Monograph

Complexometric (Chelometric)
Titrations
Peter Bruttel, revised by Iris Kalkman and Lucia Meier
Table of contents
Preface 06
Theoretical fundamentals 07–23
Indication of the equivalence point of the titration 09–23
Visual and photometric 09
Potentiometric 10–11
Commonly used complexing agents/titrants 12
Buffer solutions 13
Masking 14
Color indicators 15–21
Preparation of the standard solutions 22
Titer determinations 22–23
Practical examples 24–39
Water hardness, calcium, and magnesium 24–29
Potentiometric titration with the Ca-ISE 25–26
Potentiometric titration with the Cu-ISE 26–27
Photometric titration with the Optrode at 610 nm 27–29
Aluminum and magnesium, alloys and antacids 29–31
Potentiometric titration with the Cu-ISE 31–33
Magnesium and zinc 31–33
Potentiometric titration with the Cu-ISE 31–33
Aluminum, calcium, iron, and magnesium in cement and clinker 33–37
Photometric titrations with the Optrode at 610 nm 33–37
Sulfate 38–39
Potentiometric with the Ca-ISE 38–39
Single determinations 39–92
AI – Aluminum 39–42
General 39–40
Potentiometric with the Cu-ISE 40–41
Photometric with the Optrode at 610 nm 41–42
Ba – Barium and Sr – Strontium 43–45
General 43
Potentiometric with the Cu-ISE 44
Photometric with the Optrode at 574 nm 45
Bi – Bismuth 46–48
General 46
Potentiometric with the Cu-ISE 46–47
Photometric with the Optrode at 520 nm 47–48
Ca – Calcium 48–51
General 48–49
Potentiometric with the Ca-ISE 49–50
Potentiometric with the Cu-ISE 50
Photometric with the Optrode at 610 nm 51
 Cd – Cadmium 52–54
General 52
Potentiometric with the Cu-ISE 52–53
Photometric with the Optrode at 610 nm 53–54
Co – Cobalt 54–56
General 54
Potentiometric with the Cu-ISE 55
Photometric with the Optrode at 574 nm 56
Cu – Copper 57–59
General 57
Potentiometric with the Cu-ISE 58
Photometric with the Optrode at 520 nm 59
Fe – Iron 60–62
General 60
Potentiometric with the Cu-ISE 61
Photometric with the Optrode at 610 nm 62
Ga – Gallium and In – Indium 63–66
General 63
Potentiometric with the Cu-ISE 63–64
Photometric with the Optrode at 610 nm 65
Hg – Mercury 66–67
General 66
Photometric with the Optrode at 502 nm 67
Mg – Magnesium 68–70
General 68
Potentiometric with the Cu-ISE 68–69
Photometric with the Optrode at 610 nm 69–70
Mn – Manganese 70–73
General 70–71
Potentiometric with the Cu-ISE 71–72
Photometric with the Optrode at 610 nm 72–73
Ni – Nickel 73–76
General 73–74
Potentiometric with the Cu-ISE 74–75
Photometric with the Optrode at 574 nm 75–76
Pb – Lead 76–79
General 76–77
Potentiometric with the Cu-ISE 77–78
Photometric with the Optrode at 574 nm 78–79
Pd – Palladium 79–80
General 79
Photometric with the Optrode at 610 nm 80
 Sn – Tin 81–82
General 81
Photometric with the Optrode at 574 nm 81–82
Th – Thorium 82–84
General 82–83
Photometric with the Optrode at 574 nm 83–84
TI – Thallium 84–86
General 84
Potentiometric with the Cu-ISE 85–86
Photometric with the Optrode at 610 nm 86
Zn – Zinc 87–89
General 87
Potentiometric with the Cu-ISE 87–88
Photometric with the Optrode at 610 nm 88–89
Zr – Zirconium and Hf – Hafnium 89–92
General 89–90
Potentiometric with the Cu-ISE 90–91
Photometric with the Optrode at 520 nm 91–92
Appendix 93–95
Index 93–94
Photometric indication of the equivalence point of the titration 95
Table of figures 96–98
 Preface

06 In 1945, Gerold Schwarzenbach dis-

covered that aminocarboxylic acids
be titrated. The use of new metal
indicators and masking agents also
(e.g., NTA, EDTA) form stable com- enabled determinations of metal
plexes with metal ions. On the basis ion mixtures. Nowadays, together
of this discovery, he developed the with acid/base, redox, and precipi-
complexometric titration technique, tation titrations, complexometric
which became increasing popular titrations are the most frequently
from 1950 onwards, particularly for used volumetric methods, and are
determining water hardness. Soon, recommended in many international
in addition to calcium and magne- stand­ards and directives.
sium, other metal ions could also
Theoretical fundamentals

The term complex refers to species com-

posed of individual ions or molecules
The effective complex formation con-
stants are generally lowered in the pres-
07
±z
with the formula [MLn] . ence of protons (acids) because these
compete with the metal ions in the reac-
The coordination number specifies how tion with the complexing agent, for
many monodentate ligands (or complex- example, by protonating the carboxyl
ing agents) are bound. Cations are usu- group(s).
ally present in aqueous solutions as aqua
2+
complexes with the formula [M(OH2)4] As a general rule:
2+
or [M(OH2)6] . • Complex formation constant < 10;
2+ 2+
alkaline titration (e.g., Ca , Mg )
The term denticity refers to the number • Complex formation constant > 15;
3+ 2+
of coordination sites of the respective slightly acidic titration (e.g., Al , Pb )
3+ 3+
ligand. Complexes with multidentate (Fe and Bi can even be titrated at
ligands are known as chelates. pH = 2).

The stability of a complex is determined Titrations must be carried out in buffered

by thermodynamic and kinetic factors. A solutions because the complexation
measure of the thermodynamic stability is ­reaction always liberates protons. This is
the complex formation constant Kf or the illustrated briefly by the following exam-
dissociation constant K = 1/Kf. ples:

2+
The stability of metal complexes can be Ca + Na2H2EDTA + 2 H2O →
2– + +
described, for example, by the following [CaEDTA] + 2 Na + 2 H3O
simplified equation, which uses EDTA as
3+
ligand: Al + Na2H2EDTA + 2 H2O →
– + +
[AlEDTA] + 2 H3O + 2 Na
+ 2
MeEDTA 2- H 3O
Kf = 2+ 2-
Me H 2 EDTA Apart from a few exceptions, the chelat-
ing agents used for titration form 1:1
The complex formation constant is usu- complexes with metal ions, regardless of
ally given as log Kf in data tables. The whether the metal ions have a charge
stability of the complex increases with z = 2+ or z = 3+.
increasing magnitude of log Kf.
08 The following table contains a few selected complex formation constants (log Kf) for
common titrants and metal ions:
1 2 2 2 2
Metal ion EDTA EGTA DCTA DTPA NTA
Al(III) 16.4 13.9 18.6 18.4 9.5
Ba(II) 7.9 8.4 8.6 8.6 4.8
a
Bi(III) 27.8 23.8 31.2 29.7 –
Ca(II) 10.7 11.0 12.5 10.7 6.4
Cd(II) 16.5 16.7 19.2 19.3 9.5
Co(II) 16.5 12.5 18.9 18.4 10.4
Co(III) 41.4 – – – –
a
Cr(II) 13.6 – – – –
a
Cr(III) 23.4 2.5 – – > 10.0
Cu(II) 18.8 17.8 21.3 21.5 13.0
Fe(II) 14.3 11.9 16.3 16.6 8.8
Fe(III) 25.1 20.5 28.1 28.6 15.9
Ga(III) 21.7 – 22.9 23.0 13.6
Hf(IV) 29.5 – – 35.4 20.3
Hg(II) 21.5 23.1 24.3 27.0 14.6
In(III) 24.9 – 28.8 29.0 16.9
Mg(II) 8.8 5.2 10.3 9.3 5.5
Mn(II) 13.9 12.3 16.8 15.6 7.4
Ni(II) 18.4 13.6 19.4 20.3 11.5
Pb(II) 18.0 14.7 19.7 18.8 11.4
a
Pd(II) 25.6 – – – –
b
Sn(II) 18.3 23.9 – – –
Sr(II) 8.7 8.5 10.5 9.7 5.0
Th(IV) 23.2 – 29.3 28.8 12.4
Tl(I) 6.4 – 5.3 6.0 4.8
Tl(III) 35.3 – 38.3 48.0 18.0
Zn(II) 16.5 14.5 18.7 18.8 10.7
Zr(IV) 29.3 – 20.7 36.9 20.85

DCTA trans-Diaminocyclohexanetetraacetic acid

DTPA Diethylenetriaminepentaacetic acid
EDTA Ethylenediaminetetraacetic acid
EGTA Ethylene glycol bis-(2-aminoethyl)tetraacetic acid
NTA Nitrilotriacetic acid

The following conclusions can be drawn from the above table:

• Metal ions with a triple positive charge form stronger complexes than metal ions
2+ 3+
with a double positive charge (cf. Fe – Fe ).
• Ligands with a higher denticity form stronger complexes (cf. NTA – DTPA).
• The weakest complex is formed between Ba and NTA, and the strongest
3+
between Tl and DTPA.
1
If not otherwise indicated, the values are based on measurements at 25 °C and an ionic strength of 0.1 mol/L.
a
Values measured at 20 °C and an ionic strength of 0.1 mol/L.
b
Values measured at 20 °C and an ionic strength of 1 mol/L.
th
Harris, Daniel (2007): Quantitative Chemical Analysis. 7 ed., New York.
2
Values were taken from Dojindo Molecular Technologies (publisher) http://www.dojindo.com
(Issued 28.9.2015).
Indication of the equivalence point of
the titration
Visual or photometric
Visual indication with color indicators is The color indicators react with the ana-
09
the oldest method of determining the lyte metal ions to form a color complex
equivalence point of a titration, and it is whose color suddenly changes when all
still frequently used. It is inexpensive and the metal ions have been (re)complexed
requires little equipment. The particular or titrated by the titrant.
drawback of this method is that it can-
not be automated and is difficult to vali- Photometric titration is carried out with
date. The color sensitivity of individuals fiber-optic sensors. These comprise a
differs, and also depends on the lighting light source, two glass fiber (optical)
conditions. Furthermore, the endpoint is conductors, and an amplifier.
even more difficult to observe in colored Monochromatic light exits the fiber-
and/or turbid solutions. optic conductor and enters the solution
where its color is partially absorbed.
The endpoint detection can be improved Depending on the design of the photo-
by the use of photometric indication. In metric sensor, the optical signal is sent
this case, the subjective human eye is to a photodiode directly or via a concave
replaced by an objective sensor. This mirror and a second fiber-optic conduc-
kind of indication can be automated and tor. This generates a voltage signal in the
validated – provided that the correct amplifier that is sent to the titrator via its
color indicator is chosen and the solu- electrode input.
tions are not too turbid before or during
the titration. During photometric titrations, attention
should be paid to the fact that air bub-
Color indicators do not have a precise bles in the sample solution may have an
color change point – rather, they have a unfavorable effect on the shape of the
color change range. This has a consider- titration curve, and may also influence
able influence on the accuracy of the the results, leading to spikes or equiva-
results of titrations where visual indica- lence point artifacts.
tion of the equivalence point is
employed. As a general rule: the human
eye can perceive a color change when
the concentration ratio changes from
roughly 1/10 to 10/1. It is thus expedient
to select color indicators that have a
sharp color change with very different
colors.
10 The following procedure generally applies:
• Stirring is adjusted so that the solution
If a suitable measuring setup is used, the
potential U measured between the two
is thoroughly mixed, but no air bub- electrodes depends only on the measur-
bles are entrained. ing solution, or to be more precise, on
• The solution is degassed under vacu- the activity ai of the measuring ion, since
um or in an ultrasonic bath before the only dissociated ions are measured. In
analysis. If necessary, the sample solu- case of ISE measurements, this relation-
tion is diluted with dist. H2O and pre- ship is described by the Nernst equation:
neutralized.
2.303 R T
Potentiometric U = U0 + log ai = U 0 + U N log ai
z F
The measuring setup for potentiometric
measurements always consists of two U: Measured potential between
electrodes – an indicator electrode (meas­ measuring and reference elec-
uring electrode) and a reference elec- trodes
trode. These do not measure potentials U0: Standard potential of the
(also known as Galvanic potentials), but measuring chain (depends
potential differences (voltages). on its configuration)
2.303: Conversion factor from the
The indicator electrode (ion-selective elec- natural to the decadic logarithm
trode, ISE) provides an electrode potential R: Gas constant (8.31441 J/K/mol)
that depends on the composition of the T: Absolute temperature in Kelvin
measuring solution (specifically, the con- (273.15 + x °C)
centration of the measuring ion). z: Charge of the measuring ion,
including algebraic sign (e.g.,
2+
The reference electrode (usually Ag/AgCl) +2 for Ca )
provides an electrode signal (reference F: Faraday constant
potential) that is as independent as possi- (96484.56 C/mol)
ble from the measuring solution. ai: Activity of the measuring ion
UN: Nernst slope (e.g., 29.58 mV at
The potential is measured under almost 25 °C and z = +2)
zero-current conditions using a voltmeter
(e.g., the titrator) with a high-resistance
meas­ uring input. This is important
because it avoids voltage drops.
The Nernst slope UN is the theoretical
electrode slope. It corresponds to a
on the temperature of the meas­ uring
solution and on the charge z of the mea-
11
potential change induced by a change in suring ion. The following table illustrates
ai by one order of magnitude. It depends these dependencies:

Temperature / °C U / mV, z = +1 U / mV, z = +2

0 54.20 27.10
10 56.18 28.09
20 58.17 29.09
25 59.16 29.58
30 60.15 30.08
40 62.14 31.07
50 64.12 32.06

Ion-selective electrodes
As their name indicates, ion-selective This involves treating the measuring solu-
electrodes respond more or less selec- tion with an auxiliary complexing agent
tively to the ion for whose measurement (acetylacetone in TRIS buffer). If the mix-
they are designed. This suggests that a ture is then titrated with EDTA, Ca is com-
corresponding ISE is required for each plexed first. When there is no Ca left, the
measuring ion to be determined, which auxiliary complexing agent comes into
would make indication of the equiva- play. Mg reacts with CaEDTA to form
lence point using ion-selective electrodes MgEDTA. The corresponding quantity of
extremely unattrac­ tive. Furthermore, Ca is liberated and can then be titrated
such a concept would be much too with EDTA.
expensive and also difficult to imple-
ment with certain measuring ions. How The determination of sulfate exploits the
to manage with only one ion-selective cross-sensitivity of Ca ISE with respect to
electrode is explained in the chapter Ba ions. The sulfate is precipitated with
Cu-ISE. BaCl2, and the excess Ba is then back-
titrated with EDTA. In the presence of
a) Ca-ISE Ca, the titration has two equivalence
The Ca-ISE is a polymer membrane elec- points. The first equivalence point cor-
trode and, as its name indicates, it is par- responds to that of Ca and the second
ticularly responsive to Ca ions. It is there- to that of Ba.
fore mainly used in the titration of calci-
um. However, there is a trick that allows More details of these two strategies are
simultaneous titration of Ca and Mg (e.g., given in the practical examples (determi-
to determine the water hardness). nation of water hardness and of sulfate).
12 b) Cu-ISE
The Cu-ISE is a crystal membrane elec- Additional complexing agents were
trode. In theory, it responds only to Cu developed for special purposes (e.g.,
ions. However, once again a trick allows better selectivity, higher complex forma-
it to be used not only for titrating Cu tion constants, better separation of mix-
ions. To do this, a small amount of tures); however, most of them are rela-
CuEDTA is added to the sample solution. tively expensive.
CuEDTA is a very stable complex, and
liberates only a very small fraction of the Commercially available complexing
Cu(II) ions. However, in alkaline solutions agents include:
and in the presence of Ni(II) ions, for
example, all Cu(II) ions are liberated from NTA
the complex, and the NiEDTA complex • Nitrilotriacetic acid C6H9NO6;
forms instead. If the mixture is then MR = 191.14 g/mol
titrated with EDTA, the concentration of • Nitrilotriacetic acid trisodium salt
the Cu(II) ions decreases continuously monohydrate C6H6NNa3O6∙H2O;
until it reaches its very small initial value MR = 275.12 g/mol
at the equivalence point. The following EDTA
equations illustrate the three steps: • Ethylenediaminetetraacetic acid
C10H16N2O8; MR = 292.25 g/mol
CuEDTA → Cu(II) + EDTA • Ethylenediaminetetraacetic acid
CuEDTA + Ni(II) → NiEDTA + Cu(II) disodium salt dihydrate
Cu(II) + EDTA → CuEDTA C10H14N2Na2O8∙2H2O;
MR = 372.24 g/mol
Commonly used complexing EGTA
agents/titrants • Ethylene glycol-bis-(2-aminoethyl)tet-
The first complexing agent used for titra- raacetic acid C14H24N2O10;
tions was NTA or its trisodium salt. NTA MR = 380.35 g/mol
is cheap, but it has the disadvantage DCTA
that its complex formation constants are • trans-1,2-Diaminocyclohexanetetraacetic
relatively small. It was therefore soon acid monohydrate C14H22N2O6∙H2O;
replaced by EDTA, which is still the most MR = 364.36 g/mol
common agent used today, and is the DTPA
specified titrant in many national and • Diethylenetriaminepentaacetic acid
international standards. C14H23N3O10; MR = 393.35 g/mol
Buffer solutions
As already mentioned in the section on b) Acidic buffer solutions
13
theoretical fundamentals, two protons The most commonly used solution in
are liberated per metal ion during com- this case is the acetic acid/ammonium
plexation. The sample solution must be acetate buffer: a mixture of 1.4 mol/L
buffered to prevent the formation of CH3COOH and 1.5 mol/L NH4CH3COO
metal complexes being hindered at has a pH value of approx. 4.7. Buffer
lower pH. This is particularly important solutions can be prepared in the pH
for metal ions that must be titrated in range between 4 and 5, mainly by vary-
alkaline solutions. ing the amount of ­acetic acid.

2+
Ca + Na2H2EDTA + 2 H2O → Highly acidic buffer solutions (pH 2–3)
+
CaNa2EDTA + 2 H3O are prepared by adding HCl to 0.5 mol/L
glycine.
a) Alkaline buffer solutions
The most commonly buffer is probably a For all buffer solutions, it is important
mixture of ammonia and ammonium that their constituents do not form a
chloride – its pH value is approx. 10. stronger complex with the analyte metal
ion than does the titrant.
The solution normally contains
5–8 mol/L NH3 and 1 mol/L NH4Cl.

