hardness (Ca/Mg). MATi 1 is eqipped with a quick aliquoting
device for high sample throughput.
1.1. Detailed Procedure
The water analysis involves the determination of alkalinity and water hardness by
means of an automated system consisting an 815 Robotic USB Sample Processor
XL in combination with an 836 Titrando. The Aquatrode Plus is used as indicator
electrode for the alkalinity determination; the water hardness titration is indicated by
a Ca-ISE combined with the reference system of the Aquatrode Plus.
The conductivity measurement is carried out with the 712 Conductometer by
means of a conductivity cell installed on the second tower. The signal supplied by
the conductivity meter is evaluated by the 836 Titrando.
The standard rack used accommodates 59 beakers with a volume of 120 mL. The
samples are stirred by an 802 Rod Stirrer. The new overflow buret transfers the
sample to the external titration vessel using the built-in pumps of the 815 Robotic
USB Sample Processor XL. After the titration the membrane pumps of the 815
Robotic USB Sample Processor XL guarantee efficient aspiration of the spent
solution and thorough rinsing of the titration equipment.
Automation examples
2. Material
Qty Order number Designation
1 2.815.0120 815 Robotic USB Sample Processor XL (2T/4P)
1 2.786.0040 786 Swing Head (without titration head)
1 2.786.0030 786 Swing Head / titration head left
1 6.2041.840 Rack (59 x 120 mL)
1 6.1459.300 120 mL beaker PP (100 pieces)
1 2.804.0040 804 Ti Stand
1 2.802.0040 802 Rod stirrer
1 6.2001.070 Support for external titration station
1 6.1415.250 Titration vessel 250 mL
1 6.5613.000 Eco titration equipment
1 6.1805.010 FEP tubing M6/ 13 cm
1 6.2730.080 Screw nipple as 802 support
4 2.800.0010 800 Dosino
1 6.3032.210 10 mL Dosing Unit for H
2
SO
4
1 6.3032.150 5 mL Dosing Unit for Mg Standard
1 6.3032.220 20 mL Dosing Unit for EDTA
1 6.3032.220 20 mL Dosing Unit for Buffer
4 6.1608.023 Bottle with thread (1000mL)
1 6.2061.010 Reagent Organizer
1 2.836.0020 836 Titrando
1 6 2151.000 USB cable
1 6.0257.000 Aquatrode Plus with built-in Pt 1000
1 6.0508.110 Ca ISE
1 6.2106.020 Cable strand (1m)
1 6.2104.020 Electrode cable (1m)
1 6.2301.060 Conductivity standard solution
1 6.2125.060 Cable 712-PC 25-25 pins
1 6.2125.010 Cable 712-PC 25-9 pins
1 6.2304.000 Set of buffer conc. solutions (4, 7, 9)
1 6.2308.020 Electrolyte (KCl c=3 mol/L)
1 2.712.0010 712 Conductometer
1 6.0912.110 Conductivity cell with Pt 1000
1 6.2116.000 Electrode cable 2 x B plug F
1 6.9958.007 Overflow buret (100 mL)
2 6.1808.050 Olive connector
2 6.1801.000 Transparent PVC tubing
1 6.6056.102 tiamo full
Automation examples
MATi 1: Fully automated water analysis system for series of
up to 59 samples
1. Design Qualification
Fully automated and PC-controlled water analysis system based on the 836
Titrando and the 815 Robotic USB Sample Processor XL.
In particular it contains the new quick aliquoting device 6.9958.007, an overflow
buret allowing quick and precise dosing of a 100 mL sample after conductivity
measurement, necessary for alkalinity determination and the water hardness
titration. MATi 1 has all it takes to perform 59 water determinations fully automati-
cally and includes all necessary accessories and sensors. It is a ready-to-use PC-
controlled system that measures conductivity and pH, determines p and m values
as well as water hardness (Ca/Mg). MATi 1 is eqipped with a quick aliquoting
device for high sample throughput.
1.1. Detailed Procedure
The water analysis involves the determination of alkalinity and water hardness by
means of an automated system consisting an 815 Robotic USB Sample Processor
XL in combination with an 836 Titrando. The Aquatrode Plus is used as indicator
electrode for the alkalinity determination; the water hardness titration is indicated by
a Ca-ISE combined with the reference system of the Aquatrode Plus.
The conductivity measurement is carried out with the 712 Conductometer by
means of a conductivity cell installed on the second tower. The signal supplied by
the conductivity meter is evaluated by the 836 Titrando.
The standard rack used accommodates 59 beakers with a volume of 120 mL. The
samples are stirred by an 802 Rod Stirrer. The new overflow buret transfers the
sample to the external titration vessel using the built-in pumps of the 815 Robotic
USB Sample Processor XL. After the titration the membrane pumps of the 815
Robotic USB Sample Processor XL guarantee efficient aspiration of the spent
solution and thorough rinsing of the titration equipment.
175
3
.