In special cases, the following alterna-

tives can be used:
• 1 mol/L each of NaOH and H3BO3
• 0.2 mol/L tris(hydroxymethyl)amino-
methane (TRIS)
• 1 mol/L triethanolamine, adjusted to
pH 8 with HCl
14 Masking
Masking agents can be added to the second titration is then carried out at
sample solution to prevent interfering pH = 12. Magnesium is precipitated as
metal ions from reacting with the titrant. Mg(OH)2 and can thus no longer inter-
These form stronger complexes or bonds fere in the titration – only the calcium is
with the interfering ions than does the determined. However, the results for
titrant. In this case, it is important that calcium are generally too low because
the metal ion being determined is not some of it adsorbs onto the precipitate.
masked itself. This is a general problem in precipitation
masking. A further disadvantage of this
a) Masking by precipitation method is that the color indicator is
Masking by precipitation means that the often adsorbed, or its color change is
interfering metal ions are precipitated more difficult to detect.
from the solution; however, in contrast
to a physical separation, the precipitates b) Masking by complexation
are left in the solution and are not The masking agent used for masking by
removed by filtration. complexation must be a selective com-
plexing agent that binds the analyte
This method was used at an early stage metal ion as weakly as possible and the
in the photometric determination of interfering ion as strongly as possible.
water hardness. The sum of calcium and
magnesium (total hardness) is deter-
mined in a first titration at pH = 10. The

A small selection of commonly used masking agents

Masking agent Element
Ammonium fluoride Al, Ti, Be, Ca, Mg, Sr, Ba
Potassium cyanide Zn, Cd, Hg, Cu, Ag, Ni, Co
Acetylacetone Fe, Al, Pd, UO2
Tiron (dihydroxybenzenedisulfonic acid) Al, Fe, Ti
Triethanolamine Fe, Al
2,3-Dimercaptopropanol (BAL) Zn, Cd, Hg, As, Sb, Sn, Pb, Bi
Color indicators
A large number of color indicators have can be used for most complexometric
15
already been described, and all have titrations. A small overview of such
advantages and disadvantages. Some of metallochromic indicators is given below:
them have become well established and

Color with Color with-

Indicator Element
metal ion out metal ion
3+ 2+ 2+ 3+ 2+ 2+
Pyrocatechol violet Bi , Cd , Co , In , Mn , Zn blue yellow
2+
Dithizone Zn red green-violet
2+ 2+ 2+ 2+ 2+ 2+
Eriochrome Black T Ca , Cd , Hg , Mg , Pb , Zn red blue
2+
Ca in the presence of
Calconcarboxylic acid 2+ red blue
­significant Mg
Hydroxynaphthol 2+ 2+
Ca , Mg red blue
blue
2+ 2+ 2+
Murexide Co , Cu , Ni yellow violet
2+ 2+ 2+
PAN Cd , Cu , Zn red yellow
2+ 2+ 2+
Phthalein purple Ba , Ca , Sr purple colorless
3+ 2–
Tiron Fe , SO4 blue yellow
3+ 3+ 3+ 3+ 4+ 4+
Xylenol orange Al , Bi , La , Sc , Th , Zr red yellow

Most metallochromic indicators are s­ tabilized aqueous solutions. The shelf life
unstable in solution. They are thus often of the resulting indicator solution must be
added in a solid form (as tablets or tritura- determined on a case-by-case basis.
tions with NaCl) to the solution being
titrated. This circumstance, however, The visible spectra of some common
makes it poorly suited or even unsuitable indicators are shown below.
for automation purposes. This can be
overcome by preparing alcoholic or
16 a) Pyrocatechol violet
Pyrocatecholsulfonephthalein; C19H14O7S
0.1% in water

Figure 1 Overlaid Vis spectra of complexed Figure 2 Vis absorption difference spectrum
and uncomplexed pyrocatechol violet of complexed and uncomplexed pyro-
catechol violet

b) Dithizone
1,5-Diphenylthiocarbazone; C13H12N4S
Approx. 30 mg in 100 mL ethanol (shelf life of 1 month in a refrigerator)

Figure 3 Overlaid Vis spectra of complexed Figure 4 Vis absorption difference spectrum
and uncomplexed dithizone of complexed and uncomplexed dithizone
c) Eriochrome Black T
1-(1-Hydroxy-2-naphthylazo)-6-nitro-2-naphthol-4-sulfonic acid sodium salt;
17
C20H12N3NaO7S
1% triturated in NaCl or 100 mg in 100 mL ethanol or 100 mg in 100 mL water
and stabilized with 100 mg ascorbic acid

Figure 5 Overlaid Vis spectra of complexed Figure 6 Vis absorption difference spectrum
and uncomplexed Eriochrome Black T of complexed and uncomplexed Eriochrome
Black T

d) Calconcarboxylic acid (HHSNN)

2-Hydroxy-1-(2-hydroxy-4-sulfo-1-naphthylazo)-3-naphthoic acid; C21H14N2O7S
1% triturated in NaCl or 50 mg in 100 mL c(NaOH) = 0.1 mol/L (shelf life of one day)

Figure 7 Overlaid Vis spectra of complexed Figure 8 Vis absorption difference spectrum
and uncomplexed calconcarboxylic acid of complexed and uncomplexed calconcar-
boxylic acid
18 e) Hydroxynaphthol blue
2,2'-Dihydroxy-1,1'-azonaphthalene-3',4,6'-trisulfonic acid trisodium salt;
C20H11N2Na3O11S3
10% triturated in NaCl

Figure 9 Overlaid Vis spectra of complexed Figure 10 Vis absorption difference

and uncomplexed hydroxynaphthol blue spectrum of complexed and uncomplexed
hydroxynaphthol blue

f) Methylthymol blue
3,3’-Bis[N,N-di(carboxymethyl)aminomethyl]thymolsulfonephthalein tetrasodium
salt; C37H40N2Na4O13S
100 mg in 100 mL ethanol

Figure 11 Overlaid Vis spectra of complexed Figure 12 Vis absorption difference

and uncomplexed methylthymol blue spectrum of complexed and uncomplexed
methylthymol blue
g) Murexide
Ammonium purpurate; C8H8N6O6
19
1% triturated in NaCl or 50 mg in 100 mL dist. H2O

Figure 13 Overlaid Vis spectra of complexed Figure 14 Vis absorption difference

and uncomplexed murexide spectrum of complexed and uncomplexed
murexide

h) PAN
1-(2-Pyridylazo)-2-naphthol; C15H11NO3
100 mg in 100 mL ethanol

Figure 15 Overlaid Vis spectra of complexed Figure 16 Vis absorption difference spec-
and uncomplexed PAN trum of complexed and uncomplexed PAN
20 i) Phthalein purple
3,3’-Bis[bis-(carboxymethyl)-aminomethyl]-cresolphthalein; C32H32N2O12∙H2O
100 g in 100 mL dist. H2O containing 1 mL w/w(NH3) = 25% (not stable)

Figure 17 Overlaid Vis spectra of complexed Figure 18 Vis absorption difference

and uncomplexed phthalein purple spectrum of complexed and uncomplexed
phthalein purple

j) Tiron
Pyrocatechol-3,5-disulfonic acid disodium salt; C6H4Na2O2S2
Added as a solid or 2% in dist. H2O

Figure 19 Overlaid Vis spectra of complexed Figure 20 Vis absorption difference spec-
and uncomplexed Tiron trum of complexed and uncomplexed Tiron
k) Xylenol orange
3,3’-Bis[N,N-bis(carboxymethyl)aminomethyl]-cresolsulfonephthalein tetrasodium salt;
21
C31H28N2Na4O13S
100 mg are dissolved in 100 mL deion. H2O

Figure 21 Overlaid Vis spectra of complexed Figure 22 Vis absorption difference spec-
and uncomplexed xylenol orange trum of complexed and uncomplexed xylenol
orange

l) Eriochrome Cyanine R
3,3'-(1,1-Dioxido-3H-2,1-benzoxathiol-3-ylidene)bis[6-hydroxy-5-methylbenzoic acid]
trisodium salt; C23H15Na3O9S
Dissolve 40 mg in 100 mL dist. H2O

Figure 23 Overlaid Vis spectra of complexed Figure 24 Vis absorption difference

and uncomplexed Eriochrome Cyanine R spectrum of complexed and uncomplexed
Eriochrome Cyanine R
22 Preparation of standard solutions
Many standard solutions are commer-
c(CuSO4) = 0.1 mol/L
Dissolve 25.2 g CuSO4∙5 H2O (99%) in
cially available as ready-to-use products approx. 500 mL dist. H2O. Add 0.5 mL
– and these should be given precedence. w/w(H2SO4) = 96% and then make up to
The manufacturer has adjusted their titer 1 L with dist. H2O and mix.
to 1.0000 at 20 °C.
c(ZnSO4) = 0.1 mol/L
a) Direct titration Dissolve 28.9 g ZnSO4∙7 H2O (99.5%) in
Most complexing agents are available in approx. 500 mL dist. H2O. Add 0.5 mL
a pure form as an acid. These have very w/w(H2SO4) = 96% and then make up to
poor solubility in water and must be 1 L with dist. H2O and mix.
converted into their soluble di- or
­trisodium salts during preparation. The Titer determinations
substance concentration c is usually
­ Calcium carbonate is the primary standard
0.1 mol/L. The solutions have a stable for complexing agents (CA in the follow-
titer. ing). CaCO3 is dried overnight in a drying
oven at ­140 °C and then left to cool in a
The preparation of c(Na2EDTA) = 0.1 mol/L desiccator for at least 2 h.
is described as an example:
The titer is usually determined in tripli-
Weigh 29.5 g EDTA (C10H16N2O8) into a cate, and the mean value is used as titer.
glass beaker and, while stirring, slurry in
approx. 300 mL dist. H2O. Add Titer determination for direct
c(NaOH) = 5 mol/L until everything has titration:
dissolved. Allow to cool, mix, and make Weigh approx. 100 mg CaCO3 with an
up to 1 L with dist. H2O. accuracy of 0.1 mg into a titration
­beaker and add 20 mL dist. H2O. Add
b) Back titration c(HCl) = 3 mol/L while stirring until the
2+ 2+
Cu or Zn solutions are usually used for CaCO3 has completely dissolved. Add
back titrations. These solutions also have approx. 80 mL dist. H2O and 10 mL
a stable titer and are generally prepared ammoniacal buffer solution, and titrate
with a concentration of c(Me) = 0.1 mol/L. with c(CA) = 0.1 mol/L.
Calculation
mS
Examples: Titer determination of
EDTA and EGTA with CaCO3
23
Titer =
VEP1 c KB MCaCO 3

mS: Weight of CaCO3 in mg

VEP1: Volume of CA consumed up to
the first equivalence point in mL
cCA: Concentration of the complexing
agent in mol/L
MCaCO3: Molecular mass of calcium
­carbonate; 100.09 g/mol

Titer determination for back

titration: Figure 25 Titration curve of the potentio-
To a titration beaker, add approx. 50 mL metric titer determination of EDTA with the
dist. H2O, 10 mL c(CA) = 0.1 mol/L, and Ca-ISE
10 mL buffer solution (alkaline or acidic).
2+
Then titrate with c(Cu ) = 0.1 mol/L or
2+
c(Zn ) = 0.1 mol/L.

Calculation
VS fKB
Titer =
VEP1

VS: Added volume of c(CA) = 0.1

mol/L in mL
fCA: Titer of the CA solution
2+ 2+
VEP1: Volume of Cu or Zn solution
consumed up to the first equiv- Figure 26 Titration curve of the potentio-
alence point in mL metric titer determination of EGTA with the
Ca-ISE
 Practical examples
Water hardness, calcium, and magnesium
24 General
Hardness constituents in water are usually Water hardness is given in mmol/L.
calcium and magnesium ions. They are Terms such as "soft", "hard", "°dH",
mainly present as hydrogen carbonates "°fH" etc. are also used for information
and sulfates or, in rare cases, as chlorides. purposes, for example, on detergent
Barium and strontium, which are also packaging. The relationships are shown
determined in the total hardness deter- in the following table:
mination, are present only in very small
quantities, if at all, and thus do not
2+
interfere (0.1 mg/L Ba would consume
only 0.7 µL c(Na2EDTA) = 0.1 mol/L for a
sample size of 100 mL).

mg/L
mmol/L °fH °dH °USH Hardness
CaCO3
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
moderately
1.5–2.5 150–250 15–25 8.4–14.0 8.07–9.50
hard
2.5–3.2 250–320 25–32 14.0–17.92 9.50–17.22 fairly hard
3.2–4.2 320–420 32–42 17.92–23.5 17.22–22.6 hard
> 4.2 > 420 > 42 > 23.5 > 22.6 very hard

Conversion factors
mmol/L × 100 → mg/L CaCO3 leads to errors in all titrimetric methods.
mmol/L × 10 → °fH (French degree In such cases, the recommendation is to
of hardness) use a buffer solution with an accurately
2+
mmol/L × 5.6 → °dH (German degree added amount of Mg standard (e.g.,
2+
of hardness) 2.4305 mg Mg , which corresponds to
mmol/L × 5.38 → °USH (US degree of 1 mL c(Na2EDTA) = 0.1 mol/L) and then
hardness) to subtract this value during the calcula-
tion.
If the water being investigated has an
2+ 2+
unfavorable Ca /Mg ratio (small amount In the case of soft water, the best method
2+ 2+
of Mg and a large amount of Ca ), this is to titrate with c(Na2EDTA) = 0.05 mol/L.
 Potentiometric titration with the
Ca ISE
25
Reagents
• Titrant: c(Na2EDTA) = 0.1 mol/L in Calcium hardness: Calcium content in
c(KOH) = 0.1 mol/L mmol/L
• Auxiliary complex solution: weigh Magnesium hardn.: Magnesium content
24.3 g tris(hydroxymethyl)amino- in mmol/L
methane (TRIS) into a 1 L volumetric Total hardness: Total hardness in
flask and dissolve in approx. 500 mL mmol/L
dist. H2O. Add 10 mL acetylacetone, Calcium content: Calcium content in
mix, and make up to the mark with mg/L
dist. H2O. Allow the solution to stand Magnesium cont.: Magnesium content
for 24 h before use (max. shelf life is in mg/L
1 week).
VEP1: Volume of EDTA consumed up to
Analyses the first equivalence point in mL
Measure a 100 mL water sample into a VEP2: Volume of EDTA consumed up to
titration beaker and add 15 mL auxiliary the second equival. point in mL
complex solution. Using the "DET U" cEDTA: Concentration of EDTA in mol/L
mode, titrate with c(Na2EDTA) = 0.1 mol/L f: Titer of the EDTA solution
past the second equivalence point (EP2). 1000: Conversion factor
2+
EP1 corresponds to Ca and the differ- VS: Sample size in mL
2+
ence EP2 – EP1 corresponds to Mg . MCa: Molar mass of calcium;
40.078 g/mol
MMg: Molar mass of magnesium;
Calculation 24.305 g/mol
VEP1 c EDTA f 1000
Calcium hardness =
VS

(VEP2 - VEP1) c EDTA f 1000

Magnesium hardness =
VS

VEP2 c EDTA f 1000

Total hardness =
VS

VEP1 c EDTA f 1000 MCa

Calcium content =
VS
Figure 27 Titration curve of tap water from
(VEP2 - VEP1 ) c EDTA f 1000 MMg
Magnesium cont. = Herisau (Switzerland), measured with the
VS Ca-ISE
26 Further literature on this topic can
be accessed using the Application
because it would give inaccurate results).
Since only the largest equivalence point
Finder under is required, select "largest" as the EP
www.metrohm.com/applications criterion so that only one EP is shown.
• Application Bulletin AB-125 –
Simultaneous determination of calcium, Calcium (hardness)
magnesium, and alkalinity by com- Measure a 100 mL water sample into a
plexometric titration with potentio- titration beaker and add 5 mL buffer solu-
metric or photometric indication in tion. Add 0.5 mL CuEGTA, wait for 20 s
water and beverage samples while stirring, and titrate in the "MET U"
mode with c(Na2EGTA) = 0.1 mol/L past
Potentiometric with the Cu ISE the first equivalence point.
Reagents
• Titrant 1: c(Na2EDTA) = 0.1 mol/L Magnesium (hardness)
• Titrant 2: c(Na2EGTA) = 0.1 mol/L This is calculated by subtracting the cal-
• Buffer solution: dissolve 54 g NH4Cl cium hardness from the total hardness.
and 350 mL w/w(NH3) = 25% in dist.
H2O, mix, and make up to 1 L with Calculation
dist. H2O.
VEP1.1 c EDTA fEDTA 1000
• Cu complex solution: c[Cu(NH4)2EDTA] Total hardness =
VS
= 0.1 mol/L (e.g., Merck No. 105217)
• CuEGTA: dissolve 2.497 g CuSO4 ∙ VEP1.2 c EGTA fEGTA 1000
5 H2O in dist. H2O, make up to 100 Calcium hardn. =
VS
mL and mix well. Add 25.0 mL of this
solution to 25.0 mL c(Na2EGTA) = 0.1 Magnesium hardn. = total hardness -
mol/L. calcium hardness

Analysis Total hardness: Total hardness in

2+ 2+
Total hardness (sum of Ca & Mg ) mmol/L
Measure a 100 mL water sample into a Calcium hardness: Calcium content in
titration beaker and add 5 mL buffer mmol/L
solution. Add 0.5 mL Cu complex Magnesium hardn.: Magnesium content
­solution, wait for 20 s while stirring, and in mmol/L
titrate in the "MET U" mode with
VEP1.1: Volume of EDTA consumed up to
c(Na2EDTA) = 0.1 mol/L. There may be
the largest equivalence point of
two equivalence points, whereby EP2
2+ 2+ the total hardness titration in mL
corresponds to the sum Ca + Mg (EP1
cEDTA: Concentration of EDTA in mol/L
cannot be used for the calculations
fEDTA: Titer of the EDTA solution
1000: Conversion factor
VS: Sample size in mL
Further literature on this topic is
given in
27
VEP1.2: Volume of EGTA consumed up • Application Bulletin AB-101 –
to the first equivalence point of Complexometric titrations with the
the calcium hardness titration in Cu-ISE
mL • Titration Application Note AN-T-131
cEGTA: Concentration of EGTA in mol/L – Automatic determination of calci-
fEGTA: Titer of the EGTA solution um, magnesium, and total hardness
in water with the Cu-ISE

Examples: Titration curves of Herisau tap water with the Cu ISE

Figure 28 Titration curve of the total Figure 29 Titration curve of the calcium
hardness determination hardness determination

Photometric with the Optrode

at 610 nm
Reagents
• Titrant: c(Na2EDTA) = 0.1 mol/L • Na2MgEDTA∙H2O
• Buffer solution: Dissolve 54 g NH4Cl • Indicator Solution 1: Eriochrome
in dist. water and add 350 mL Black T; dissolve 100 mg Eriochrome
w/w(NH3) = 25%. Mix the solution Black T in 100 mL ethanol.
and make up to 1 L with dist. water. • Indicator Solution 2: HHSNN; dissolve
• Sodium hydroxide: c(NaOH) = 50 mg HHSNN in 100 mL c(NaOH) =
2 mol/L 0.1 mol/L.
28 General remarks
There are a few special requirements c(Na2EDTA) = 0.1 mol/L in the "MET U"
that must be taken into account when mode up to the color change.
carrying out photometric titration with
optical sensors: Magnesium (hardness)
• No interfering gas bubbles should be This is calculated by subtracting the cal-
present in the light path. For this rea- cium hardness from the total hardness.
son, we recommend degassing the
water samples before adding the buf- Calculation
fer and adjusting the stirrer speed so V EP1.1 c EDTA f 1000
that no gas bubbles are entrained. Total hardness =
VS
• During determination of the calcium
hardness, precipitation of magnesium V EP1.2 c EDTA f 1000
Calcium hardn. =
hydroxide leads to ever increasing VS
turbidity. The mixture must therefore
be titrated immediately after adding Magnesium hardn. = total hardness –
NaOH and preferably with a start vol- calcium hardness
ume. Although the resulting titration
curves are not very smooth and look Total hardness: Total hardness in
unattractive, this does not affect the mmol/L
accuracy of the results. Calcium hardness: Calcium content in
mmol/L
Analysis Magnesium hardn.: Magnesium content
2+ 2+
Total hardness (sum of Ca & Mg ) in mmol/L
Measure a 100 mL water sample into a
titration beaker, add 0.1 g Na2MgEDTA∙ VEP1.1: Volume of EDTA consumed up
H2O, 10 mL buffer solution, and 0.25 mL to the first equivalence point of
Indicator Solution 1, and titrate with the total hardness titration in
c(Na2EDTA) = 0.1 mol/L in the "MET U" mL
mode past the color change. cEDTA: Concentration of EDTA in mol/L
f: Titer of the EDTA solution
Calcium (hardness) 1000: Conversion factor
Measure a 100 mL water sample into VS: Sample size in mL
the titration beaker, add 2 mL c(NaOH) = VEP1.2: Volume of EDTA consumed up
2 mol/L (pH > 12) and 1.5 mL Indicator to the first equivalence point of
Solution 2, and titrate immediately with the calcium hardness titration in
mL
Examples: Photometric titration curves of Herisau tap water
29

Figure 30 Titration curve of the total hardness Figure 31 Titration curve of the calcium hard­
determination with the Optrode at 610 nm ness determination with the Optrode at 610 nm

Further literature on this topic is given in

• Application Bulletin AB-125 – Simultaneous determination of calcium,
magnesium, and alkalinity by complexometric titration with potentiometric or
photometric indication in water and beverage samples
• Titration Application Note AN-T-084 – Fully automatic determination of the total,
calcium and magnesium hardness of water samples using photometric titration

Aluminum and magnesium,

alloys and antacids
Potentiometric with the Cu ISE
Reagents
• Titrant 1: c(DCTA) = 0.1 mol/L; dis- Add 0.5 mL w/w(H2SO4) = 96%, mix,
solve 36.463 g trans-1,2-diaminocy- and make up to 1 L with dist. H2O.
clohexanetetraacetic acid monohy- • Buffer solution pH = 4.7: Dissolve
drate in 400 mL c(NaOH) = 0.5 mol/L. 123 g sodium acetate in approx. 200
Allow to cool, then mix and make up mL dist. H2O and add 86 mL glacial
to 1 L with dist. H2O. acetic acid. Mix and make up to 1 L
• Titrant 2: c(CuSO4) = 0.1 mol/L; with dist. H2O.
dissolve 24.968 g CuSO4∙5H2O in • Ammonia solution: w/w(NH3) = 10%
approx. 500 mL dist. H2O. • Sodium hydroxide: c(NaOH) =
2 mol/L
30 Sample preparation
Preneutralize the acidic sample solution, c(CuSO4) = 0.1 mol/L past the first equiva-
which should not contain more than lence point → aluminum content. Store
3+ 2+
12 mg Al and/or 20 mg Mg , with the value of the excess titrant of Titrant 2
c(NaOH) = 2 mol/L to pH 2–3, and then as a "common variable".
dilute with dist. H2O to approx. 50 mL.
To the completely titrated sample solu-
Analysis tion, add 20 mL ammonia solution and a
To the prepared sample solution, add 5 mL further 6 mL c(DCTA) = 0.1 mol/L. Next,
buffer solution pH 4.7 and 6 mL c(DCTA) = titrate with c(CuSO4) = 0.1 mol/L past
0.1 mol/L. Allow the mixture to react for 1 the first equivalence point → magne-
min while stirring. Next, titrate with sium content.

Calculation
(VDCTA f1 c DCTA - VEP1.1 f2 c CuSO 4 ) MAl
Al =
VS

VEx = VEnd - VEP1.1

(VDCTA f1 c DCTA - (VEP1.2 + VEx ) f2 c CuSO 4 ) MMg

Mg =
VS

βAl: Aluminum content of the sample f1: Titer of the DCTA standard solution
in g/L f2: Titer of the CuSO4 standard
βMg: Magnesium content of the sam- solution
ple in g/L cDCTA: Concentration of the DCTA
VDCTA: Added quantity of DCTA standard solution in mol/L
standard solution in mL cCuSO4: Concentration of the CuSO4
VEP1.1: Volume of CuSO4 standard solu- standard solution in mol/L
tion consumed up to the first MAl: Molar mass of aluminum;
equivalence point of the 26.982 g/mol
aluminum titration in mL MMg: Molar mass of magnesium;
VEP1.2: Volume of CuSO4 standard solu- 24.305 g/mol
tion consumed up to the first VS: Sample size in mL
equivalence point of the magne-
sium titration in mL Remarks
VEx: Excess quantity of titrant after The surface of the Cu ISE must be pol-
the aluminum titration in mL ished occasionally with aluminum oxide
VEnd: End volume of the aluminum power (e.g., polishing set 6.2802.000).
titration in mL
 31
3+ 2+
Example: Al and Mg in aqueous solution

Figure 32 Titration curve of the potentiomet- Figure 33 Titration curve of the potentiomet-
ric aluminum determination with the Cu-ISE ric magnesium determination with the Cu-ISE

Further literature on this topic is given in

• Application Bulletin AB-181 – Automated potentiometric titration of aluminum
and magnesium in the same solution
• Titration Application Note No. AN-T-117 – Automatic determination of alumi-
num and magnesium mixtures with ion-selective copper electrode (Cu-ISE)

Magnesium and zinc

Potentiometric with the Cu ISE

Reagents
• Titrant 1: c(Na2EDTA) = 0.1 mol/L cial acetic acid. Mix and make up to
• Titrant 2: c(CuSO4) = 0.1 mol/L; 1 L with dist. H2O.
dissolve 24.968 g CuSO4∙5 H2O in • Ammonia buffer, pH = 10: Dissolve
approx. 500 mL dist. H2O. Add 54 g NH4Cl in approx. 500 mL dist.
0.5 mL w/w(H2SO4) = 96%, mix, and H2O and add 350 mL w/w(NH3) =
make up to 1 L with dist. H2O. 25%. Mix and make up to 1 L with
• Acetate buffer, pH = 4.7: Dissolve dist. H2O.
123 g sodium acetate in approx. • Sodium hydroxide: c(NaOH) =
500 mL dist. H2O and add 86 mL gla- 1 mol/L
32 Sample preparation
If necessary, dilute the sample solution, lence point → zinc content. Store the
which should not contain more than value of the excess titrant of Titrant 2 as
2+ 2+
50 mg Zn and/or 20 mg Mg , with dist. a "common variable".
H2O to approx. 50 mL and adjust to pH
4–4.5 with c(NaOH) = 1 mol/L. To the completely titrated sample solu-
tion, add 10 mL ammonia buffer and a
Analysis further 10 mL c(DCTA) = 0.1 mol/L. Next,
To the prepared sample solution, add titrate with c(CuSO4) = 0.1 mol/L past
5 mL acetate buffer and 10 mL c(DCTA) = the first equivalence point → magne-
0.1 mol/L, and allow the mixture to react sium content.
for 1 min while stirring. Next, titrate with
c(CuSO4) = 0.1 mol/L past the first equiva-

Calculation
(VDCTA f1 c DCTA - VEP1.1 f2 c CuSO 4 ) MZn
Zn =
VS

VEx = VEnd - VEP1.1

(VDCTA f1 c DCTA - (VEP1.2 + VEx ) f2 c CuSO 4 ) MMg

Mg = VS

βZn: Zinc content of the sample in g/L f1: Titer of the DCTA standard solution
βMg: Magnesium content of the sample f2: Titer of the CuSO4 standard solution
in g/L cDCTA: Concentration of the DCTA
VDCTA: Added quantity of DCTA standard standard solution in mol/L
solution in mL cCuSO4: Concentration of the CuSO4
VEP1.1: Volume of CuSO4 standard solution standard solution in mol/L
consumed up to the first equiva- MZn: Molar mass of zinc;
lence point of the zinc titration in 65.409 g/mol
mL MMg: Molar mass of magnesium;
VEP1.2: Volume of CuSO4 standard solution 24.305 g/mol
consumed up to the first equiva- VS: Sample size in mL
lence point of the magnesium titra-
tion in mL Remarks
VEx: Excess quantity of titrant after the The surface of the Cu-ISE must be polished
zinc titration in mL occasionally with aluminum oxide power
VEnd: End volume of the zinc titration (e.g., polishing set 6.2802.000).
in mL
 33
2+ 2+
Example: Zn and Mg in aqueous solution

Figure 34 Titration curve of the potentio- Figure 35 Titration curve of the potentio-
metric zinc determination with the Cu-ISE metric magnesium determination with the
Cu-ISE

Further literature on this topic is given in

• Titration Application Note AN-T-118 – Automatic determination of zinc and
magnesium mixtures with ion-selective copper electrode (Cu-ISE)

Aluminum, calcium, iron, and

magnesium in cement and clinker
Photometric with the Optrode at
610 nm
Reagents
3+
• Hydrochloric acid: w/w(HCl) = 36% • Titrant 2 for Fe : c(Na2EDTA) =
• Nitric acid: w/w(HNO3) = approx. 65% 0.025 mol/L
3+
• Sodium hydroxide: w/w(NaOH) > 99% • Titrant 3 for Al : c(Bi(NO3)3) =
• Ammonia: w/w(NH3) = 25% 0.05 mol/L; dissolve 24.25 g
• Ammonium chloride: NH4Cl p.a. Bi(NO3)3∙5H2O in approx. 500 mL
2+ 2+
• Titrant 1 for Ca and Mg : HNO3 (2 mol/L) and transfer into a 1 L
c(Na2EDTA) = 0.1 mol/L volumetric flask. Next, make up to 1 L
with dist. H2O.
34
3+
• Ammonia: c(NH3) = 2 mol/L; add • Indicator solution for Al , xylenol
144 mL w/w(NH3) = 25% to a 1 L orange: dissolve 100 mg xylenol
volumetric flask and make up to the orange disodium salt in 100 mL dist.
mark with dist. H2O. H2O.
• Sodium hydroxide: c(NaOH) = 2 mol/L;
dissolve 80 g NaOH in approx. Sample preparation
600 mL dist. H2O, transfer into a 1 L Mix approx. 4 g cement with 4 g NH4Cl,
volumetric flask, and make up to the add 48 mL c(HCl) = 6 mol/L and 3 mL
mark with dist. H2O. c(HNO3) = 2 mol/L. Heat the mixture and
• Hydrochloric acid: c(HCl) = 6 mol/L; boil for a while. Stir the mixture with a
add 590 mL w/w(HCl) = 37% to a 1 L magnetic stirrer for approx. 60 min. Take
volumetric flask that already contains up the mixture in 50 mL hot dist. H2O
approx. 200 mL dist. H2O. After the and filter it through a black band filter
solution has cooled, make up to the into a 500 mL volumetric flask. Rinse the
mark with dist. H2O. filter thoroughly with hot dist. H2O.
• Nitric acid: c(HNO3) = 2 mol/L; Allow to cool, then mix the combined
add 192 mL w/w(HNO3) = 65% to a filtrates and make up to the mark with
1 L volumetric flask that already con- dist. H2O.
tains approx. 500 mL dist. H2O. After
the solution has cooled, make up to Analyses
the mark with dist. H2O. Carry out all analyses with the Optrode
• Acetate buffer: Dissolve 60 g ammoni- at a wavelength of 610 nm.
um acetate in approx. 200 mL dist.
H2O and add 400 mL glacial acetic Calcium
acid. Mix and make up to 1 L with To a 2.5 mL sample solution, add approx.
dist. H2O. 70 mL dist. H2O and adjust to pH 12
• Ammonia buffer: Dissolve 54 g NH4Cl with c(NaOH) = 2 mol/L. Add a spatula
in approx. 200 mL dist. H2O and add tip of murexide indicator, then titrate the
350 mL w/w(NH3) = 25%. Mix and solution with c(Na2EDTA) = 0.1 mol/L
make up to 1 L with dist. H2O. past the second breakpoint. Store the
2+
• Indicator for Ca , murexide: triturate titrant consumption up to BP2 as a "com-
100 mg murexide with 10 g NaCl. mon variable" because it will be used in
2+ 2+
• Indicator for Mg , methylthymol blue: the determination of the Mg content.
triturate 100 mg methylthymol blue
with 10 g NaCl.
3+
• Indicator solution for Fe , sulfosalicylic
acid: dissolve 4 g sulfosalicylic acid in
100 mL dist. H2O.
Calculation Calculation
35
VBP2 c EDTA fEDTA 40 MCaO (VEP1 - VCa, BP2) c EDTA fEDTA 40 MMgO
CaO % = MgO % =
mS mS

CaO%: Calcium content as calcium MgO%: Magnesium content as mag-

oxide in % nesium oxide in %
VBP2: Volume of EDTA consumed up VEP1: Volume of EDTA consumed up
to the second breakpoint in mL to the first equivalence point
cEDTA: Concentration of EDTA in in mL
mol/L; c(EDTA) = 0.1 mol/L VCa, BP2: Volume of EDTA consumed in
fEDTA: Titer of the EDTA solution the calcium determination in
40: Conversion factor mL
MCaO: Molar mass of calcium oxide; cEDTA: Concentration of EDTA in
56.08 g/mol mol/L; c(EDTA) = 0.1 mol/L
mS: Sample size in g fEDTA: Titer of the EDTA solution
40: Conversion factor
Magnesium MMgO: Molar mass of magnesium
This titration is used to determine the oxide; 40.32 g/mol
2+ 2+
sum of Ca and Mg , and to calculate mS: Sample size in g
the magnesium content by subtracting
2+
the titrant consumption for the Ca Iron
determination from the total consump- Pipette 10 mL of the digested solution
tion. into a titration beaker, dilute with dist.
H2O, and add 1 mL sulfosalicylic acid
Pipette 2.5 mL of the digested solution indicator. Adjust the mixture to pH 1.5–2
into a titration beaker and dilute to with c(NH3) = 2 mol/L or with c(HCl) =
approx. 80(VmL -with dist.
VCa, BP2 ) Hc2EDTA
O. Adjust
fEDTAthe40 6 Mmol/L, as appropriate. Next, titrate
MgO
MgO % = to EP1
solution pH 10 with c(NaOH) = 2 with c(Na2EDTA) = 0.025 mol/L past the
mS
mol/L, and add a spatula tip of methyl- first breakpoint. (Use small volume incre-
thymol blue. Next, titrate the solution ments – e.g., 25 µL).
with c(Na2EDTA) = 0.1 mol/L past the
first equivalence point. Store the titrant consumption up to BP1
as a "common variable" because it will
3+
be used in the determination of Al .
36 Calculation
VEP1 c EDTA f EDTA 10 M Fe 2 O 3
Aluminum
2+
As in the Mg determination, this is also
3+
Fe 2 O 3 % = a cumulative determination method. Al
mS 2 3+
and Fe are detected together. The alu-
Fe2O3%: Iron content as iron oxide in % minum content is then calculated by
VEP1: Volume of EDTA consumed up subtracting the titrant consumption for
3+
to the first equivalence point the Fe determination from the total
in mL consumption.
cEDTA: Concentration of EDTA in
mol/L; c(EDTA) = 0.025 mol/L Pipette 10 mL sample into a glass beaker
fEDTA: Titer of the EDTA solution and add 70 mL dist. H2O. Add 10 mL
10: Conversion factor acetate buffer, adjust to pH 3.5 with
MFe2O3: Molar mass of iron oxide; c(HCl) = 6 mol/L, and add 1.25 mL
159.69 g/mol c(Na2EDTA) = 0.1 mol/L and 1 mL xylenol
mS: Sample size in g orange indicator solution. Titrate the
2: Stoichiometric factor solution with c(Bi(NO3)3) = 0.05 mol/L
past the first equivalence point.

Calculation
(( VEDTA1 c EDTA1 fEDTA1) - (VEDTA2 c EDTA2 fEDTA2 ) - (VEP1 c Bi fBi )) MAl 2 O 3 10
Al 2 O 3 % =
mS 2

Al2O3%: Aluminum content as alumi- fEDTA2: Titer of the Na2EDTA solution

num oxide in % c(Na2EDTA) = 0.025 mol/L
VEDTA1: Initial volume of c(Na2EDTA) = VEP1: Volume of c(Bi(NO3)3) =
0.1 mol/L in mL 0.05 mol/L consumed up to
cEDTA1: Concentration of the Na2EDTA the first equivalence point in
solution in mol/L; c(EDTA) = mL
0.1 mol/L cBi: Concentration of the Bi(NO3)3
fEDTA1: Titer of the Na2EDTA solution solution in mol/L;
c(Na2EDTA) = 0.1 mol/L c(BiNO3)3) = 0.05 mol/L
VEDTA2: Volume of c(Na2EDTA) = fBi: Titer of the Bi(NO3)3 solution;
0.025 mol/L consumed for the c(Bi(NO3)3) = 0.05 mol/L
iron determination in mL 10: Conversion factor
cEDTA2: Concentration of the Na2EDTA MAI2O3: Molar mass of aluminum
solution in mol/L; oxide; 101.96 g/mol
c(EDTA) = 0.025 mol/L mS: Sample size in g
2: Stoichiometric factor
Examples: Titration curves of a cement sample
37

Figure 36 Titration curve of the photometric Figure 37 Titration curve of the photometric
determination of calcium in cement with the determination of magnesium in cement with
Optrode at 610 nm the Optrode at 610 nm

Figure 38 Titration curve of the photometric Figure 39 Titration curve of the photometric
determination of iron in cement with the determination of aluminum in cement with
Optrode at 610 nm the Optrode at 610 nm

Further literature on this topic is given in

• Application Bulletin AB-063 – Determination of silicon, calcium, magnesium,
iron, and aluminum in digested cement samples by photometric titrations
• Titration Application Note AN-T-078 – Determination of aluminum in cement
using photometric titration
• Titration Application Note AN-T-079 – Determination of calcium in cement by
photometric titration of the solubilized product according to EN 196-2
• Titration Application Note AN-T-080 – Determination of iron in cement using
photometric titration
• Titration Application Note AN-T-081 – Determination of magnesium in cement
using photometric titration
 Sulfate

38 Potentiometric with the Ca ISE

Reagents
Analysis
If necessary, dilute the sample solution,
• Titrant: c(Na2EGTA) = 0.05 mol/L; slurry which should not contain more than
19.4 g ethylene glycol-bis(2-amino­ethyl­ 20 mg sulfate, with dist. H2O to approx.
ether)tetraacetic acid (w = 98%) 50 mL and adjust to pH < 4 with c(HNO3)
2+
in approx. 200 mL dist. H2O. Add = 1 mol/L. Add 0.5 mL Ca ­standard
2+
c(NaOH) = 10 mol/L while stirring until (c(Ca ) = 0.1 mol/L) and 7.5 mL c(BaCl2)
everything has dissolved. Allow to cool, = 0.05 mol/L, and allow to react for 3 min
mix, and make up to 1 L with dist. H2O. while stirring. Add 5 mL buffer solution
• Barium chloride solution: c(BaCl2) = pH 10, allow to react for a further 30 s,
0.05 mol/L; dissolve 12.34 g and titrate with c(Na2EGTA) = 0.05 mol/L
BaCl2∙2H2O (w = 99%) in c(HCl) = past the second equivalence point.
0.01 mol/L, mix, and make up to 1 L
with dist. H2O. Calculation
• Buffer solution pH = 10: dissolve 9 g
Blank - VEP2 - VEP1 c EGTA f MSO42-
NH4Cl and 60 mL w/w(NH3) = 25% in 2- =
SO 4 VS
dist. H2O, mix, and make up to 1 L
with dist. H2O. βSO42-: Sulfate content of the sample
2+ 2+
• Ca standard: c(Ca ) = 0.1 mol/L; in g/L
e.g., Metrohm No. 6.2301.070 Blank: Blank value in mL
• Nitric acid: c(HNO3) = 1 mol/L VEP2: Volume of EGTA standard solu-
tion consumed up to the second
Blank value determination equivalence point in mL
To a glass beaker, add approx. 50 mL dist. VEP1: Volume of EGTA standard solu-
2+
H2O, 1 mL c(HNO3) = 1 mol/L, 0.5 mL Ca tion consumed up to the first
2+
standard (c(Ca ) = 0.1 mol/L), and 7.5 mL equivalence point in mL
c(BaCl2) = 0.05 mol/L. Allow to react for cEGTA: Concentration of the EGTA
3 min while stirring. Add 5 mL buffer ­standard solution in mol/L
solution pH 10, allow to react for a fur- f: Titer of the EGTA standard
ther 30 s, and titrate with c(Na2EGTA) = solution
0.05 mol/L past the second equivalence MSO42-: Molar mass of sulfate;
point. EP1 corresponds to the calcium 96.063 g/mol
content and the difference EP2–EP1 to the VS: Sample size in mL
barium content. Store EP2–EP1 (mL) as
blank value (common variable).
Example: Sulfate in aqueous solution
39

Figure 40 Titration curve of the blank value Figure 41 Titration curve of the sulfate
determination with the Ca ISE determination with the Ca ISE

Further literature on this topic is given in

• Application Bulletin AB-140 – Titrimetric sulfate determination
• Titration Application Note AN-T-116 – Automatic sulfate determination in
aqueous solution using a combined ion-selective calcium electrode (Ca-ISE)

Single determinations
Al – Aluminum
General
The complexometric titration of alumi- procedures were formerly carried out in
num is associated with a particularities a hot solution. However, if the titrant
that should be taken into consideration excess is sufficiently large (> 50%), the
when determining this metal. reaction is fast and the titration can be
performed at room temperature. Hence,
3+
Reaction rate Al can be determined by back titration.
Complexation is slow at room tempera-
ture. For this reason, many titration
40 Formation of hydroxo complexes
Al forms hydroxo complexes that react the addition), thus falsifying the result. Al
very sluggishly (if at all) with the complex- is best titrated at pH values between 4
ing agent. Al must thus be titrated in and 5.
acidic solutions. If the preneutralization is
carried out by adding hydroxide ions, for Since the titration is carried out in slight-
2+ 2+
example, this must be taken into account ly acidic solution, Ca and Mg do not
3+
and the solution should only be neutral- interfere, if present. Fe is also detected
ized to pH ≈ 4. Otherwise, these hydroxo quantitatively and must be determined
complexes may form (also locally during separately.