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Automation examples
3.1. Special configuration
Connection of the 6.9958.007 overflow buret to pumps and valves.
Automation examples
4. Method
4.1. Reagents
4.1.1. Conductivity
- 6.2301.060 Conductivity KCl
standard solution
- Dist. water
4.1.2. p-value, m-value and acid
average
- c(H
2
SO
4
) = 0.05 mol/L
- TRIS-(hydroxymethyl)-
aminomethan (Fluka, 93350)
- 6.2307.100 buffer (pH 4)
- 6.2307.110 buffer (pH 7)
- 6.2307.100 buffer (pH 9)
- dist. water
4.1.3. Complexation
- c(acetylacetone) = 0.1 mol/L ,
(Fluka, 11012/1) with c(TRIS) = 0.2
mol/L (Fluka 93350)
- dist. water
4.1.4. Ca2+/ Mg2+ titration
- c(Na
2
EDTA) = 0.05 mol/L, (Fluka,
418283/1) with c(KOH) = 0.1
mol/L, (Fluka, 423543/1)
- dist. water
4.2. Presteps
- Prepare all solutions and titrants
- The exact concentration of all
titrants have to be determined by a
titer determination see AB 206
- Determine cell constant of
6.0912.110 conductivity cell.
- Calibrate 6.0257.000 Aquatrode
Plus in a three-point calibration.
- Before measuring, place
6.0508.110 Ca-ISE for conditioning
about 10 minutes in a solution of
c(CaCl
2
) = 0.01 mol/L.
4.2.1. Sample preparation and
analysis
There are no special sample
preparation steps necessary. Fill
more than 100 mL of water sample
into the sample beakers and place
them on the rack, enter sample data
and start the method.
4.3. Method
Methods used for water analysis:
- conductivity measurement
- pH value measurement
- p and m value by SET pH
- Ca /Mg by DET U
4.4. Calculation
4.4.1 Conductivity
conductivity [S/cm] =
1000*TextToNumber(MV.cond)
4.4.2. pH
pH = MEAS pH.LP.MEA
4.4.3. p-value
p value [mmol/L] = SET
pH.EP{1}.VOL*SET
pH.CONC*2*1000*SET pH.TITER /
MV.Sample size
EP1 = endpoint volume at pH 8.2
[mL]
CONC = concentration of H
2
SO
4
[mol/L]
2 = stoichiometric molar factor for
H
2
SO
4
1000 = factor for converting L to mL
TITER = titer of H
2
SO
4
MV.Sample size = sample size [mL]
4.4.4. m-value
m value [ mmol/L ] = SET
pH.EP{2}.VOL*SET
pH.CONC*2*1000*SET pH.TITER /
MV.Sample size
[mL]
[mL]
CONC = concentration of H
2
SO
4
[mol/L]
2 = stoichiometric molar factor for
H
2
SO
4
TITER = titer of H
2
SO
4
4.4.5. Ca
2+
Ca++ [mmol/L] = DET
U.EP{1}.VOL*DET U.CONC*DET
U.TITER*1000/ MV.Sample size
EP1 = endpoint volume [mL]
CONC = concentration of Ca/Mg
titrant [mol/L]
TITER = titer of Ca/Mg titrant
4.4.6. Mg
2+
Mg++ [mmol/L] = DET U.EP{2}.VOL-
DET U.EP{1}.VOL *DET
U.CONC*DET U.TITER*1000/
MV.Sample size
CONC = concentration of EDTA
[mol/L]
TITER = titer of EDTA
4.4.7. Total water hardness
total water hardness [mmol/L] = DET
U.EP{2}.VOL*DET U.CONC*DET
U.TITER*1000/ MV.Sample size
CONC = concentration of EDTA
[mol/L]
TITER = titer of EDTA
Automation examples
4. Method
4.1. Reagents
4.1.1. Conductivity
- 6.2301.060 Conductivity KCl
standard solution
- Dist. water
4.1.2. p-value, m-value and acid
average
- c(H
2
SO
4
) = 0.05 mol/L
- TRIS-(hydroxymethyl)-
aminomethan (Fluka, 93350)
- 6.2307.100 buffer (pH 4)
- 6.2307.110 buffer (pH 7)
- 6.2307.100 buffer (pH 9)
- dist. water
4.1.3. Complexation
- c(acetylacetone) = 0.1 mol/L ,
(Fluka, 11012/1) with c(TRIS) = 0.2
mol/L (Fluka 93350)
- dist. water
4.1.4. Ca2+/ Mg2+ titration
- c(Na
2
EDTA) = 0.05 mol/L, (Fluka,
418283/1) with c(KOH) = 0.1
mol/L, (Fluka, 423543/1)
- dist. water
4.2. Presteps
- Prepare all solutions and titrants
- The exact concentration of all
titrants have to be determined by a
titer determination see AB 206
- Determine cell constant of
6.0912.110 conductivity cell.
- Calibrate 6.0257.000 Aquatrode
Plus in a three-point calibration.
- Before measuring, place
6.0508.110 Ca-ISE for conditioning
about 10 minutes in a solution of
c(CaCl
2
) = 0.01 mol/L.
4.2.1. Sample preparation and
analysis
There are no special sample
preparation steps necessary. Fill
more than 100 mL of water sample
into the sample beakers and place
them on the rack, enter sample data
and start the method.
4.3. Method
Methods used for water analysis:
- conductivity measurement
- pH value measurement
- p and m value by SET pH
- Ca /Mg by DET U
4.4. Calculation
4.4.1 Conductivity
conductivity [S/cm] =
1000*TextToNumber('MV.cond')
5
.