Table of equivalent masses

1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent:
Formula Molar mass in g/mol Equivalent in mg
Al 26.982 2.698
Al(OH)3 78.004 7.800
Al2O3 101.961 5.098
AlCl3 133.341 13.334
Al(NO3)3 212.996 21.300
Al(NO3)3∙9 H2O 375.134 37.513
Al2(SO4)3 342.151 17.108
Al2(SO4)3∙18 H2O 666.426 33.321

Potentiometric with the Cu-ISE

Reagents Analysis
• Titrant 1: c(Na2EDTA) = 0.1 mol/L If necessary, dilute the sample solution,
• Titrant 2: c(CuSO4) = 0.1 mol/L; which should not contain more than
3+
dissolve 24.97 g CuSO4∙5 H2O in 15 mg Al , with dist. H2O to approx.
approx. 500 mL dist. H2O, add 50 mL. Add 5 mL acetate buffer and
0.5 mL w/w(H2SO4) = 96%, mix, and 10 mL c(Na2EDTA) = 0.1 mol/L, allow to
make up to 1 L with dist. H2O. react for 1–3 min while stirring, and
• Acetate buffer, pH = 4.7: Dissolve titrate with c(CuSO4) = 0.1 mol/L past the
116 g ammonium acetate in approx. first equivalence point.
200 mL dist. H2O and add 86 mL gla-
cial acetic acid. Mix and make up to
1 L with dist. H2O.
 Calculation
(VEDTA f1 c EDTA - VEP1 f2 c CuSO 4 ) MAl
41
Al =
VS

βAl: Aluminum content of the sample

in g/L
VEDTA: Added volume of EDTA standard
solution in mL
f1: Titer of the EDTA standard
solution
cEDTA: Concentration of the EDTA
standard solution in mol/L Figure 42 Example curve of a potentiometric
VEP1: Volume of CuSO4 standard solu- aluminum determination
tion consumed up to the first
equivalence point in mL Further literature on this topic is
f2: Titer of the CuSO4 standard given in
solution • Application Bulletin AB-101 –
CCuSO4: Concentration of the CuSO4 Complexometric titrations with the
standard solution in mol/L Cu-ISE
MAl: Molar mass of aluminum; • Titration Application Note AN-T-103
26.982 g/mol – Fully automated determination of
VS: Sample size in mL aluminum in aqueous solution

Photometric with the Optrode at

610 nm
Reagents
• Titrant: c(Bi(NO3)3) = 0.05 mol/L; solution has cooled, make up to the
dissolve 24.25 g Bi(NO3)3∙5 H2O in mark with dist. H2O.
approx. 500 mL HNO3 (2 mol/L) and • Acetate buffer: Dissolve 60 g ammoni-
transfer into a 1 L volumetric flask. um acetate in approx. 200 mL dist.
Next, make up to 1 L with dist. H2O. H2O and add 400 mL glacial acetic
• Auxiliary solution: c(Na2EDTA) = acid. Mix and make up to 1 L with dist.
0.1 mol/L H2O.
• Hydrochloric acid: c(HCl) = 6 mol/L; • Indicator solution: Xylenol orange;
add 590 mL w/w(HCl) = 37% to a 1 L dissolve 100 mg xylenol orange
volumetric flask that already contains disodium salt in 100 mL dist. H2O.
approx. 200 mL dist. H2O. After the
42 Analysis
Pipette 10 mL sample solution into a glass tor solution. Titrate the solution with
beaker and add 70 mL dist. H2O. Add 10 c(Bi(NO3)3) = 0.05 mol/L past the first
mL acetate buffer, adjust to pH 3.5 with equivalence point.
c(HCl) = 6 mol/L, and then add 1.25 mL
c(Na2EDTA) = 0.1 mol/L and 1 mL indica-

Calculation
(( VEDTA c EDTA fEDTA ) - (VEP1 c Bi fBi )) MAl 2 O 3 10
Al 2 O 3 % =
mS 2

Al2O3%: Aluminum content as aluminum

oxide in %
VEDTA: Added volume of EDTA
standard solution in mL
cEDTA: Concentration of the EDTA
standard solution in mol/L
fEDTA: Titer of the EDTA standard
solution
VEP1: Volume of c(Bi(NO3)3) =
0.05 mol/L consumed up to the
first equivalence point in mL Figure 43 Example of a photometric titration
cBi: Concentration of the Bi(NO3)3 curve of aluminum at 610 nm
solution in mol/L
fBi: Titer of the Bi(NO3)3 solution; Further literature on this topic is
c(Bi(NO3)3) = 0.05 mol/L given in
10: Conversion factor • Application Bulletin AB-063 –
MAI2O3: Molar mass of aluminum oxide; Determination of silicon, calcium,
101.96 g/mol magnesium, iron, and aluminum in
mS: Sample size in g digested cement samples by
2: Stoichiometric factor photometric titrations
Ba – Barium and Sr – Strontium

General
Barium and strontium can be titrated The following table contains some solu-
43
either directly or indirectly in alkaline solu- bility products as pKsp values as a guide
2+ 2+
tion. Ca and Mg are also determined.
2+
Ba can be separated by precipitation as Ksp = a[A] ∙ a[B]
BaSO4 (Caution: BaSO4 dissolves in excess
Na2EDTA). Heavy metal ions are masked pKsp is the negative logarithm of Ksp. As
by adding KCN. Since the titration can pKsp increases, the solubility of the respec-
only be performed in alkaline solution, in tive compound decreases.
which both barium and strontium form
sparingly soluble carbonates, the results Compound pKsp
of the determination may be too low. This BaCO3 8.2
is why the determinations are often car- BaSO4 10.0
ried out using back titration. CaCO3 7.9
CaSO4 4.3
MgCO3 3.8
SrCO3 8.8
SrSO4 6.6

Table of equivalent masses

1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Ba 137.327 13.733
BaCO3 197.336 19.734
BaCl2 208.233 20.823
Ba(NO3)2 261.337 26.134
BaO 153.326 15.333
Ba(OH)2 171.342 17.134
BaSO4 233.390 23.339
Sr 87.620 8.762
SrCO3 147.629 14.763
SrCl2 158.526 15.853
Sr(NO3)2 211.630 21.163
SrO 103.619 10.362
Sr(OH)2 121.635 12.164
SrSO4 183.683 18.368
44 Potentiometric with the Cu-ISE
Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L VEP1 f c EDTA MBa/Sr
• Cu complex solution: c[Cu(NH4)2EDTA] Ba/Sr =
VS
= 0.1 mol/L (e.g., Merck No. 105217)
• Ammonia buffer, pH = 10: Dissolve βBa/Sr: Barium or strontium content of the
54 g NH4Cl in approx. 200 mL dist. sample in g/L
H2O and add 350 mL w/w(NH3) = VEP1: Volume of EDTA standard solution
25%. Mix and make up to 1 L with consumed up to the first equiva-
dist. H2O. lence point in mL
• Sodium hydroxide: c(NaOH) = f: Titer of the EDTA standard solution
1 mol/L cEDTA: Concentration of the EDTA
standard solution in mol/L
Analysis MBa/Sr: Molar mass of barium and
Preneutralize very acidic sample solu- strontium; 137.327 g/mol and
tions to approx. pH 4 with c(NaOH) = 87.620 g/mol, respectively
1 mol/L. If necessary, dilute the sample VS: Sample size in mL
solution with dist. H2O to approx. 50 mL.
Add 1 mL Cu complex solution and 5 mL
ammonia buffer, wait for 10–20 s while
stirring, and then titrate with c(Na2EDTA)
= 0.1 mol/L past the first equivalence
point.

Figure 44 Example of a potentiometric

titration curve of barium with the Cu-ISE

Further literature on this topic is given in

• Application Bulletin AB-101 – Complexometric titrations with the copper ion-
selective electrode
• Titration Application Note AN-T-104 – Fully automated determination of barium
in aqueous solution
Photometric with the Optrode at
574 nm
45
Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L
VEP1 f c EDTA MBa/Sr
• Indicator solution: Phthalein purple; Ba/Sr =
VS
dissolve 0.1 g phthalein purple in
approx. 75 mL dist. H2O and 1 mL βBa/Sr: Barium or strontium content of
w/w(NH3) = 25%. Mix and make up the sample in g/L
to 100 mL with dist. H2O. VEP1: Volume of EDTA standard solution
• Ammonia: w/w(NH3) = 25% consumed up to the first equiva-
• Sodium hydroxide: c(NaOH) = lence point in mL
1 mol/L f: Titer of the EDTA standard solution
cEDTA: Concentration of the EDTA
Analysis standard solution in mol/L
Preneutralize very acidic samples to pH 4–5 MBa/Sr: Molar mass of barium and
with c(NaOH) = 1 mol/L. To 50 mL sample strontium; 137.327 g/mol and
solution, which should not contain more 87.620 g/mol, respectively
2+ 2+
than 100 mg Ba or 80 mg Sr , add 100 VS: Sample size in mL
mL dist. H2O. Add 5 mL w/w(NH3) = 25%
and 0.5 mL indicator solution, and titrate
immediately with c(Na2EDTA) = 0.1 mol/L
past the first equivalence point (colorless).

Figure 45 Photometric titration curve of

barium with the Optrode at 574 nm

Further literature on this topic is given in

• Titration Application Note AN-T-142 – Determination of barium using automatic
photometric titration
 Bi – Bismuth

46 General
3+ 3+
Similar to Al , Bi also forms hydroxo metric determination of Bi is thus very
3+
complexes in aqueous solutions. Bi selective. Interference can only be
reacts sluggishly with the complexing expected from metal ions whose com-
3+
agent but, on the other hand, Bi com- plex formation constant is > 20 (Fe ,
2+ 2+ 4+
plexes have a very high complex forma- Hg , Sn , Sn ). Determination of Bi in
3+
tion constant. This enables Bi to be some pharmaceuticals (e.g., Bi subgal-
titrated without problems even in very late, Bi subsalicylate) is carried out after
acidic solutions (pH 1–2). Com­ plexo­ digestion of the sample.

Table of equivalent masses

1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Bi 208.980 20.898
Bi(OH)3 261.013 26.101
Bi2O3 465.959 23.298
(BiO)2CO3 509.969 25.498
BiONO3∙H2O 305.000 30.500
Bi(NO3)3 394.995 39.500

Potentiometric with the Cu ISE

Reagents Analysis
• Titrant 1: c(Na2EDTA) = 0.1 mol/L If necessary, dilute the acidic sample solu-
• Titrant 2: c(CuSO4) = 0.1 mol/L; tion, which should not contain more than
3+
dissolve 24.97 g CuSO4∙5 H2O in 160 mg Bi , with dist. H2O to approx.
approx. 500 mL dist. H2O. Add 0.5 mL 50 mL. Add 5 mL acetate buffer and
w/w(H2SO4) = 96%, mix, and make up 10 mL c(Na2EDTA) = 0.1 mol/L, and, if
to 1 L with dist. H2O. necessary, adjust to pH 4.7 with w/w(NH3)
• Acetate buffer, pH = 4.7: Dissolve = 25%. Allow to react for approx. 1 min
116 g ammonium acetate in approx. while stirring, and titrate with c(CuSO4) =
200 mL dist. H2O and add 86 mL gla- 0.1 mol/L past the first equivalence point.
cial acetic acid. Mix, and make up to
1 L with dist. H2O.
• Ammonia: w/w(NH3) = 25%
 Calculation
(VEDTA f1 c EDTA - VEP1 f2 c CuSO 4 ) MBi
47
Bi = VS

βBi: Bismuth content of the sample

in g/L
VEDTA: Added volume of EDTA standard
solution in mL
f1: Titer of the EDTA standard solution
cEDTA: Concentration of the EDTA
standard solution in mol/L
Figure 46 Potentiometric titration curve of
VEP1: Volume of CuSO4 standard solu-
bismuth with the Cu-ISE
tion consumed up to the first
equivalence point in mL
f2: Titer of the CuSO4 standard Further literature on this topic is
solution given in
CCuSO4: Concentration of the CuSO4 • Application Bulletin AB-101 –
standard solution in mol/L Complexometric titrations with the
MBi: Molar mass of bismuth; Cu-ISE
208.980 g/mol • Titration Application Note AN-T-105
VS: Sample size in mL – Fully automated determination of
bismuth(III) in aqueous solution

Photometric with the Optrode at

520 nm
Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L
VEP1 f c EDTA MBi
• Nitric acid: w/w(HNO3) = 65% Bi =
VS
• Indicator solution: Xylenol orange;
dissolve 100 mg xylenol orange βBi: Bismuth content of the sample
disodium salt in 100 mL dist. H2O. in g/L
VEP1: Volume of titrant consumed up to
Analysis the first equivalence point in mL
Dissolve the sample in a small amount of f: Titer of the EDTA standard solution
w/w(HNO3) = 65%, and dilute to approx. cEDTA: Concentration of the EDTA
100 mL with dist. H2O. Add 0.5 mL indi- standard solution in mol/L
cator solution, and titrate with c(Na2EDTA) MBi: Molar mass of bismuth;
= 0.1 mol/L past the first equivalence 208.980 g/mol
point. VS: Sample size in mL
48 Further literature on this topic is
given in
• Titration Application Note AN-T-088
– Photometric EDTA titration of bis-
muth nitrate according to Ph. Eur.
and USP

Figure 47 Example of a photometric

titration curve of bismuth at 520 nm

Ca – Calcium

General
2+
Ca is one of the first metals that was as CaCO3. If the titration is carried out
determined using complexometric titra- too quickly, this could lead to incorrect
tion. Since then, hundreds, if not thou- results that are too low. (CaCO3 reacts
sands, of publications on this topic have slowly with the titrant, which is acting as
appeared. In this chapter, we will only a complexing agent, and the resulting
2+
discuss the determination of Ca . If the turbidity interferes, particularly in the
2+ 2+
sample contains both Ca with Mg , case of photometric titration).
please refer to the section on "Water
2+
hardness". If Ca is to be determined in the pres-
2+
ence of Mg , the EDTA can be replaced
2+
Since Ca is always titrated in alkaline by EGTA, which is a more selective
solution, there is always a risk that it may titrant (or by the Cu-EGTA complex if a
absorb CO2 from the air and precipitate Cu ISE is used).
Table of equivalent masses
1 mL c(CA) = 0.1 mol/L = x mg equivalent (CA = complexing agent)
49
Formula Molar mass in g/mol Equivalent in mg
Ca 40.078 4.008
CaC2O4 128.097 12.810
CaCO3 100.087 10.009
CaCl2 110.984 11.098
Ca(NO3)2 164.088 16.409
CaO 56.077 5.608
Ca(OH)2 74.093 7.409
CaSO3 120.141 12.014
CaSO4 136.141 13.614

Potentiometric with the Ca-ISE

Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L VEP1 f c EDTA MCa
• Buffer solution: Dissolve 54 g NH4Cl Ca =
VS
in approx. 200 mL dist. H2O and add
350 mL w/w(NH3) = 25%. Mix and βCa: Calcium content of the sample
make up to 1 L with dist. H2O. in g/L
• Sodium hydroxide: c(NaOH) = VEP1: Volume of EDTA standard solution
1 mol/L consumed up to the first equiva-
lence point in mL
Analysis f: Titer of the EDTA standard solution
Preneutralize acidic sample solutions cEDTA: Concentration of the EDTA
with c(NaOH) = 1 mol/L to pH 5–7 and standard solution in mol/L
dilute, if necessary, with dist. H2O to MCa: Molar mass of calcium;
approx. 50 mL. Add 5 mL buffer solution 40.078 g/mol
and titrate with c(Na2EDTA) = 0.1 mol/L VS: Sample size in mL
past the first equivalence point.

Figure 48 Example curve of a potentiometric

calcium determination with the Ca-ISE
50 Further literature on this topic is
given in
Calculation
VEP1 f c EDTA MCa
• Application Bulletin AB-125 – Ca =
VS
Simultaneous determination of
­calcium, magnesium, and alkalinity βCa: Calcium content of the sample
by complexometric titration with in g/L
potentiometric or photometric indi- VEP1: Volume in mL of EDTA standard
cation in water and beverage samples solution consumed up to the first
equivalence point
Potentiometric with the Cu ISE f: Titer of the EDTA standard solution
Reagents cEDTA: Concentration of the EDTA
• Titrant: c(Na2EDTA) = 0.1 mol/L standard solution in mol/L
• Buffer solution: Dissolve 54 g NH4Cl MCa: Molar mass of calcium;
in approx. 200 mL dist. H2O and add 40.078 g/mol
350 mL w/w(NH3) = 25%. Mix and VS: Sample size in mL
make up to 1 L with dist. H2O.
• Cu complex solution: c[Cu(NH4)2EDTA]
= 0.1 mol/L (e.g., Merck No. 105217)
• Sodium hydroxide: c(NaOH) =
1 mol/L

Analysis
Preneutralize acidic sample solutions
with c(NaOH) = 1 mol/L to pH 5–7 and
dilute, if necessary, with dist. H2O to
approx. 50 mL. Add 5 mL buffer solution
and 0.5 mL Cu complex solution, wait
Figure 49 Potentiometric titration curve of
20 s while stirring, and titrate with the determination of calcium in milk with the
c(Na2EDTA) = 0.1 mol/L past the first Cu-ISE
equivalence point.

Further literature on this topic is given in

• Application Bulletin AB-101 – Complexometric titrations with the Cu-ISE
• Titration Application Note AN-T-106 – Fully automated determination of calcium
in milk
Photometric with the Optrode at
610 nm
51
Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L
VEP1 f c EDTA MCa
• Sodium hydroxide: c(NaOH) = Ca =
VS
1 mol/L
• Indicator solution: HHSNN; dissolve βCa: Calcium content of the sample
20 mg HHSNN in 50 mL ethanol. in g/L
VEP1: Volume of EDTA standard solution
Analysis consumed up to the first equiva-
Preneutralize acidic sample solutions with lence point in mL
c(NaOH) = 1 mol/L to pH 5–7 and dilute, f: Titer of the EDTA standard solution
if necessary, with dist. H2O to approx. cEDTA: Concentration of the EDTA
50 mL. Add 4 mL c(NaOH) = 1 mol/L and standard solution in mol/L
1.5 mL indicator solution, and titrate MCa: Molar mass of calcium;
immediately with c(Na2EDTA) = 0.1 mol/L 40.078 g/mol
past the first equivalence point. VS: Sample size in mL

Figure 50 Example of a photometric

titration curve of the calcium determination
with the Optrode at 610 nm

Further literature on this topic is given in

• Application Bulletin AB-125 – Simultaneous determination of calcium,
magnesium, and alkalinity by complexometric titration with potentiometric or
photometric indication in water and beverage samples
 Cd – Cadmium

52 General
The complexation behavior of Cd is
2+ 2+
problems. However, Ca and Mg inter-
2+

very similar to that of zinc. It can be fere if present because they are also
titrated in alkaline solution without determined.

Table of equivalent masses

1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Cd 112.411 11.241
CdCO3 172.420 17.242
CdCl2 183.317 18.332
Cd(NO3)2 236.421 23.642
Cd(NO3)2∙2H2O 272.451 27.245
CdO 128.410 12.841
Cd(OH)2 146.426 14.643
CdSO4 208.474 20.847

Potentiometric with the Cu-ISE

Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L VEP1 f c EDTA MCd
• Ammonia buffer: Dissolve 54 g NH4Cl Cd =
VS
in approx. 200 mL dist. H2O and add
350 mL w/w(NH3) = 25%. Mix and βCd: Cadmium content of the sample
make up to 1 L with dist. H2O. in g/L
• Cu complex solution: c[Cu(NH4)2EDTA] VEP1: Volume of EDTA standard solution
= 0.1 mol/L (e.g., Merck No. 105217) consumed up to the first equiva-
• Sodium hydroxide: c(NaOH) = lence point in mL
1 mol/L f: Titer of the EDTA standard solution
cEDTA: Concentration of the EDTA
Analysis standard solution in mol/L
Preneutralize acidic sample solutions MCd: Molar mass of cadmium;
with c(NaOH) = 1 mol/L to pH 4–5 and 112.411 g/mol
dilute, if necessary, with dist. H2O to VS: Sample size in mL
approx. 50 mL. Add 5 mL ammonia buf-
fer and 0.5 mL Cu complex solution,
wait 20 s while stirring, and titrate with
c(Na2EDTA) = 0.1 mol/L past the first
equivalence point.
 Further literature on this topic is
given in
53
• Application Bulletin AB-101 –
Complexometric titrations with the
Cu-ISE
• Titration Application Note AN-T-125
– Automatic determination of
cadmium in aqueous solution with
the Cu-ISE

Figure 51 Potentiometric titration curve of

cadmium with the Cu-ISE

Photometric with the Optrode at

610 nm
Reagents Calculation
• Titrant 1: c(Na2EDTA) = 0.1 mol/L
(VEDTA f1 c EDTA - VEP1 f2 c ZnSO 4 ) MCd
• Titrant 2: c(ZnSO4) = 0.1 mol/L; Cd =
VS
dissolve 28.8 g ZnSO4∙7 H2O in
approx. 500 mL dist. H2O, add 0.5 mL βCd: Cadmium content of the sample
w/w(H2SO4) = 96%, mix, and make up in g/L
to 1 L with dist. H2O. VEDTA: Added volume of EDTA standard
• Ammonia buffer, pH = 10: Dissolve solution in mL
54 g NH4Cl in approx. 200 mL dist. f1: Titer of the EDTA standard solution
H2O and add 350 mL w/w(NH3) = cEDTA: Concentration of the EDTA
25%. Mix and make up to 1 L with standard solution in mol/L
dist. H2O. VEP1: Volume of ZnSO4 standard solution
• Sodium hydroxide: c(NaOH) = 1 mol/L consumed up to the first equiva-
• Indicator solution: Eriochrome Black T; lence point in mL
dissolve 100 mg Eriochrome Black T in f2: Titer of the ZnSO4 standard
100 mL ethanol. solution
cZnSO4: Concentration of the ZnSO4
Analysis standard solution in mol/L
Preneutralize acidic sample solutions MCd: Molar mass of cadmium;
with c(NaOH) = 1 mol/L to approx. pH 5 112.411 g/mol
and dilute, if necessary, with dist. H2O to VS: Sample size in mL
approx. 50 mL. Add 5 mL ammonia buf-
fer, 10 mL c(Na2EDTA) = 0.1 mol/L, and
0.25 mL indicator solution. Then titrate
with c(ZnSO4) = 0.1 mol/L past the first
equivalence point.
54 Further literature on this topic is
given in
• Titration Application Note AN-T-153
– Determination of cadmium using
automatic photometric titration

Figure 52 Photometric titration curve of the

cadmium determination with the Optrode at
610 nm

Co – Cobalt
General
The complexation behavior of cobalt is used by various authors for the complexo-
similar to that of nickel, and it has almost metric determination of cobalt with
the same complex formation constants. In enhanced selectivity. These methods, how-
alkaline solution and in the presence of ever, did not gain acceptance because the
2+
excess EDTA as well as added H2O2, Co quantity of added H2O2 is critical and, in the
forms extremely robust and strongly col- case of photometric titration, the intrinsic
3+ 3+
ored Co -EDTA complexes that are also color of the Co complex interferes with
stable in acidic media. This situation was the color change of the indicator.

Table of equivalent masses

1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Co 58.933 5.893
Co(CH3COO)2∙4 H2O 249.083 24.908
CoCO3 118.942 11.894
CoCl2 129.839 12.984
CoCl2 ∙ 6H2O 237.930 23.793
Co(NO3)2 182.943 18.294
Co(NO3)2∙6 H2O 291.034 29.103
CoO 74.933 7.493
Co2O3 165.865 8.293
CoSO4 154.996 15.500
CoSO4∙7H2O 281.103 28.110
Potentiometric with the Cu-ISE
Reagents Calculation
55
• Titrant: c(Na2EDTA) = 0.1 mol/L VEP1 f c EDTA MCo
• Cu complex solution: c[Cu(NH4)2EDTA] Co =
VS
= 0.1 mol/L (e.g., Merck No. 105217)
• Ammonia buffer: Dissolve 54 g NH4Cl βCo: Cobalt content of the sample
in approx. 200 mL dist. H2O and add in g/L
350 mL w/w(NH3) = 25%. Mix and VEP1: Volume of EDTA standard solution
make up to 1 L with dist. H2O. consumed up to the first equiva-
• Sodium hydroxide: c(NaOH) = lence point in mL
1 mol/L f: Titer of the EDTA standard solution
cEDTA: Concentration of the EDTA
Analysis standard solution in mol/L
If necessary, dilute the sample solution MCo: Molar mass of cobalt;
with dist. H2O to approx. 50 mL and pre- 58.933 g/mol
neutralize, if necessary, to pH 4–5 with VS: Sample size in mL
c(NaOH) = 1 mol/L. Add 5 mL ammonia
buffer and 0.5 mL Cu complex solution,
wait for 10–20 s while stirring, and titrate
with c(Na2EDTA) = 0.1 mol/L past the first
equivalence point.

Figure 53 Example of a potentiometric

titration curve of cobalt with the Cu-ISE

Further literature on this topic is given in

• Application Bulletin AB-101 – Complexometric titrations with the Cu-ISE
• Titration Application Note AN-T-126 – Automatic determination of cobalt in
aqueous solution with the Cu-ISE
56 Photometric with the Optrode at
574 nm
Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L VEP1 f c EDTA MCo
• Indicator solution: murexide; dissolve Co =
VS
0.2 g murexide (triturated 1:100 with
NaCl) in 50 mL dist. H2O. βCo: Cobalt content of the sample
• Ammonia buffer: Dissolve 54 g NH4Cl in g/L
in approx. 500 mL dist. H2O and add VEP1: Volume of EDTA standard solution
350 mL w/w(NH3) = 25%. Adjust to consumed up to the first equiva-
pH 9 with c(HCl) = 6 mol/L, mix, and lence point in mL
make up to 1 L with dist. H2O. f: Titer of the EDTA standard solution
cEDTA: Concentration of the EDTA
Analysis standard solution in mol/L
If necessary, dilute the acidic sample solu- MCo: Molar mass of cobalt;
tion, which should not contain more than 58.933 g/mol
2+
40 mg Co , with dist. H2O to 100 mL and VS: Sample size in mL
degas. Add 10 mL ammonia buffer solu-
tion and 5 mL indicator solution, and
then titrate with c(Na2EDTA) = 0.1 mol/L
past the first equivalence point.

Figure 54 Photometric titration curve of

cobalt with the Optrode at 574 nm

Further literature on this topic is given in

• Titration Application Note AN-T-143 – Determination of cobalt using automatic
photometric titration
Cu – Copper

General
Owing to its relatively high complex for- Keep adding NH3 to the sample solution
57
mation constant, copper can be titrated until Cu(OH)2 precipitates. Then add fur-
in both alkaline and slightly acidic solu- ther NH3 until everything has re-dissolved.
2+
tions. Only the Cu ion can be deter- Dilute with dist. H2O to at least 1:1. Add
mined. In case of photometric titration murexide, and titrate with c(Na2EDTA) =
in an ammoniacal solution, the ammo- 0.1 mol/L.
nia excess should not be too large and
the titrations should always be carried Better results are obtained by photomet-
out in dilute solutions. This is because ric titration at pH = 5.0 with PAN as indi-
2+
the Cu -amine complex is relatively sta- cator. To avoid having to titrate at high
ble and strongly colored and thus com- temperatures, dilute the sample solution
petes with the color indicator (e.g., with ethanol in an approx. 1:1 ratio.
murexide).

Table of equivalent masses

1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Cu 63.546 6.355
Cu(CH3COO)2∙H2O 199.650 19.965
CuCN 89.564 8.956
Cu(CN)2 115.581 11.558
CuCl2 134.452 13.445
CuCl2∙2 H2O 170.842 17.084
Cu(NO3)2 187.556 18.756
Cu(NO3)2∙3 H2O 241.601 24.160
CuO 79.544 7.954
Cu(OH)2 97.561 9.756
CuSO4 159.600 15.960
CuSO4∙5 H2O 249.680 24.968
58 Potentiometric with the Cu-ISE
Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L VEP1 f c EDTA MCu
• Ammonia buffer, pH = 10: Dissolve Cu =
VS
54 g NH4Cl in approx. 200 mL dist.
H2O and add 350 mL w/w(NH3) = βCu: Copper content of the sample
25%. Mix and make up to 1 L with in g/L
dist. H2O. VEP1: Volume of EDTA standard solution
• Sodium hydroxide: c(NaOH) = consumed up to the first equiva-
1 mol/L lence point in mL
f: Titer of the EDTA standard solution
Analysis cEDTA: Concentration of the EDTA
If necessary, dilute acidic sample solu- standard solution in mol/L
tions with dist. H2O to approx. 50 mL MCu: Molar mass of copper;
and preneutralize to pH 4–5 with 63.546 g/mol
c(NaOH) = 1 mol/L. Add 5 mL ammonia VS: Sample size in mL
buffer, and titrate with c(Na2EDTA) =
0.1 mol/L past the first equivalence
point.

Figure 55 Potentiometric titration curve of

copper with the Cu-ISE

Further literature on this topic is given in

• Application Bulletin AB-101 – Complexometric titrations with the Cu-ISE
• Titration Application Note AN-T-127 – Automatic determination of copper in
aqueous solution with the Cu-ISE
Photometric with the Optrode at
520 nm
59
Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L
VEP1 f c EDTA MCu
• Acetate buffer, pH = 5.0: dissolve Cu =
VS
116 g ammonium acetate in approx.
500 mL dist. H2O. Adjust to pH 5.0 βCu: Copper content of the sample
with glacial acetic acid, mix, and in g/L
make up to 1 L with dist. H2O. VEP1: Volume of EDTA standard solution
• Sodium hydroxide: c(NaOH) = consumed up to the first equiva-
1 mol/L lence point in mL
• Ethanol: w/w(ethanol) = 96–98% f: Titer of the EDTA standard solution
• Indicator solution: PAN; dissolve cEDTA: Concentration of the EDTA
100 mg PAN in 100 mL ethanol. standard solution in mol/L
MCu: Molar mass of copper;
Analysis 63.546 g/mol
If necessary, dilute acidic sample solutions VS: Sample size in mL
with dist. H2O to approx. 50 mL and then
preneutralize to approx. pH 4–5 with
c(NaOH) = 1 mol/L. Add 50 mL ethanol
and degas. Add 5 mL acetate buffer and
0.5 mL indicator solution, and titrate with
c(Na2EDTA) = 0.1 mol/L past the first
equivalence point.

Figure 56 Photometric titration curve of

copper with the Optrode at 520 nm

Further literature on this topic is given in

• Titration Application Note AN-T-124 – Photometric copper determination in
aqueous solution
 Fe – Iron

60 General
Iron forms complexes in both its divalent
2+
As a general rule, titration of Fe ions is
and trivalent states. The complex forma- not advisable. Owing to the relatively low
tion constants, however, are very differ- complex formation constant, it must be
ent (approx. 12 orders of magnitude). titrated in alkaline solution under inert
3+ 3+
Fe forms very strong complexes that are gas to prevent oxidation to Fe .
3+
also stable in acidic solution. This means Conversely, interfering Fe can be masked
that Fe can be titrated in the presence of by reducing it, for example, with ascorbic
3+
other metal ions almost without interfer- acid. Thus, only the Fe ion is titrated in
2+
ence. In the presence of, for example, practice. Fe can be oxidized using H2O2
2+
EDTA, Fe becomes a very strong reduc- or peroxydisulfate.
ing agent (standard potential -0.1 V),
+
which can even reduce Ag to its metal.

Table of equivalent masses

1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Fe 55.845 5.585
FeCO3 115.856 11.586
FeCl2 126.753 12.675
FeCl2∙4H2O 198.813 19.881
FeCl3 162.206 16.221
FeCl3∙6H2O 270.297 27.030
Fe(NO3)3 241.862 24.186
Fe(NO3)3∙6H2O 349.953 34.995
FeO 71.846 7.185
Fe2O3 159.692 7.985
FeSO4 151.910 15.191
FeSO4∙7H2O 278.010 27.801
Fe2(SO4)3 399.870 19.994
Fe2(SO4)3∙9H2O 562.010 28.101
Fe(NH4)2(SO4)2∙6H2O 392.130 39.213
Fe(NH4)(SO4)2∙12H2O 482.180 48.218
Potentiometric with the Cu-ISE
Reagents Calculation
61
• Titrant 1: c(Na2EDTA) = 0.1 mol/L (VEDTA f1 c EDTA - VEP1 f2 c CuSO 4 ) MFe
• Titrant 2: c(CuSO4) = 0.1 mol/L; Fe =
VS
dissolve 24.97 g CuSO4∙5 H2O in
approx. 500 mL dist. H2O, add βFe: Iron content of the sample in g/L
0.5 mL w/w(H2SO4) = 96%, mix, and VEDTA: Added volume of EDTA standard
make up to 1 L with dist. H2O. solution in mL
• Acetate buffer, pH = 4.7: Dissolve f1: Titer of the EDTA standard solution
116 g ammonium acetate in approx. cEDTA: Concentration of the EDTA
200 mL dist. H2O and add 86 mL gla- standard solution in mol/L
cial acetic acid. Mix and make up to VEP1: Volume of CuSO4 standard solu-
1 L with dist. H2O. tion consumed up to the first
• Sodium hydroxide: c(NaOH) = equivalence point in mL
1 mol/L f2: Titer of the CuSO4 standard
solution
Analysis cCuSO4: Concentration of the CuSO4
If necessary, dilute the acidic sample solu- standard solution in mol/L
tion, which should not contain more than MFe: Molar mass of iron; 55.845 g/mol
3+
50 mg Fe , with dist. H2O to approx. VS: Sample size in mL
50 mL, add 5 mL acetate buffer, and
adjust to pH 4.7 with c(NaOH) = 1 mol/L.
Add 10 mL c(Na2EDTA) = 0.1 mol/L, allow
to react for 1–2 min while stirring, and
titrate with c(CuSO4) = 0.1 mol/L past the
first equivalence point.

Figure 57 Example of a potentiometric

titration curve of iron with the Cu-ISE

Further literature on this topic is given in

• Application Bulletin AB-101 – Complexometric titrations with the Cu-ISE
• Titration Application Note AN-T-107 – Fully automated determination of total
iron in cement
62 Photometric with the Optrode at
610 nm
Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L VBP1 f c EDTA MFe
• Ammonia: w/w(NH3) = 25% Fe =
VS
• Indicator solution: sulfosalicylic acid;
dissolve 4 g sulfosalicylic acid in βFe: Iron content of the sample in g/L
100 mL dist. H2O. VBP1: Volume of EDTA standard solu-
• Glycine tion consumed up to the first
equivalence point in mL
Analysis f: Titer of the EDTA standard
If necessary, dilute the acidic sample solu- solution
tion with dist. H2O to approx. 100 mL. cEDTA: Concentration of the EDTA
Add 0.5 g glycine and 1 mL indicator standard solution in mol/L
solution, and adjust to pH 1.5–2 with MA: Molar mass of iron;
w/w(NH3) = 25%. Heat the mixture to 55.847 g/mol
50 °C to dissolve the glycine. Allow to VS: Sample size in mL
cool, then titrate with c(Na2EDTA) =
0.1 mol/L past the first equivalence point.