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178 Metrohm Monograph 8.038.5003 180
6. Troubleshooting
6.1. Set up
- Check the liquid level of flasks and canister used (to avoid flooding or to have
enough solution).
- Ensure that all accessories mounted in the titration head are in their correct
position (see picture, 3.1 special configuration).
- Check that the overflow buret is correctly connected to the pumps (see picture,
3.1 special configuration).
- Adjust the stirring rate to avoid air bubbles on the Ca-ISE surface.
6.2. Application
- Determine the titer of the titrant used before titrations.
- Condition the Ca ISE in CaCl
2
before measuring (see ISE manual).
- If the sample water has a too low content of Mg, a Mg standard solution should
be added.
Remark: Two methods were developed and tested: one with rinsing of the whole
volume of the overflow buret between samples and one without rinsing
of the overflow buret. Repeatability was slightly better with the method
without rinsing, and this also when two different samples were
measured.
Automation examples
Ion chromatography
Metrohm inline ultrafiltration
MIC 2 Modular anion system with chemical suppression plus
838 Advanced IC Filtration Sample Processor
In modern ion chromatography you are recommended to filter all samples before
injection. Separating columns with a particle size below 10 m require absolutely
particle-free sample solutions. Unfiltered solutions can cause increased column
pressures and therefore, in some cases, result in vastly reduced column lives.
Manual filtration is usually carried out by using disposable filter cartridges with a
pore size of 0.45 m or less. These become blocked very quickly, particularly with
samples containing very fine particles. Sample changers with Filter Caps are used
as an alternative. In this case the pore size is frequently larger than with dispo-
sable filters. These are expensive and there is also a risk of blockage.
With the 838 Advanced IC Filtration Sample Processor a sample introduction
instrument with built-in ultrafiltration is available. The ultrafiltration cell combines
inline filtration with automatic sample introduction.
The samples are placed directly on the turntable. As the samples are processed
they are led into the lower chamber of the ultrafiltration cell and along the mem-
brane to the waste vessel. The peristaltic pump creates a vacuum in the upper
chamber and this draws the sample solution through the ultrafiltration membrane.
The filtered sample solution enters the injection loop and is then injected. Less
than 20% of the original solution is removed as filtrate. The rest flows directly into
the waste container. This, together with the geometrical arrangement of the cell,
prevents to a large extent the formation of a filter cake that would block the
membrane.
Ultrafiltration with the 838 Advanced IC Filtration Sample Processor is particularly
suitable for samples with a low to medium load, such as drinking water, surface
water, wastewater, digestion solutions, extracts, etc.
Particle-free samples can be injected directly. Those with a high load such as
juices containing fruit pulp, emulsions and dispersions should be processed by
inline dialysis.
Ion chromatography
The ultrafiltration cell is the
heart of the MIC 2 system with
ultrafiltration. The membrane
prevents particles from getting
onto the separation column.
Gravitation and the high flow
rate prevent premature
blocking of the membrane.
MIC 2 Modular anion system with chemical suppression plus 838 Advanced
IC Sample Processor in the ultrafiltration version.
C = column; D = conductivity detector; E = eluent; P = high-pressure pump; PP =
peristaltic pump; T = transfer water
Automation examples
Example
Chromatogram of rain water after ultrafiltration.
1 Fluoride 3.05 0.057
2 Chloride 5.77 0.353
3 Nitrite 8.12 0.028
4 Nitrate 13.4 5.279
5 Phosphate 17.4 not quantified
6 Sulfate 21.8 2.697
Ion chromatography
Instrument MIC-2 Advanced system with 838 Advanced IC Filtration Sample
Processor (2.838.0210) and standard sample rack (6.2041.440) for
up to 148 samples
Detection Conductivity
Column Metrosep Dual 2 (6.1006.100)
Precolumn Metrosep RP Guard (6.1011.020)
2
CO
3
, 1.7 mmol/L NaHCO
3
Flow 0.8 mL/min
Loop 20 L
Ion chromatography
Metrohm inline dialysis
MIC 7 Modular Anion system with chemical suppression and dialysis
Ion chromatography is an accepted method for simultaneously determining various
anions and cations in water samples and various matrices. Some of these sample
matrices require complex and labor-intensive preparation steps before the
determination itself can be carried out.
Metrohm Inline Dialysis allows a considerable rationalization of the whole analysis.
The only demands placed on the sample: it must either be present in liquid form or
capable of being brought into a liquid form and must be largely homogeneous. If
larger particles are present they must be removed by centrifugation. The sample
solution is then dialyzed in the 833 IC Liquid Handling Dialysis Unit or the 838
Advanced IC Dialysis Sample Processor using a method patented by Metrohm
(US Patent 5,861,097). Thanks to this special stopped-flow method a virtually
complete dialysis rate is achieved. This means that the acceptor solution has the
same ion concentrations as the original sample (equilibrium dialysis). The acceptor
solution is then injected directly into the ion chromatograph and analyzed. If the
system is programmed so that the next sample is dialyzed while the previous
sample is being determined then the total analysis time corresponds to that for a
direct injection.
In the food industry, for example, it is possible to determine the ionic contents of
milk and dairy products very simply. The time-consuming clarification with Carrez
reagents is no longer necessary. With the 833 IC Liquid Handling Dialysis Unit or
the 838 Advanced IC Dialysis Sample Processor emulsions, dispersions and even
freshly pressed orange juice with fruit pulp no longer present any problems.
Automation examples
Top view of the dialysis cell, the
simple but highly efficient purification
system for complex samples.
The method in detail
The method involves four steps. Ultrapure water is normally used as the acceptor
solution for anion determinations while dilute nitric acid is required for cation deter-
minations. Inline dialysis requires a total ion concentration of at least 1 mg/L. For
samples with a lower total ion concentration the completeness of the dialysis can-
not be guaranteed. However, such samples do not normally need to be dialyzed.
Step 1: Rinsing
The dialysis cell is conditioned, i.e. both the sample solution and the acceptor
solution are pumped through the cell. This step removes any traces of the
previous sample from the two channels.
Step 2: Dialysis
The sample solution continues to flow through the cell while the acceptor solution
remains stationary in a closed circuit. In this configuration ions can diffuse through
the membrane. The driving force is the concentration difference. As the sample
solution is continuously renewed, the ion concentrations in the sample solution
and the acceptor solution are the same at equilibrium. This equilibrium is normally
achieved with a sufficient degree of accuracy after 10 minutes.
Step 3: Transfer
After the dialysis the peristaltic pump on the sample side is stopped while the one
on the acceptor side is started, transferring the acceptor solution fraction to the
sample loop of the injector (see flow sheet).
Ion chromatography
Step 4: Sample injection
As soon as the purified sample is in the sample loop it is injected and the analysis
itself starts. The next sample can be dialyzed while the current sample is being
analyzed. In this way the duration of the analysis is reduced to the time required
for producing the chromatogram.
MIC 7 Modular anion system with chemical suppression and dialysis. The
flow sheet shows step 4: sample injection.
C = column; D = conductivity detector; E = eluent; P = high-pressure pump;
PP = peristaltic pump; T = transfer water
Automation examples
Example
Determination of anions in the inlet of a wastewater purification plant.
1 Fluoride 3.68 0.15
2 not determined 4.25
3 Chloride 5.20 72.86
4 Nitrite 6.03 1.13
5 Bromide 7.35 0.37
6 Nitrate 8.23 8.40
7 System peak 9.78
8 Phosphate 12.05 3.85
9 Sulfate 13.90 27.21
Ion chromatography
Instrument MIC-7 Advanced IC system with 838 Advanced IC Dialysis Sample
Processor (2.838.0110) and standard sample rack 6.2041.440 for up
to 148 samples
Detection Conductivity
Column Metrosep A Supp 4 250 (6.1006.430)
Precolumn Metrosep A Supp 4/5 Guard (6.1006.500)
2
CO
3
, 1.7 mmol/L NaHCO
3
+ 2% acetone
Flow 1.0 mL/min
Loop 20 L
MIC-7 Advanced IC system for strongly loaded samples, for example from
wastewater purification plants.
Automation examples
TitrIC
New possibilities in ion analysis through the unique combination
of titration and ion chromatography
TitrIC fully enables the automatic analysis of drinking water. All ionic components
are determined quickly, reliably and reproducibly. Results are presented as a
single report or stored in the integral database.
As this monograph shows, the determination of ionic components in water
samples involves four fields: direct measurement, ion chromatography, titration
and voltammetry. Metrohm accepted the challenge of combining these methods in
a single system in 1998, and the first TitrIC system was introduced. Rapid
advances in instrument development have allowed Metrohm to present a new
version of the extremely powerful TitrIC system, in which direct measurement,
titration and ion chromatography are incorporated in a single analytical unit.
TitrIC first determines the temperature, pH value and conductivity of the sample.
After this the sample material is introduced into the two IC systems, one for
anions, the other for cations, the sample portion for cation determination being
acidified before injection. This is followed by a titration that determines the p and m
values. Calcium and magnesium, which are used to calculate total hardness, can
be determined by titration or ion chromatography.
Ion chromatography determines all the inorganic ions contained in the sample.
This comprises the halides fluoride, chloride, bromide and iodide and their
oxidized and partly toxic compounds such as chlorite, chlorate, perchlorate and
bromate. The nutrient anions nitrite, nitrate and phosphate are also determined, as
is sulfate. If present, organic anions such as formate, acetate or propionate can
also be quantified. As far as cations are concerned, all alkali and alkaline earth
metals are determined. The ammonium content completes the data required for
the nitrogen balance.
The system is capable of taking decisions. Thus, for example, the sample can be
automatically diluted if the conductivity exceeds a predefined value.
The TitrIC system is highly flexible and can easily be adapted to the user's
application requirements.
TitrIC
Report
TitrIC automated drinking water analysis
Sample Drinking water Bonlanden
User Applikationslabor
Deutsche Metrohm GmbH & Co. KG
D-70772 Filderstadt
Deutschland
Date 2006-03-27
No. of determinations 5
Results RSD [%]
pH value 7.69 0.04
Conductivity 944.35 S/cm 8.14
p value 5.59 mmol/L 0.01
Na
+
25.50 mg/L 0.22
K
+
4.57 mg/L 0.14