Figure 58 Photometric titration curve of iron

with the Optrode at 610 nm

Further literature on this topic is given in

• Application Bulletin AB-063 – Determination of silicon, calcium, magnesium,
iron, and aluminum in digested cement samples by photometric titrations.
• Titration Application Note AN-T-080 – Determination of iron in cement by
photometric titration
Ga – Gallium and In – Indium

General
Gallium and indium form complexes Photometric back titration with a Mn
63
with quite high formation constants standard solution with Eriochrome Black
(e.g., InEDTA; log Kf = 24.9). However, T indicator would also be possible in
they also tend to form hydroxo com- alkaline solution. However, the usual
plexes that cannot be completely titrat- ammonia buffer pH 10 cannot be used
ed, if at all. Therefore acetate ions are for pH adjustment in this case, because
added as auxiliary complexing agents, this would lead to precipitation of Ga
and the metals are determined by back and In as Ga(OH)3 and In(OH)3., respec-
titration in slightly acidic solution. This tively. To avoid this, tartrate is added as
2+
avoids possible interference by Ca - auxiliary complexing agent before
2+
and/or Mg ions. adjusting the pH to 8.5–9 using ammo-
2+ 2+ 2+ 2+ 2+
nia. If present, Zn , Cd , Hg , Cu , Ni ,
2+
and Co can be masked with KCN.
Table of equivalent masses
1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Ga 69.723 6.972
Ga(NO3)3∙8H2O 399.860 39.986
Ga2O3 187.444 9.372
Ga2(SO4)3 427.634 21.382
Ga2(SO4)3∙18H2O 751.909 37.595
In 114.818 11.482
InCl3 221.177 22.118
In2O3 277.634 13.882
In2(SO4)3 517.824 25.891
In2(SO4)3∙9H2O 679.961 33.998

Potentiometric with the Cu-ISE

Reagents
• Titrant 1: c(Na2EDTA) = 0.1 mol/L • Acetate buffer, pH = 4.7: Dissolve
• Titrant 2: c(CuSO4) = 0.1 mol/L; 116 g ammonium acetate in approx.
dissolve 24.97 g CuSO4∙5H2O in 200 mL dist. H2O and add 86 mL gla-
approx. 500 mL dist. H2O, add cial acetic acid. Mix and make up to
0.5 mL w/w(H2SO4) = 96%, mix, and 1 L with dist. H2O.
make up to 1 L with dist. H2O. • Ammonia: w/w(NH3) = 25%
64 Analysis
If necessary, dilute the acidic sample
solution, which should not contain more
3+ 3+
than 60 mg Ga and/or 100 mg In ,
with dist. H2O to approx. 50 mL. Add
5 mL acetate buffer and 10 mL
c(Na2EDTA) = 0.1 mol/L, and, if neces-
sary, adjust to pH 4.7 with w/w(NH3) =
25%. Allow to react for approx. 30 s
while stirring, and then titrate with
c(CuSO4) = 0.1 mol/L past the first
equivalence point.
Figure 59 Potentiometric titration curve of
indium with the Cu-ISE
Calculation

(VEDTA f1 c EDTA - VEP1 f2 c CuSO 4 ) MGa/In Further literature on this topic is

Ga/In =
VS given in
βGa/In: Gallium or indium content of the • Application Bulletin AB-101 –
sample in g/L Complexometric titrations with the
VEDTA: Added volume of EDTA standard Cu-ISE
solution in mL • Titration Application Note AN-T-121
f1: Titer of the EDTA standard solution – Automatic indium determination in
cEDTA: Concentration of the EDTA aqueous solution using the ion-selec-
standard solution in mol/L tive copper electrode (Cu-ISE)
VEP1: Volume of CuSO4 standard
solution consumed up to the first
equivalence point in mL
f2: Titer of the CuSO4 standard
solution
cCuSO4: Concentration of the CuSO4
standard solution in mol/L
MGa/In: Molar mass of gallium and indium;
69.723 g/mol and 114.818 g/mol,
respectively
VS: Sample size in mL
Photometric with the Optrode at
610 nm
65
Reagents Calculation
• Titrant 1: c(Na2EDTA) = 0.1 mol/L (VEDTA f1 c EDTA - VEP1 f2 c ZnSO 4 ) MGa/In
• Titrant 2: c(ZnSO4) = 0.1 mol/L; Ga/In =
VS
dissolve 28.8 g ZnSO4∙7H2O in
approx. 500 mL dist. H2O, add βGa/In: Gallium or indium content of the
0.5 mL w/w(H2SO4) = 96%, mix, and sample in g/L
make up to 1 L with dist. H2O. VEDTA: Added volume of EDTA standard
• Acetate buffer, pH = 4.7: Dissolve solution in mL
116 g ammonium acetate in approx. f1: Titer of the EDTA standard solution
200 mL dist. H2O and add 86 mL gla- cEDTA: Concentration of the EDTA
cial acetic acid. Mix and make up to standard solution in mol/L
1 L with dist. H2O. VEP1: Volume of ZnSO4 standard solution
• Indicator solution: xylenol orange; consumed up to the first
dissolve 25 mg xylenol orange equivalence point in mL
disodium salt in 100 mL dist. H2O. f2: Titer of the ZnSO4 standard
solution
Analysis cZnSO4: Concentration of the ZnSO4
If necessary, dilute the acidic sample standard solution in mol/L
solution, which should not contain more MGa/In: Molar mass of gallium and indium;
3+ 3+
than 60 mg Ga and/or 100 mg In , 69.723 g/mol and 114.818 g/mol,
with dist. H2O to approx. 100 mL and respectively
degas. Add 5 mL acetate buffer, 10 mL VS: Sample size in mL
c(Na2EDTA) = 0.1 mol/L, and 2 mL indi-
cator solution and titrate with c(ZnSO4) =
0.1 mol/L past the first equivalence
point.

Figure 60 Example of a photometric titration

curve of gallium with the Optrode at 610 nm

Further literature on this topic is given in

• Titration Application Note AN-T-158 – Determination of gallium using
automatic photometric titration
 Hg – Mercury

66 General
Mercury forms relatively strong complexes The Cu-ISE cannot be used for potentio-
2+
and is thus suitable for titration. However, metric indication because Hg poisons
2+ +
it must be present as Hg because Hg the crystal membrane, making the elec-
2+
disproportionates into Hg and metallic trode inoperable.
2+
Hg in the presence of, e.g., EDTA. Hg
can be masked relatively easily. It can be Hg complexes are serious environmental
precipitated as HgI2 by adding potassium pollutants! The solutions used during the
iodide solution, which liberates the corre- titration should thus be collected and
sponding amount of complexing agent detoxified. We recommend the follow-
(e.g., EDTA). This allows consecutive titra- ing procedure for this:
tions, for example, in the presence of
2+
Cu . The collected solutions are made alkaline,
for example, by adding NaOH. Excess
2+
In some pharmaceutical formulations, Hg sodium sulfide solution is then added to
can be titrated directly without having to the stirred mixture. The precipitated (very
separate it from the organic matrix before- sparingly soluble) Hg2S can be collected
hand. and disposed of separately.

Table of equivalent masses

1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Hg 200.590 20.059
HgCl2 271.496 27.150
Hg(NO3)2 324.600 32.460
Hg(NO3)2∙H2O 342.615 34.262
HgO 216.589 21.659
HgSO4 296.653 29.665
Photometric with the Optrode at
502 nm
67
Reagents Calculation
• Titrant 1: c(Na2EDTA) = 0.1 mol/L (VEDTA f1 c EDTA - VEP1 f2 c ZnSO 4 ) MHg
• Titrant 2: c(ZnSO4) = 0.1 mol/L; Hg =
VS
dissolve 28.8 g ZnSO4∙7H2O in dist.
H2O, mix, and make up to 1 L with βHg: Mercury content of the sample
dist. H2O. in g/L
• Ammonia buffer, pH = 10: dissolve VEDTA: Added volume of EDTA standard
54 g NH4Cl in approx. 200 mL dist. solution in mL
H2O and add 350 mL w/w(NH3) = f1: Titer of the EDTA standard solution
25%. Mix, and make up to 1 L with cEDTA: Concentration of the EDTA
dist. H2O. standard solution in mol/L
• Sodium hydroxide: c(NaOH) = VEP1: Volume of ZnSO4 standard solution
1 mol/L consumed up to the first
• Indicator solution: Eriochrome Black T; equivalence point in mL
dissolve 100 mg Eriochrome Black T f2: Titer of the ZnSO4 standard
in 100 mL ethanol. solution
cZnSO4: Concentration of the ZnSO4
Analysis standard solution in mol/L
If necessary, dilute the acidic sample solu- MHg: Molar mass of mercury;
tion, which should not contain more than 200.590 g/mol
2+
75 mg Hg , with dist. H2O to approx. VS: Sample size in mL
50 mL. Add 5.00 mL c(Na2EDTA) =
0.1 mol/L and neutralize the solution with
c(NaOH) = 1 mol/L to approx. pH 5–7.
Add 5 mL ammonia buffer and 1 mL
indicator solution, and titrate with
c(ZnSO4) = 0.1 mol/L past the first equiva-
lence point.

Figure 61 Photometric titration curve of

mercury with the Optrode at 502 nm
Further literature on this topic is given in
• Titration Application Note AN-T-144 – Mercury analysis using automatic
photometric titration
 Mg – Magnesium

68 General
Along with calcium, magnesium was one
2+
Interfering metals, such as Cu , Ni ,
2+

2+ 3+ 2+
of the first metals to be titrated com- Co , Fe , and Mn can be eliminated
plexometrically. The titration is generally by precipitating them with Na2S solu-
carried out in a buffered ammoniacal tion. The sample should then be filtered
solution at pH = 10 and can be per- and the excess sulfides destroyed by
2+
formed directly. Since Mg is very often oxidizing them to sulfate (e.g., with
2+
accompanied by Ca , please refer to the H2O2).
separate determination of the two metals
in the section on "Water hardness".

Table of equivalent masses

1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent

Formula Molar mass in g/mol Equivalent in mg

Mg 24.305 2.431
Mg(CH3COO)2∙4H2O 214.450 21.445
MgCO3 84.318 8.432
MgCl2 95.211 9.521
MgCl2∙6H2O 203.302 20.330
Mg(NO3)2 148.315 14.832
Mg(NO3)2∙6H2O 256.406 25.641
MgO 40.304 4.030
Mg(OH)2 58.320 5.832
MgSO4 120.360 12.036
MgSO4∙H2O 138.380 13.838
MgSO4∙7H2O 246.470 24.647

Potentiometric with the Cu-ISE

Reagents Analysis
• Titrant: c(Na2EDTA) = 0.1 mol/L If necessary, dilute acidic sample solutions
• Cu complex solution: c[Cu(NH4)2EDTA] with dist. H2O to approx. 50 mL and pre-
= 0.1 mol/L (e.g., Merck No. 105217) neutralize to approx. pH 4–5 with
• Ammonia buffer, pH = 10: Dissolve w/w(NH3) = 25%. Add 0.5 mL Cu com-
54 g NH4Cl in approx. 200 mL dist. plex solution and 5 mL ammonia buffer,
H2O and add 350 mL w/w(NH3) = wait for 10–20 s while stirring, and titrate
25%. Mix and make up to 1 L with with c(Na2EDTA) = 0.1 mol/L past the first
dist. H2O. equivalence point.
• Ammonia: w/w(NH3) = 25%
Calculation
VEP1 f c EDTA MMg
69
Mg =
VS

βMg: Magnesium content of the sample

in g/L
VEP1: Volume of EDTA standard solution
consumed up to the first
equivalence point in mL
f: Titer of the EDTA standard solution
cEDTA: Concentration of the EDTA
Figure 62 Example of a potentiometric
standard solution in mol/L
titration curve of magnesium with the Cu-ISE
MMg: Molar mass of magnesium;
24.305 g/mol
VS: Sample size in mL

Further literature on this topic is given in

• Application Bulletin AB-101 – Complexometric titrations with the Cu-ISE
• Titration Application Note AN-T-128 – Automatic determination of magnesium
in aqueous solution with the Cu-ISE

Photometric with the Optrode at

610 nm
Reagents Analysis
• Titrant: c(Na2EDTA) = 0.1 mol/L If necessary, dilute acidic sample solutions
• Ammonia buffer, pH = 10: Dissolve with dist. H2O to approx. 100 mL and
54 g NH4Cl in approx. 200 mL dist. preneutralize to approx. pH 4–5 with
H2O and add 350 mL w/w(NH3) = w/w(NH3) = 25%. Add 5 mL ammonia
25%. Mix and make up to 1 L with buffer and 0.5 mL indicator solution, and
dist. H2O. titrate with c(Na2EDTA) = 0.1 mol/L past
• Ammonia: w/w(NH3) = 25% the first equivalence point.
• Indicator solution: Eriochrome Black T;
dissolve 100 mg Eriochrome Black T
in 100 mL ethanol.
70 Calculation
VEP1 f c EDTA MMg
Mg =
VS

βMg: Magnesium content of the sample

in g/L
VEP1: Volume of EDTA standard solution
consumed up to the first
equivalence point in mL
f: Titer of the EDTA standard solution
Figure 63 Photometric titration curve of
cEDTA: Concentration of the EDTA
magnesium with the Optrode at 610 nm
standard solution in mol/L
MMg: Molar mass of magnesium;
24.305 g/mol
VS: Sample size in mL

Further literature on this topic is given in

• Application Bulletin AB-125 – Simultaneous determination of calcium, magne-
sium, and alkalinity by complexometric titration with potentiometric or photo-
metric indication in water and beverage samples

Mn – Manganese
General
2+
Manganese behaves very similarly to Mg to prevent precipitation of Mn(OH)2. This
3+ 3+ 2+ 2+
in complexometric titrations. However, also masks Fe and Al ions. Co , Ni ,
2+ 2+ 2+ 2+
account must be taken of the fact that Cu , Zn , Cd , Hg , and the Pt-group
2+
only Mn can be titrated. In alkaline solu- metals can be masked with KCN in case
2+ 2+
tion, Mn(OH)2 forms first and then, by of photometric titration. Ca and Mg
reaction with atmospheric oxygen, are also determined. If they are present,
Mn(OH)3. Therefore, some precautions manganese must be separated before-
must be taken when performing a photo- hand, for example, as MnO2. (MnO2 can
metric titration. Ascorbic acid is added to be reduced by oxalic acid).
3+
the sample solution to reduce any Mn ,
as well as ­triethanolamine hydrochloride
Table of equivalent masses
1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
71
Formula Molar mass in g/mol Equivalent in mg
Mn 54.938 5.494
MnCO3 114.974 11.497
MnCl2 125.844 12.584
MnCl2∙4H2O 197.905 19.791
Mn(NO3)2∙4H2O 251.009 25.101
MnO 70.937 7.094
MnO2 86.937 8.694
Mn(OH)2 88.953 8.895
MnSO4 151.000 15.100
MnSO4∙H2O 169.015 16.902
MnSO4∙4H2O 223.060 22.306

Potentiometric with the Cu ISE

Reagents Calculation
• Titrant 1: c(Na2EDTA) = 0.1 mol/L (VEDTA f1 c EDTA - VEP1 f2 c CuSO 4 ) MMn
• Titrant 2: c(CuSO4) = 0.1 mol/L; Mn =
VS
dissolve 24.97 g CuSO4∙5H2O in dist.
H2O, mix, and make up to 1 L with βMn: Manganese content of the sample
dist. H2O. in g/L
• Ammonia buffer: Dissolve 54 g NH4Cl VEDTA: Added volume of EDTA standard
in approx. 200 mL dist. H2O and add solution in mL
350 mL w/w(NH3) = 25%. Mix and f1: Titer of the EDTA standard solution
make up to 1 L with dist. H2O. cEDTA: Concentration of the EDTA
• Ammonia: w/w(NH3) = 25% standard solution in mol/L
VEP1: Volume of CuSO4 standard
Analysis solution consumed up to the first
If necessary, dilute the acidic sample equivalence point in mL
solution, which should not contain more f2: Titer of the CuSO4 standard
2+
than 45 mg Mn , with dist. H2O to solution
approx. 50 mL and then, if necessary, cCuSO4: Concentration of the CuSO4
preneutralize to pH 3–4 with w/w(NH3) = standard solution in mol/L
25%. Add 10 mL c(Na2EDTA) = 0.1 mol/L MMn: Molar mass of manganese;
and 5 mL ammonia buffer, and titrate 54.938 g/mol
with c(CuSO4) = 0.1 mol/L past the first VS: Sample size in mL
equivalence point.
72 Further literature on this topic is
given in
• Application Bulletin AB-101 –
Complexometric titrations with the
Cu-ISE
• Titration Application Note AN-T-120
– Automatic manganese determina-
tion in aqueous solution using the
ion-selective copper electrode (Cu-ISE)

Figure 64 Potentiometric titration curve of

manganese with the Cu-ISE

Photometric with the Optrode at

610 nm
Reagents Analysis
• Titrant: c(Na2EDTA) = 0.1 mol/L To the acidic sample solution, add 10 mL
• Triethanolamine hydrochloride: w/w(C6H15NO3∙ HCl) = 20% and a spatula
w/w(C6H15NO3 ∙ HCl) = 20%; dissolve tip of ascorbic acid. If necessary, dilute to
100 g C6H15NO3 ∙ HCl in dist. H2O, approx. 75 mL with dist. H2O. Preneutralize
mix, and make up to 500 mL with with c(NaOH) = 1 mol/L to approx. pH 7.
dist. H2O. Add 5 mL ammonia buffer and 0.25 mL
• Ascorbic acid: (vitamin C), p.a. indicator solution, and titrate with
• Ammonia buffer: Dissolve 54 g NH4Cl c(Na2EDTA) = 0.1 mol/L past the first
in approx. 200 mL dist. H2O and add equivalence point.
350 mL w/w(NH3) = 25%. Mix and
make up to 1 L with dist. H2O.
• Sodium hydroxide: c(NaOH) =
1 mol/L
• Indicator solution: Eriochrome Black T;
dissolve 100 mg Eriochrome Black T
in 100 mL ethanol.
Calculation
VEP1 f c EDTA MMn
73
Mn =
VS

βMn: Manganese content of the sample

in g/L
VEP1: Volume of EDTA standard solution
consumed up to the first
equivalence point in mL
f: Titer of the EDTA standard solution
Figure 65 Example of a photometric
cEDTA: Concentration of the EDTA
titration curve of manganese with the
standard solution in mol/L Optrode at 610 nm
MMn: Molar mass of manganese;
54.938 g/mol
VS: Sample size in mL

Further literature on this topic is given in

• Titration Application Note AN-T-141 – Automatic photometric determination of
manganese using the Optrode

Ni – Nickel

General
2+
Nickel can be titrated very successfully in Ni can be separated from interfering
2+
ammoniacal solutions. However, alkaline metal ions (exception Pd ) by precipitat-
earth ions are also determined if they are ing it with dimethylglyoxime. The precipi-
present in large quantities. High concen- tate is dissolved in conc. HCl, treated with
3+ 3+ 2+
trations of Al , Fe , and Mn can be excess Na2EDTA, and the pH is adjusted
masked by adding triethanolamine. to 10 with NH3 before being titrated with,
2+
for example, a Zn standard solution and
Eriochrome Black T indicator.
74 Table of equivalent masses
1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Ni 58.693 5.869
NiCO3 118.702 11.870
NiCl2 129.599 12.960
NiCl2∙6H2O 237.691 23.769
Ni(NO3)2 182.703 18.270
Ni(NO3)2∙6H2O 290.795 29.080
NiO 74.693 7.469
NiSO4 154.756 15.476
NiSO4∙7H2O 280.863 28.086