Ca
2+
127.10 mg/L 1.40
Mg
2+
20.88 mg/L 0.36
F
0.15 mg/L 0.01

Cl
34.33 mg/L 0.32

NO
3
14.26 mg/L 0.13

SO
4
2
79.84 mg/L 0.42
Z anions 9.29 mEq/L 0.02
Z cations 9.29 mEq/L 0.10
Ionic balance 0.00 mEq/L 0.11
Ionic balance 0.01 %
Application Bulletin no. 288 Comprehensive tap water analysis with TitrIC 1
short IC run
long IC run
Automation examples
Schematic of the fully automated TitrIC system for water analysis. The central
component is the 855 Robotic Titrosampler, which carries out the titrations, con-
trols the Dosinos and transfers the sample to the two 861 Advanced Compact IC.
- German standard methods for the examination of water, waste water and
sludge. Beuth Verlag GmbH, Berlin
- Compilation of US EPAs Sampling and Analysis Methods. Lewis Publishers,
Boca Raton USA
- ISO standards. ISO/IEC Information Center, CH-1211 Geneva 20
www.iso.org
- WHO Guidelines for drinking-water quality, 2
nd
ed., Vol 1 & 2. World Health
Organization, Geneva (1996)
- Council Directive 98/83/EC of 3 November 1998 on the quality of water
intended for human consumption. Official Journal of the European Communities
L 330/32 (1998-12-05)
- FRESHWATER FUTURE Adressing freshwater challenges beyond 2003,
designated the International Year of Freshwater by the United Nations. Tudor
Rose Holdings Ltd. UK (2003) ISBN 0-9536140-3-4
Metrohm monographs dealing with the analytical methods used
Appendix
Metrohm monographs dealing with the analytical
methods used
You can obtain these monographs free of charge from your Metrohm distributor.
- Conductometry
- Practical ion chromatography an introduction
- Sample preparation techniques for ion chromatography
- Practical titration a training manual for titrimetric analysis
- Practical voltammetry with the VA Computrace
Drinking water quality requirements
Maximum permissible values
Parameter Switzerland European
Union
US EPA
Temperature 8...15 C
pH value 6.8...8.2 6.5...9.5
Electrical conductivity 200...800
S/cm
2.5 mS/cm
Chlorine 0.8 mg/L
Bound chlorine <3 mg/L
Oxygen 30...100% of
saturation
Oxidizability <3 mg/L O
2
5 mg/L O
2
Ammonium <50 g/L 0.5 mg/L 1 mg/L
Al <50 g/L 0.2 mg/L
As <2 g/L 10 g/L 50 g/L
Ba 2 mg/L
Ca <200 mg/L
Cd <0.5 g/L 5 g/L 5 g/L
Appendix
Parameter Switzerland European
Union
US EPA
Cr(VI) <1 g/L
Cr total 50 g/L 0.1 mg/L
Cu <20 g/L 2 mg/L 1.3 mg/L
Fe <50 g/L 0.2 mg/L
Hg <1 g/L 1 g/L 2 g/L
K <5 mg/L
Mg 50...125
mg/L9F
10
Mn <20 g/L 50 g/L
Na <20 mg/L 200 mg/L
Ni 20 g/L
Pb <1 g/L 10 g/L 15 g/L
Sb 5 g/L 6 g/L
Se <1 g/L 10 g/L 50 g/L
Tl 2 g/L 0.5 g/L
U 30 g/L
Zn <0.1 mg/L
Bromate 10 g/L 10 g/L
Chloride <20 mg/L 250 mg/L
Chlorite 1 mg/L
Cyanide 50 g/L 0.1 mg/L
Fluoride <0.5 mg/L 1.5 mg/L 4 mg/L
Haloacetic acids 60 g/L
Nitrate <25 mg/L 50 mg/L 40 mg/L
Nitrite <10 g/L 0.5 mg/L 1 mg/L
Perchlorate
Phosphate <50 g/L
Sulfate <50 mg/L 250 mg/L
Sulfide n.d.10F
11

10
Depends on the sulfate content, as MgSO
4
affects the taste of the water.
11
Must not be organoleptically detectable according to Swiss legislation
SR 817.021.23 of 26 June 1995 (latest revision: 10 October 2006).
Element traces in water
Element traces in water
g/L (ppb)
Element Lake
Constance11F
12
Sea water Rhine river12F
13
Ag 0.10.3
Al 0.4
As 2.7 0.8 2.8
B 24 43
Bi 0.010.1
Cd 0.3 0.22 7
Co 1 0.010.4 1.9
Cr 3 0.28 14
Cu 4.6 25 8.6
Fe 3060
Hg 0.020.08
Iod (iodide/iodate) 5060
Mn 25
Mo 1
Ni 2.1 0.810 2.8
Pb 1.2 15 3.2
Pt 0.0002
Sb 312
Se 0.9 0.1 6
Sn 0.0010.007
Ti 0.04
U 24
V 13
W 0.01
Zn 45 310 89

12
Lake of Constance (Bodensee in German) borders on Germany, Austria and Switzer-
land and, with a surface of over 500 km
2
, is the third largest lake in Europe after Lake
Balaton and Lake Geneva.
13
The Rhine, at 1320 km one of the longest rivers in Europe, has its two sources in the
Grisons (south-eastern Switzerland), from where it passes through the Lake of
Constance. It enters Germany at Basel and continues to the Netherlands, where it
flows into the North Sea.
Appendix
Sweet water: typical values of the relevant parameters
Parameter Ground water Storage lake River, loaded
Temperature C 10.0 3.6 6.8
S/cm at 25 C
537 140 914
pH value 7.62 7.63 7.95
Acid capacity K
A4.3
mmol/L
5.07 0.52 3.37
Oxygen mg/L O
2
9.2 12.9 10.1
Total hardness mmol/L 2.88 0.47 3.30
Carbonate hardness
mmol/L
2.54 0.27 1.68
Ca mg/L 82.4 12.9 101
Mg mg/L 19.6 3.5 19.0
Na mg/L 3.4 5.2 48
K mg/L 1.0 0.9 5.0
Fe mg/L <0.01 0.05 0.12
Mn mg/L <0.01 0.01 0.17
Ammonium mg/L <0.05 <0.01 0.28
Nitrite mg/L NO
2
<0.005 0.006 1.00
Nitrate mg/L NO
3
8.5 4.3 24.0
Chloride mg/L Cl
-
5.5 7.5 87.0
Sulfate mg/L SO
4
25.0 22.6 136
Phosphate mg/L PO
4
<0.01 <0.01 0.29
Oxidizability mg/L O
2
<0.5 2.3 3.5
A Physical parameters ................... 1
Temperature .................................. 1
General remarks ........................ 1
Recommended accessories....... 1
Water temperature ..................... 1
Air temperature .......................... 1
pH value......................................... 2
General remarks ........................ 2
Two-point calibration of a pH
glass electrode........................... 3
Measuring the pH value ............. 3
Relevant Metrohm literature....... 3
Redox potential .............................. 4
General remarks ........................ 4
Checking and treatment of the
combined Pt electrode................ 4
Measuring the redox potential .... 5
Calculating the redox potential ... 5
Example ..................................... 6
Relevant Metrohm literature....... 6
Electrical conductivity .................... 6
General remarks ........................ 6
Measuring the electrical
conductivity ................................ 9
Relevant Metrohm literature..... 12
B Overall parameters................... 13
Permanganate index
(oxidizability) ............................... 13
General remarks...................... 13
Recommended accessories .... 13
Reagents ................................. 13
Analysis ................................... 14
Calculations............................. 14
Remarks .................................. 14
Acid and base capacity ............... 17
General remarks...................... 17
Reagents ................................. 17
Analyses.................................. 17
Water hardness........................... 22
General remarks...................... 22
Reagents ................................. 23
Analyses.................................. 23
Two alternative titrimetric
methods for determining total
water hardness........................ 26
Relevant Metrohm literature .... 31
Kjeldahl nitrogen ......................... 32
General remarks...................... 32
Reagents ................................. 32
Sample preparation ................. 33
Analysis ................................... 33
Calculations............................. 33
Detailed list of contents
Hydrogen peroxide and
its adducts....................................35
General remarks.......................35
Recommended accessories .....35
Reagents..................................35
Analysis....................................36
Calculations..............................36
Remarks...................................36
Example: H
2
O
2
in a laundry
wastewater ...............................36
Relevant Metrohm literature .....37
Complexing capacity....................38
General remarks and
relevant literature......................38
C Gaseous water constituents......40
Free and total chlorine .................40
General remarks.......................40
Reagents..................................40
Titer determination ...................41
Analysis....................................41
Calculations..............................41
Remarks...................................42
Example: Free and total
chlorine in tap water .................42
Relevant Metrohm literature .....43
Dissolved oxygen.........................43
General remarks.......................43