Potentiometric with the Cu-ISE

Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L VEP1 f c EDTA MNi
• Cu complex solution: Ni =
VS
c[Cu(NH4)2EDTA] = 0.1 mol/L
(e.g., Merck No. 105217) βNi: Nickel content of the sample in g/L
• Ammonia buffer: Dissolve 54 g NH4Cl VEP1: Volume of EDTA standard solution
in approx. 200 mL dist. H2O and add consumed up to the first
350 mL w/w(NH3) = 25%. Mix and equivalence point in mL
make up to 1 L with dist. H2O. f: Titer of the EDTA standard solution
• Sodium hydroxide: c(NaOH) = cEDTA: Concentration of the EDTA
1 mol/L standard solution in mol/L
MNi: Molar mass of nickel;
Analysis 58.693 g/mol
If necessary, dilute the sample solution VS: Sample size in mL
with dist. H2O to approx. 50 mL and pre-
neutralize, if necessary, to pH 4–5 with
c(NaOH) = 1 mol/L. Add 5 mL ammonia
buffer and 0.5 mL Cu complex solution,
wait for 10–20 s while stirring, and titrate
with c(Na2EDTA) = 0.1 mol/L past the first
equivalence point.
 Further literature on this topic is
given in
75
• Application Bulletin AB-101 –
Complexometric titrations with the
Cu-ISE
• Titration Application Note AN-T-129
– Automatic determination of nickel
in aqueous solution with the Cu-ISE

Figure 66 Potentiometric titration curve of

nickel with the Cu-ISE

Photometric with the Optrode at

574 nm
Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L VEP1 f c EDTA MNi
• Ammonia buffer: dissolve 54 g NH4Cl Ni =
VS
and 350 mL w/w(NH3) = 25% in dist.
H2O, mix, and make up to 1 L with βNi: Nickel content of the sample in g/L
dist. H2O. VEP1: Volume of EDTA standard solution
• Sodium hydroxide: c(NaOH) = consumed up to the first
1 mol/L equivalence point in mL
• Indicator solution: murexide; dissolve f: Titer of the EDTA standard solution
0.2 g murexide (mixed 1:100 with cEDTA: Concentration of the EDTA
NaCl) in 50 mL dist. H2O. standard solution in mol/L
MNi: Molar mass of nickel;
Analysis 58.693 g/mol
If necessary, dilute the sample solution VS: Sample size in mL
with dist. H2O to approx. 50 mL and then
preneutralize, if necessary, to pH 4–5 with
c(NaOH) = 1 mol/L. Add 5 mL ammonia
buffer and 5 mL indicator solution, and
then titrate with c(Na2EDTA) = 0.1 mol/L
past the first equivalence point. Titrate
slowly when close to the color change.
76 Further literature on this topic is
given in
• Titration Application Note AN-T-150
– Determination of nickel using
automatic photometric titration

Figure 67 Example of a photometric titration

curve of nickel with the Optrode at 574 nm

Pb – Lead

General
2+
Complexometric titration of Pb can be the effective stability constant of the indi-
carried out directly, via displacement reac- cator (Eriochrome Black T) or of the
tions (e.g., with MgEDTA), or by back PbEDTA complex would be lowered too
titration in alkaline solution. Sulfates much.
should not be present, if possible, because
2+
Pb precipitates as PbSO4 in their pres- Furthermore, photometric titration in
ence. The alkaline solution should be slightly acidic medium enables determina-
adjusted to pH 10 with NaOH, and tar- tion of Pb in the presence of phosphate
trate should be used as an auxiliary com- and alkaline earth ions and is also suitable
plexing agent. This prevents precipitation for determinations in low concentration
2+
of Pb as Pb(OH)2. However, the tartrate ranges.
excess must not be too large otherwise
Table of equivalent masses
1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
77
Formula Molar mass in g/mol Equivalent in mg
Pb 207.200 20.720
Pb(CH3COO)2 325.288 32.529
Pb(CH3COO)2∙3H2O 379.334 37.933
Pb(CH3CH2)4 323.444 32.344
PbCO3 267.209 26.721
PbCl2 278.106 27.811
PbO 223.199 22.320
Pb(OH)2 241.215 24.122
Pb3(PO4)2 811.543 27.051
PbSO4 303.263 30.326
Pb(NO3)2 331.210 33.121

Potentiometric with the Cu-ISE

Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L VEP1 f c EDTA MPb
• Cu complex solution: c[Cu(NH4)2EDTA] Pb =
VS
= 0.1 mol/L (e.g., Merck No. 105217)
• Ammonia buffer: Dissolve 54 g NH4Cl βPb: Lead content of the sample in g/L
in approx. 200 mL dist. H2O and add VEP1: Volume of EDTA standard solution
350 mL w/w(NH3) = 25%. Mix and consumed up to the first
make up to 1 L with dist. H2O. equivalence point in mL
• Sodium hydroxide: c(NaOH) = f: Titer of the EDTA standard solution
2 mol/L cEDTA: Concentration of the EDTA
• Ammonium tartrate solution: standard solution in mol/L
β((NH4)2C4H4O6) = 250 g/L MPb: Molar mass of lead;
207.200 g/mol
Analysis VS: Sample size in mL
If necessary, preneutralize acidic sample
solutions to pH 4–5 with c(NaOH) =
2 mol/L. Add 50 mL ammonium tartrate,
1 mL ammonia buffer, 0.5 mL Cu com-
plex solution, and 5 mL c(NaOH) =
2 mol/L, wait for 30 s while stirring, and
then titrate with c(Na2EDTA) = 0.1 mol/L
past the first equivalence point.
78 Further literature on this topic is
given in
• Application Bulletin AB-101 –
Complexometric titrations with the
Cu-ISE
• Titration Application Note AN-T-130
– Automatic determination of lead in
aqueous solution with the Cu-ISE

Figure 68 Potentiometric titration curve of

lead with the Cu-ISE

Photometric with the Optrode at

574 nm
Reagents Calculation
• Titrant 1: c(Na2EDTA) = 0.1 mol/L (VEDTA f1 c EDTA - VEP1 f2 c ZnSO 4 ) MPb
• Titrant 2: c(ZnSO4) = 0.1 mol/L; dis- Pb =
VS
solve 28.8 g ZnSO4∙7H2O in dist. H2O,
mix, and make up to 1 L with dist. βPb: Lead content of the sample in g/L
H2O. VEDTA: Added volume of EDTA standard
• Acetate buffer: Dissolve 123 g sodi- solution in mL
um acetate in approx. 200 mL dist. f1: Titer of the EDTA standard solution
H2O and add 50 mL glacial acetic cEDTA: Concentration of the EDTA
acid. Mix and make up to 1 L with standard solution in mol/L
dist. H2O. VEP1: Volume of ZnSO4 standard solution
• Sodium hydroxide: c(NaOH) = consumed up to the first
1 mol/L equivalence point in mL
• Indicator solution: Xylenol orange; f2: Titer of the ZnSO4 standard
dissolve 50 mg xylenol orange solution
disodium salt in 50 mL dist. H2O. cZnSO4: Concentration of the ZnSO4
standard solution in mol/L
Analysis MPb: Molar mass of lead;
If necessary, dilute the sample solution 207.200 g/mol
with dist. H2O to approx. 50 mL and VS: Sample size in mL
adjust, if necessary, to pH 5–6 with
c(NaOH) = 1 mol/L. Add 10 mL acetate
buffer, 5 mL c(Na2EDTA) = 0.1 mol/L, and
0.5 mL indicator solution. Allow to react
for 1 min, and titrate with c(ZnSO4) =
0.1 mol/L past the first equivalence point.
 Further literature on this topic is
given in
79
• Titration Application Note AN-T-140
– Automated photometric determi-
nation of lead using the Optrode

Figure 69 Example of a photometric titration

curve of lead with the Optrode at 574 nm

Pd – Palladium
General
There is relatively little data in the litera- back-titrated with xylenol orange indica-
4+ 3+
ture on complexometric titration of the tor and Th at pH = 3.0 or Tl at pH 4 to
2+
platinum group metals. Pd is usually 5. In our example, we titrate at pH 4–5
determined by back titration of excess with xylenol orange indicator using the
2+
EDTA. This excess is titrated with a suit- less toxic Zn as the titrant.
able standard solution, for example, with
2+
Zn in alkaline solution and Eriochrome Since Pt forms very stable complexes
2+
Black T indicator. (In this case, the solu- with chloride ions, Pd can be deter-
tion must be made alkaline with NaOH mined alongside Pt without interference
2+
because Pd reacts with ammonia to in the presence of chloride ions.
form very stable, non-titratable Pd-amine
complexes). The excess EDTA is then

Table of equivalent masses

1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Pd 106.420 10.642
PdCl2 177.326 17.733
PdCl2∙2H2O 213.357 21.336
PdCl4 248.232 24.823
PdCl6 319.138 31.914
Pd(NO3)2 230.430 23.043
PdO 122.419 12.242
PdSO4 202.483 20.248
PdSO4∙2H2O 238.513 23.851
80 Photometric with the Optrode at
610 nm
Reagents Calculation
• Titrant 1: c(Na2EDTA) = 0.1 mol/L (VEDTA f1 c EDTA - VEP1 f2 c ZnSO 4 ) MPd
• Titrant 2: c(ZnSO4) = 0.1 mol/L; Pd =
VS
dissolve 28.8 g ZnSO4∙7H2O in approx.
500 mL dist. H2O. Add 0.5 mL βPd: Palladium content of the sample
w/w(H2SO4) = 96%, mix, and make up in g/L
to 1 L with dist. H2O. Mix 100 mL of VEDTA: Added volume of EDTA standard
this solution, and make up to 1 L with solution in mL
dist. H2O. f1: Titer of the EDTA standard solution
• Acetate buffer, pH = 4.7: Dissolve cEDTA: Concentration of the EDTA
123 g sodium acetate in approx. 200 standard solution in mol/L
mL dist. H2O and add 50 mL glacial VEP1: Volume of ZnSO4 standard solution
acetic acid. Mix and make up to 1 L consumed up to the first
with dist. H2O. equivalence point in mL
• Indicator solution: Xylenol orange; f2: Titer of the ZnSO4 standard
dissolve 100 mg xylenol orange solution
disodium salt in 100 mL dist. H2O. cZnSO4: Concentration of the ZnSO4
standard solution in mol/L
Analysis MPd: Molar mass of palladium;
If necessary, dilute the acidic sample solu- 106.420 g/mol
tion, which should not contain more than VS: Sample size in mL
2+
20 mg Pd , with dist. H2O to approx.
100 mL and degas. Add 10 mL acetate
buffer, 5 mL c(Na2EDTA) = 0.1 mol/L, and
10 mL indicator solution, and titrate with
c(ZnSO4) = 0.1 mol/L past the first equiva-
lence point.

Figure 70 Photometric titration curve of

palladium with the Optrode at 610 nm

Further literature on this topic is given in

• Titration Application Note AN-T-145 – Determination of palladium using
automatic photometric titration
Sn – Tin

General
Both valence states of tin (II and IV) form impossible to titrate. Preneutralization
81
stable complexes, for example with EDTA, must be carried out carefully with vigor-
which can be titrated in acidic solutions ous stirring.
owing to their high complex formation
2+
constants (log Kf = approx. 22). Interfering Pb ions are usually precipi-
tated as PbSO4 and then removed from
Furthermore, acidic solutions should also the solution by filtration.
be used because tin ions form stable
hydroxo complexes that are difficult or

Table of equivalent masses

1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Sn 118.710 11.871
SnCl2 189.616 18.962
SnCl2∙2H2O 225.647 22.565
SnCl4 260.522 26.052
SnCl4∙5H2O 350.598 35.060
SnF2 156.707 15.671
SnF4 194.704 19.470
SnO 134.709 13.471
SnO2 150.709 15.071
Sn(OH)2 152.725 15.273
Sn(OH)4 186.739 18.674
SnSO4 214.773 21.477

Photometric with the Optrode at

574 nm
Reagents
• Titrant: c(Na2EDTA) = 0.1 mol/L metric flask and make up to the mark
• Buffer: pH = 2.1; dissolve 5.88 g citric with dist. H2O.
acid and 3.58 g NaCl in 700 mL • Indicator solution: Xylenol orange;
c(HCl) = 0.1 mol/L, and then adjust dissolve 25 mg xylenol orange
to pH 2.1 with c(NaOH) = 2 mol/L. disodium salt in 100 mL dist. H2O.
Transfer the solution into a 1 L volu-
82 Analysis
To the very acidic sample solution, which
should not contain more than 100 mg
2+ 4+
Sn or Sn , add 10 mL of buffer pH 2.1
and 80 mL deion. H2O. Next, add 0.5 mL
indicator solution, and titrate with
c(Na2EDTA) = 0.1 mol/L past the first
equivalence point.

Calculation
Figure 71 Example of a photometric titration
VEP1 f c EDTA MSn curve of tin with the Optrode at 574 nm
Sn =
VS
βSn: Tin content of the sample in g/L
VEP1: Volume of EDTA standard solution Further literature on this topic is
consumed up to the first given in
equivalence point in mL • Titration Application Note AN-T-146
f: Titer of the EDTA standard solution – Automatic determination of tin
cEDTA: Concentration of the EDTA using photometric titration
standard solution in mol/L
MSn: Molar mass of tin;
118.710 g/mol
VS: Sample size in mL

Th – Thorium

General
Thorium reacts with complexing agents authors (Pribil, R., Burger, K., Milner, G.
to form very strong complexes with high W. C., Edwards, J. W.) have pointed out
complex formation constants. Thus it can that thorium can form even stronger
even be titrated at pH < 1, for example, complexes with sulfates so that EDTA can
with Na2EDTA and xylenol orange indica- be liberated again at pH > 1. They exploit-
2+ 4+
tor. Divalent cations (except Hg ) do not ed this situation to determine Th in the
4+ 4+ 4+
interfere at such low pH values. Some presence of Zr . The sum of Th and Zr
is determined in the first step by back-
titrating excess EDTA at pH 2.5–2.7 with a
then approx. 2 g ammonium sulfate is
added. The thus liberated EDTA molecules
83
3+ 3+
Bi standard solution and xylenol orange are subsequently titrated with Bi stand­
indicator. Next, the fully titrated solution is ard solution and the same indicator.
acidified with HNO3 to pH 1.2–1.3, and

Table of equivalent masses

1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Th 232.038 23.204
Th(NO3)4∙5H2O 570.134 57.013
ThO2 264.037 26.404
Th(OH)4 300.067 30.007
Th(SO4)2 424.150 42.415
Th(SO4)2∙9H2O 586.290 58.629

Photometric with the Optrode at

574 nm
Reagents Calculation
• Titrant: c(Na2EDTA) = 0.1 mol/L
VEP1 f c EDTA MTh
• Acetate buffer: add 123 g sodium Th =
VS
acetate and 50 mL w/w(NH3) = 25%
to a 1 L volumetric flask, mix, and βTh: Thorium content of the sample
make up to the mark with dist. H2O. in g/L
• Indicator solution: Xylenol orange; VEP1: Volume of EDTA standard solution
dissolve 50 mg xylenol orange consumed up to the first
disodium salt in 50 mL dist. H2O. equivalence point in mL
f: Titer of the EDTA standard solution
Analysis cEDTA: Concentration of the EDTA
If necessary, dilute the sample solution standard solution in mol/L
with dist. H2O to approx. 100 mL. Degas MTh: Molar mass of thorium;
the mixture, and add 0.5 mL indicator 232.038 g/mol
solution and 10 mL acetate buffer. VS: Sample size in mL
Titrate with c(Na2EDTA) = 0.1 mol/L past
the first equivalence point.
84 Further literature on this topic is
given in
• Titration Application Note AN-T-149
– Determination of thorium using
automatic photometric titration

Figure 72 Photometric titration curve of

thorium with the Optrode at 574 nm

Tl – Thallium

General
+
Tl forms very weak complexes, whereas (mixture of HNO3 and HCl) because nitric
3+
Tl forms strong complexes with a high acid alone is insufficient. The sample is
complex formation constant. This metal treated with aqua regia and then evapo-
is thus titrated in its trivalent state. The rated until it is almost dry.
determinations are carried out in slightly
+
acidic solution so that there is no inter- Tl can be separated well from interfering
ference, for example, from any alkaline metal ions by adding some potassium
earth ions that may be present. iodide solution to the sample solution.
The thus precipitated TlI is removed by
3+
Thallium is often present in its monova- filtration and then oxidized to Tl with
+
lent state (Tl ). The best method of oxi- aqua regia as described above.
3+
dizing it to Tl is to use aqua regia
Table of equivalent masses
1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
85
Formula Molar mass in g/mol Equivalent in mg
Tl 204.383 20.438
Tl2CO3 468.775 23.439
TlCl 239.836 23.439
TlCl3 310.742 31.074
TlI 331.287 33.129
TlNO3 266.387 26.639
Tl(NO3)3 444.765 44.477
Tl2O 424.762 21.238
Tl2O3 456.764 22.838
Tl2SO4 504.829 25.241
Tl2(SO4)3∙7H2O 823.061 41.153

Potentiometric with the Cu-ISE

Reagents Calculation
• Titrant 1: c(Na2EDTA) = 0.1 mol/L (VEDTA f1 c EDTA - VEP1 f2 c CuSO 4 ) MTl
• Titrant 2: c(CuSO4) = 0.1 mol/L Tl =
VS
dissolve 24.97 g CuSO4∙5 H2O in
approx. 500 mL dist. H2O, add βT : Thallium content of the sample
l

0.5 mL w/w(H2SO4) = 96%, mix, and in g/L

make up to 1 L with dist. H2O. VEDTA: Added volume of EDTA standard
• Acetate buffer, pH = 4.7: Dissolve solution in mL
116 g ammonium acetate in approx. f1: Titer of the EDTA standard solution
200 mL dist. H2O and add 86 mL gla- cEDTA: Concentration of the EDTA
cial acetic acid. Mix and make up to standard solution in mol/L
1 L with dist. H2O. VEP1: Volume of CuSO4 standard
• Ammonia: w/w(NH3) = 25% solution consumed up to the first
equivalence point in mL
Analysis f2: Titer of the CuSO4 standard
If necessary, dilute the acidic sample solution
solution, which should not contain more cCuSO4: Concentration of the CuSO4
3+
than 150 mg Tl , with dist. H2O to standard solution in mol/L
approx. 50 mL. Add 5 mL acetate buffer MTl: Molar mass of thallium;
and 10 mL c(Na2EDTA) = 0.1 mol/L, and 204.383 g/mol
then, if necessary, adjust to pH 4.5–4.7 VS: Sample size in mL
with w/w(NH3) = 25%. Next, titrate with
c(CuSO4) = 0.1 mol/L past the first
equivalence point.
86 Analysis
To the acidic sample solution, add 5 mL
acetate buffer and, if necessary, dilute
with dist. H2O to approx. 100 mL. Degas
the mixture, add 0.5 mL indicator solu-
tion, and titrate with c(Na2EDTA) = 0.1
mol/L past the first equivalence point.