Reagents..................................44
Sample preparation..................44
Analysis....................................45
Calculation................................45
Remarks...................................45
Example: Oxygen content
of a river water..........................47
Ozone.......................................... 48
General remarks ...................... 48
Recommended accessories..... 48
Reagents ................................. 48
Sampling.................................. 48
Analysis ................................... 48
Calculation............................... 49
Example: Freshly prepared
swimming-pool water ............... 49
D Anions ...................................... 51
D1 Titration: Chloride................ 51
General remarks ...................... 51
Reagents ................................. 51
Analysis ................................... 52
Calculations ............................. 52
Example: Chloride in
tap water (Herisau) .................. 53
D1 Titration: Cyanide................ 55
General remarks ...................... 55
Reagents ................................. 55
Analysis ................................... 55
Calculations ............................. 56
Remarks .................................. 56
Example: Cyanide in an
electroplating wastewater
(direct titration) ......................... 57
D1 Titration: Sulfate.................. 59
General remarks ...................... 59
Reagents ................................. 59
Blank value determination........ 59
Analysis ................................... 60
Calculations.............................. 60
Remarks................................... 60
Example: Titration curves for
blank consumption and sulfate
in a ground-water sample......... 61
D1 Titration: Sulfides and
hydrogen sulfide .......................... 63
General remarks ...................... 63
Reagents.................................. 63
Analysis.................................... 63
Calculations.............................. 63
Remarks................................... 64
Example: Sulfide in a
wastewater sample .................. 64
D2 Ion chromatography:
Introduction.................................. 66
Publications in scientific
journals..................................... 66
D2 Anion determination
with IC.......................................... 68
General remarks ...................... 68
Reagents.................................. 69
Sample preparation methods ... 69
Analysis.................................... 69
Examples ................................. 70
Additional literature .................. 72
D2 Oxyhalides with IC: Chlorate,
chlorite, bromate.......................... 73
General remarks ...................... 73
Reagents.................................. 73
Sample preparation methods ... 74
Analysis ................................... 74
Additional literature.................. 77
D2 Bromate with IC.................. 77
General remarks...................... 77
Reagents ................................. 79
Sample preparation methods... 80
Analysis ................................... 80
D2 Perchlorate with IC ............. 84
General remarks...................... 84
Reagents ................................. 85
Analysis ................................... 86
D2 Chromate Cr(VI) with IC .. 89
General remarks...................... 89
Reagents ................................. 90
Analysis ................................... 91
D2 Silicate
dissolved silicic acid with IC........ 94
General remarks...................... 94
Reagents ................................. 94
Analysis ................................... 95
Metrohm literature concerning
silicate determination with IC....97
D2 Sulfite, sulfate and thiosulfate
with IC..........................................97
General remarks.......................97
Reagents..................................98
Sample preparation methods ...98
Analysis....................................98
Relevant Metrohm literature ...100
D2 Organic acids with IC.........100
General remarks.....................100
Recommended accessories ...100
Reagents................................101
Sample preparation methods .101
Analysis..................................101
D3 Chromate/dichromate
Cr(VI) with VA............................104
General remarks.....................104
Reagents................................104
Polarographic analysis ...........105
Stripping voltammetric
analysis ..................................106
D3 Cyanide with VA................108
General remarks.....................108
Reagents................................108
Polarographic analysis ...........109
Stripping-voltammetric
analysis ..................................109
D3 Sulfides and hydrogen sulfide
with VA...................................... 111
General remarks .................... 111
Recommended accessories... 111
Reagents ............................... 111
Analysis ................................. 112
Relevant Metrohm literature... 112
Additional literature................ 113
D3 Sulfite with VA................... 113
General remarks .................... 113
Reagents ............................... 113
Analysis ................................. 114
E Cations ................................... 116
E1 Titration: Calcium and
magnesium................................ 116
E2 Cation determination
with IC ....................................... 116
General remarks .................... 116
Reagents ............................... 116
Sample preparation methods. 117
Analysis ................................. 117
Additional literature................ 124
E2 Amines, e.g.methylamine,
ethanolamine with IC................. 124
General remarks .................... 124
Reagents ............................... 125
Sample preparation methods. 125
Analysis ................................. 125
E2 Transition metals
zinc, manganese etc. with IC..... 128
General remarks .................... 128
Reagents................................ 128
Sample preparation methods . 129
Analysis.................................. 129
E3 VA methods: Introduction .. 134
E3 Determination of Cu, Cd,
Pb, Zn with VA........................... 139
Reagents................................ 139
Sample preparation................ 139
Analysis.................................. 140
E3 Determination of Co and
Ni with VA.................................. 144
Reagents................................ 144
Analysis.................................. 145
E3 Determination of Fe
with VA....................................... 146
General remarks .................... 146
Reagents................................ 147
Analysis.................................. 147
E3 Determination of Mo
with VA....................................... 148
General remarks .................... 148
Reagents ............................... 149
Analysis ................................. 149
Relevant Metrohm literature .. 150
E3 Determination of U
with VA...................................... 150
General remarks.................... 150
Recommended accessories .. 151
Sample preparation ............... 151
Reagents ............................... 151
Analysis ................................. 151
E3 Determination of Ti
with VA...................................... 153
General remarks.................... 153
Reagents ............................... 153
Analysis ................................. 154
E3 Determination of Sb
with VA...................................... 155
General remarks.................... 155
Reagents ............................... 156
Analysis ................................. 156
E3 Determination of Se
with VA...................................... 157
General remarks.................... 157
Reagents ............................... 158
Analysis ................................. 158
E3 Determination of Pt and
Rh with VA.................................160
General remarks.....................160
Sample preparation................160
Determination of platinum.......160
Determination of rhodium.......162
Examples: Pt and Rh in
snow water .............................163
F Specific water constituents......164
F1 Ion chromatography:
NTA, EDTA and DTPA...............164
General remarks.....................164
Reagents................................164
Analysis..................................165
Additional literature.................167
F2 VA method:
NTA and EDTA in wastewater ...167
General remarks.....................167
Reagents................................167
Preparation of the columns
for solid-phase extraction .......169
Sampling and sample
preparation .............................169
Automation examples ................... 173
Potentiometric/titrimetric
analyses .................................... 173
MATi 1: Fully automated
water analysis system for
series of up to 59 samples..... 173
Ion chromatography................... 182
Metrohm inline ultrafiltration... 182
Ion chromatography................... 185
Metrohm inline dialysis........... 185
TitrIC.......................................... 190
Report .................................... 191
Literature................................ 192
Appendix....................................... 193
Metrohm monographs dealing
with the analytical methods
used........................................... 193
Drinking water quality
requirements ............................. 193
Element traces in water ............. 195
Sweet water: typical values of
the relevant parameters............. 196
Analysis..................................169
Remarks.................................170
Example: NTA and EDTA
contents of an industrial
wastewater .............................171

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Peter A.

Bruttel and Nadine Seifert

ions. At the neutral point, these ions are

are good conductors. If hydration occurs

can be determined. HCN, as shown by its

in c(NaOH) = 0.4 mol/L.

) = 100 mg/L, make up to the mark with

the recovery rate for 5 ng/L Pt is approx. 50%.

0.15 mg/L 0.01

34.33 mg/L 0.32

14.26 mg/L 0.13

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