Calculation
VEP1 f c EDTA MTl
Figure 73 Potentiometric titration curve of Tl =
VS
thallium with the Cu-ISE
βTl: Thallium content of the sample
Further literature on this topic is in g/L
given in VEP1: Volume of EDTA standard solution
• Application Bulletin AB-101 – consumed up to the first
Complexometric titrations with the equivalence point in mL
Cu-ISE f: Titer of the EDTA standard solution
• Titration Application Note AN-T-122 cEDTA: Concentration of the EDTA
– Automatic thallium determination standard solution in mol/L
in aqueous solution using the ion- MTl: Molar mass of thallium;
selective copper electrode (Cu-ISE) 204.383 g/mol
VS: Sample size in mL
Photometric with the Optrode at
574 nm
Reagents
• Titrant: c(Na2EDTA) = 0.1 mol/L
• Acetate buffer, pH = 4.9: Dissolve
123 g sodium acetate in approx. 200
mL dist. H2O and add 50 mL glacial
acetic acid. Mix and make up to 1 L
with dist. H2O.
• Indicator solution: Xylenol orange;
dissolve 50 mg xylenol orange Figure 74 Example of a photometric titration
disodium salt in 50 mL H2O. curve of thallium with the Optrode at 610 nm

Metrohm Literature on this topic

• Titration Application Note AN-T-147 – Determination of thallium using
automatic photometric titration
Zn – Zinc

General
2+
The complexation behavior of Zn is very Na2EDTA is determined by means of a
87
similar to that of cadmium. It can be consecutive titration, for example, back
titrated in alkaline solution without prob- titration with MgSO4 standard solution.
2+ 2+
lems. However, Ca and Mg interfere if
present because they are also determined. However, it is much simpler to carry out
In alkaline solution, a possible strategy is the (photometric) titration at approx. pH 5
2+ 2+
to use a first titration to determine the because Ca and Mg no longer interfere.
2+ 2+ 2+
total sum of Zn plus Ca and Mg with
Eriochrome Black T indicator. Next, the
2+
Zn is masked with KCN and the liberated

Table of equivalent masses

1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Zn 65.409 6.541
Zn(CH3COO)2 183.497 18.350
Zn(CH3COO)2∙2 H2O 219.528 21.953
Zn(CN)2 117.444 11.744
ZnCO3 125.418 12.542
ZnCl2 136.315 13.632
Zn(NO3)2 189.419 18.942
Zn(NO3)2∙6 H2O 297.510 29.751
ZnO 81.408 8.142
Zn(OH)2 99.424 9.942
ZnSO4 161.472 16.147
ZnSO4∙7 H2O 287.579 28.758

Potentiometric with the Cu-ISE

Reagents
• Titrant: c(Na2EDTA) = 0.1 mol/L • Cu complex solution: c[Cu(NH4)2EDTA]
• Ammonia buffer: Dissolve 54 g NH4Cl = 0.1 mol/L (e.g., Merck No. 105217)
in approx. 200 mL dist. H2O and add • Sodium hydroxide: c(NaOH) =
350 mL w/w(NH3) = 25%. Mix and 1 mol/L
make up to 1 L with dist. H2O.
88 Analysis
If necessary, preneutralize acidic sample
solutions with c(NaOH) = 1 mol/L to
approx. pH 5–7 and, if necessary, make
up to approx. 50 mL with dist. H2O. Add
5 mL buffer solution and 1 mL Cu com-
plex solution, wait for 20 s while stirring,
and titrate with c(Na2EDTA) = 0.1 mol/L
past the first equivalence point.
Figure 75 Potentiometric titration curve of
Calculation zinc with the Cu-ISE
VEP1 f c EDTA MZn
Zn = Further literature on this topic is
VS
given in
βZn: Zinc content of the sample in g/L • Application Bulletin AB-101 –
VEP1: Volume of EDTA standard solution Complexometric titrations with the
consumed up to the first Cu-ISE
equivalence point in mL • Titration Application Note AN-T-108
f: Titer of the EDTA standard solution – Fully automated determination of
cEDTA: Concentration of the EDTA zinc(II) in aqueous solution
standard solution in mol/L
MZn: Molar mass of zinc;
65.409 g/mol
VS: Sample size in mL

Photometric with the Optrode at

610 nm
Reagents Analysis
• Titrant: c(Na2EDTA) = 0.1 mol/L If necessary, preneutralize acidic sample
• Ammonia buffer, pH = 10: dissolve solutions with c(NaOH) = 1 mol/L to
54 g NH4Cl in approx. 200 mL dist. approx. pH 5 and dilute, if necessary, with
H2O and add 350 mL w/w(NH3) = dist. H2O to approx. 50 mL. Add 5 mL
25%. Mix and make up to 1 L with ammonia buffer and 0.25 mL indicator
dist. H2O. solution, and titrate with c(Na2EDTA) =
• Indicator solution: Eriochrome Black T; 0.1 mol/L past the first equivalence point.
dissolve 100 mg each of Eriochrome
Black T and ascorbic acid in 100 mL
dist. H2O.
• Sodium hydroxide: c(NaOH) =
1 mol/L
Calculation
VEP1 f c EDTA MZn
89
Zn =
VS

βZn: Zinc content of the sample in g/L

VEP1: Volume of EDTA standard solution
consumed up to the first
equivalence point in mL
f: Titer of the EDTA standard solution
Figure 76 Example of a photometric titration
cEDTA: Concentration of the EDTA
curve of zinc with the Optrode at 610 nm
standard solution in mol/L
MZn: Molar mass of zinc;
65.409 g/mol
VS: Sample size in mL

Metrohm Literature on this topic

• Titration Application Note AN-T-090 – Photometric EDTA titration of zinc sulfate
according to Ph. Eur. and USP

Zr – Zirconium and Hf – Hafnium

General
3+ 4+
Similar to Al , zirconium has a tendency to Hafnium behaves exactly like Zr and is
form hydroxo complexes and must there- titrated using the same procedures.
3+
fore be titrated in acidic solution. Fe ions Titrimetric separation of the two metals
interfere, but they can be reduced to non- is not possible.
2+
interfering Fe ions by adding ascorbic
acid (vitamin C) (only applies to photomet- The EDTA complexes of both metals are
ric titration). relatively stable (log Kf Zr = 19.4 / log Kf Hf
= 19.1).
90 Table of equivalent masses
1 mL c(Na2EDTA) = 0.1 mol/L = x mg equivalent
Formula Molar mass in g/mol Equivalent in mg
Hf 178.490 17.849
HfCl4 320.302 32.030
Hf(NO3)4 426.510 42.651
HfO2 210.489 21.049
HfSO4 274.553 27.455
Zr 91.224 9.122
ZrCl4 233.036 23.304
ZrOCl2∙8H2O 322.252 32.225
Zr(NO3)4 339.244 33.924
Zr(NO3)4∙5H2O 429.320 42.932
ZrO2 123.223 12.322
Zr(OH)4 159.253 15.925
Zr(SO4)2 283.349 28.335
Zr(SO4)2∙4H2O 355.410 35.541

Potentiometric with the Cu-ISE

Reagents Analysis
• Titrant 1: c(Na2EDTA) = 0.1 mol/L If necessary, dilute the acidic sample solu-
• Titrant 2: c(CuSO4) = 0.1 mol/L; tion, which should not contain more than
4+ 4+
dissolve 24.97 g CuSO4∙5H2O in 70 mg Zr and/or 130 mg Hf , with dist.
approx. 500 mL dist. H2O. Add H2O to approx. 50 mL. Add 5 mL acetate
0.5 mL w/w(H2SO4) = 96%, mix, and buffer and 10 mL c(Na2EDTA) = 0.1 mol/L,
make up to 1 L with dist. H2O. and, if necessary, adjust to pH 4.7 with
• Acetate buffer, pH = 4.7: Dissolve w/w(NH3) = 25%. Allow to react for
116 g ammonium acetate in approx. approx. 1 min while stirring, and titrate
200 mL dist. H2O and add 86 mL gla- with c(CuSO4) = 0.1 mol/L past the first
cial acetic acid. Mix and make up to equivalence point.
1 L with dist. H2O.
• Ammonia: w/w(NH3) = 25%
 Calculation
91
(VEDTA f1 c EDTA - VEP1 f2 c CuSO 4 ) MZr/Hf
Zr/Hf =
VS

βZr/Hf: Zirconium or hafnium content of

the sample in g/L
VEDTA: Added volume of EDTA standard
solution in mL
f1: Titer of the EDTA standard solution
cEDTA: Concentration of the EDTA
standard solution in mol/L Figure 77 Example of a potentiometric
VEP1: Volume of CuSO4 standard titration curve of zirconium with the Cu-ISE
solution consumed up to the first
equivalence point in mL
f2: Titer of the CuSO4 standard
solution
cCuSO4: Concentration of the CuSO4
standard solution in mol/L
MZr/Hf: Molar mass of zirconium and
hafnium; 91.224 g/mol and
178.490 g/mol, respectively
VS: Sample size in mL

Further literature on this topic is given in

• Application Bulletin AB-101 – Complexometric titrations with the Cu-ISE
• Titration Application Note AN-T-123 – Automatic zirconium determination in
aqueous solution with ion-selective copper electrode (Cu-ISE)

Photometric with the Optrode at

520 nm
Reagents Analysis
• Titrant: c(Na2EDTA) = 0.1 mol/L To the acidic sample solution, which
4+
• Buffer pH = 1 (glycine / hydrochloric should not contain more than 70 mg Zr
4+
acid): e.g., Merck 109881 and/or 130 mg Hf , add 10 mL of buffer
• Indicator solution: Eriochrome Cyanine; pH 1 and 1 mL indicator solution. To the
dissolve 40 mg Eriochrome Cyanine solution, add 80 mL dist. H2O and titrate
in 100 mL dist. H2O. with c(Na2EDTA) = 0.1 mol/L past the first
equivalence point.
92 Calculation
VEP1 f c EDTA MZr/Hf
Zr/Hf =
VS

βZr/Hf: Zirconium or hafnium content of

the sample in g/L
f: Titer of the EDTA standard solution
cEDTA: Concentration of the EDTA
standard solution in mol/L
VEP1: Volume of EDTA standard solution
Figure 78 Photometric titration curve of
consumed up to the first
zirconium with the Optrode at 520 nm
equivalence point in mL
MZr/Hf: Molar mass of zirconium and
hafnium; 91.224 g/mol and
178.490 g/mol, respectively
VS: Sample size in mL

Further literature on this topic is given in

• Titration Application Note AN-T-148 – Determination of zirconium using
automatic photometric titration
Appendix

Index
93
Species Remarks Sensor Pages
Al General Cu-ISE 40–41
Al General Optrode at 610 nm 41–42
Al and Mg Alloys, antacids Cu-ISE 29–31
Al, Ca, Fe, Mg Cement, clinker Optrode at 610 nm 33–37
Ba General Cu-ISE 44
Ba General Optrode at 574 nm 45
Bi General Cu-ISE 46–47
Bi General Optrode at 520 nm 47–48
Ca General Ca-ISE 49–50
Ca General Cu-ISE 50
Ca General Optrode at 610 nm 51
Ca, Al, Fe, Mg Cement, clinker Optrode at 610 nm 33–37
Cd General Cu-ISE 52–53
Cd General Optrode at 610 nm 53–54
Co General Cu-ISE 55
Co General Optrode at 574 nm 56
Cu General Cu-ISE 58
Cu General Optrode at 520 nm 59
Fe General Cu-ISE 61
Fe General Optrode at 610 nm 62
Fe, Al, Ca, Mg Cement, clinker Optrode at 610 nm 33–37
Ga General Cu-ISE 63–64
Ga General Optrode at 610 nm 65
Hf General Cu-ISE 90–91
Hf General Optrode at 520 nm 91–92
Hg General Optrode at 502 nm 67
In General Cu-ISE 63–64
In General Optrode at 610 nm 65
Mg General Cu-ISE 68–69
Mg General Optrode at 610 nm 69–70
94 Index
Species Remarks Sensor Pages
Mg and Al Alloys, antacids Cu-ISE 29–31
Mg and Zn General Cu-ISE 31–33
Mg, Al, Ca, Fe Cement, clinker Optrode at 610 nm 33–37
Mn General Cu-ISE 71–72
Mn General Optrode at 610 nm 72–73
Ni General Cu-ISE 74–75
Ni General Optrode at 574 nm 75–76
Pb General Cu-ISE 77–78
Pb General Optrode at 574 nm 78–79
Pd General Optrode at 610 nm 80
Sn General Optrode at 574 nm 81–82
Sr General Cu-ISE 44
Sr General Optrode at 574 nm 45
Sulfate General Ca-ISE 38–39
Th General Optrode at 574 nm 83–84
Tl General Cu-ISE 85–86
Tl General Optrode at 574 nm 86
Water hardness Ca and Mg Ca-ISE 25–26
Water hardness Ca and Mg Cu-ISE 26–27
Water hardness Ca and Mg Optrode at 610 nm 27–29
Zn General Cu-ISE 87–88
Zn General Optrode at 610 nm 88–89
Zn and Mg General Cu-ISE 31–33
Zr General Cu-ISE 90–91
Zr General Optrode at 520 nm 91–92
Photometric indication of the titration equivalence point
95
Species Indicator Wavelength
Al Xylenol orange 610 nm
Al in cement Xylenol orange 610 nm
Ba Phthalein purple 574 nm
Bi Xylenol orange 520 nm
Ca HHSNN 610 nm
Ca in cement Murexide 610 nm
Cd Eriochrome Black T 610 nm
Co Murexide 574 nm
Cu PAN 520 nm
Fe Sulfosalicylic acid 610 nm
Fe in cement Sulfosalicylic acid 610 nm
Ga Xylenol orange 610 nm
Hf Eriochrome Cyanine 520 nm
Hg Eriochrome Black T 502 nm
In Xylenol orange 610 nm
Mg Eriochrome Black T 610 nm
Mg in cement Methylthymol blue 610 nm
Mn Eriochrome Black T 610 nm
Ni Murexide 574 nm
Pb Xylenol orange 574 nm
Pd Xylenol orange 610 nm
Sn Xylenol orange 574 nm
Sr Phthalein purple 574 nm
Th Xylenol orange 574 nm
Tl Xylenol orange 574 nm
Water, calcium hardness HHSNN 610 nm
Water, total hardness Eriochrome Black T 610 nm
Zn Eriochrome Black T 610 nm
Zr Eriochrome Cyanine 520 nm
 Table of figures

96 Figure 1
Figure 2
Overlaid Vis spectra of complexed and uncomplexed pyrocatechol violet
Vis absorption difference spectrum of complexed and uncomplexed pyro-
16
16
catechol violetl
Figure 3 Overlaid Vis spectra of complexed and uncomplexed dithizone 16
Figure 4 Vis absorption difference spectrum of complexed and uncomplexed dithi- 16
zone
Figure 5 Overlaid Vis spectra of complexed and uncomplexed Eriochrome Black T 17
Figure 6 Vis absorption difference spectrum of complexed and uncomplexed 17
Eriochrome Black T
Figure 7 Overlaid Vis spectra of complexed and uncomplexed calconcarboxylic acid 17
Figure 8 Vis absorption difference spectrum of complexed and uncomplexed calcon- 17
carboxylic acid
Figure 9 Overlaid Vis spectra of complexed and uncomplexed hydroxynaphthol blue 18
Figure 10 Vis absorption difference spectrum of complexed and uncomplexed 18
hydroxynaphthol blue
Figure 11 Overlaid Vis spectra of complexed and uncomplexed methylthymol blue 18
Figure 12 Vis absorption difference spectrum of complexed and uncomplexed methyl- 18
thymol blue
Figure 13 Overlaid Vis spectra of complexed and uncomplexed murexide 19
Figure 14 Vis absorption difference spectrum of complexed and uncomplexed murex- 19
ide
Figure 15 Overlaid Vis spectra of complexed and uncomplexed PAN 19
Figure 16 Vis absorption difference spectrum of complexed and uncomplexed PAN 19
Figure 17 Overlaid Vis spectra of complexed and uncomplexed phthalein purple 20
Figure 18 Vis absorption difference spectrum of complexed and uncomplexed phtha- 20
lein purple
Figure 19 Overlaid Vis spectra of complexed and uncomplexed Tiron 20
Figure 20 Vis absorption difference spectrum of complexed and uncomplexed Tiron 20
Figure 21 Overlaid Vis spectra of complexed and uncomplexed xylenol orange 21
Figure 22 Vis absorption difference spectrum of complexed and uncomplexed xylenol 21
orange
Figure 23 Overlaid Vis spectra of complexed and uncomplexed Eriochrome Cyanine R 21
Figure 24 Vis absorption difference spectrum of complexed and uncomplexed 21
Eriochrome Cyanine R
Figure 25 Titration curve of the potentio­metric titer determination of EDTA with the 23
Ca-ISE
Figure 26 Titration curve of the potentio­metric titer determination of EGTA with the 23
Ca-ISE
Figure 27 Titration curve of tap water from Herisau (Switzerland), measured with the 25
Ca-ISE
Figure 28 Titration curve of the total hardness determination 27
Figure 29 Titration curve of the calcium hardness determination 27
Figure 30 Titration curve of the total hardness determination with the Optrode at
610 nm
29
97
Figure 31 Titration curve of the calcium hardness determination with the Optrode at 29
610 nm
Figure 32 Titration curve of the potentiometric aluminum determination with 31
the Cu-ISE
Figure 33 Titration curve of the potentiometric magnesium determination with the 31
Cu-ISE
Figure 34 Titration curve of the potentiometric zinc determination with the Cu-ISE 33
Figure 35 Titration curve of the potentiometric magnesium determination with the 33
Cu-ISE
Figure 36 Titration curve of the photometric determination of calcium in cement with 37
the Optrode at 610 nm
Figure 37 Titration curve of the photometric determination of magnesium in cement 37
with the Optrode at 610 nm
Figure 38 Titration curve of the photometric determination of iron in cement with the 37
Optrode at 610 nm
Figure 39 Titration curve of the photometric determination of aluminum in cement 37
with the Optrode at 610 nm
Figure 40 Titration curve of the blank value determination with the Ca-ISE 39
Figure 41 Titration curve of the sulfate determination with the Ca-ISE 39
Figure 42 Example curve of a potentiometric aluminum determination 41
Figure 43 Example of a photometric titration curve of aluminum at 610 nm 42
Figure 44 Example of a potentiometric titration curve of barium with the Cu-ISE 44
Figure 45 Photometric titration curve of barium with the Optrode at 574 nm 45
Figure 46 Potentiometric titration curve of bismuth with the Cu-ISE 47
Figure 47 Example of a photometric titration curve of bismuth at 520 nm 48
Figure 48 Example curve of a potentiometric calcium determination with the Ca-ISE 49
Figure 49 Potentiometric titration curve of the determination of calcium in milk with 50
the Cu-ISE
Figure 50 Example of a photometric titration curve of the calcium determination with 51
the Optrode at 610 nm
Figure 51 Potentiometric titration curve of cadmium with the Cu-ISE 53
Figure 52 Photometric titration curve of the cadmium determination with the 54
Optrode at 610 nm
Figure 53 Example of a potentiometric titration curve of cobalt with the Cu-ISE 55
Figure 54 Photometric titration curve f of or cobalt with the Optrode at 574 nm 56
Figure 55 Potentiometric titration curve of copper with the Cu-ISE 58
Figure 56 Photometric titration curve of copper with the Optrode at 520 nm 59
Figure 57 Example of a potentiometric titration curve of iron with the Cu-ISE 61
Figure 58 Photometric titration curve of iron with the Optrode at 610 nm 62
Figure 59 Potentiometric titration curve of indium with the Cu-ISE 64
98 Figure 60 E xample of a photometric titration curve of gallium with the Optrode at
610 nm
65

Figure 61 Photometric titration curve of mercury with the Optrode at 502 nm 67

Figure 62 Example of a potentiometric titration curve of magnesium with the Cu-ISE 69
Figure 63 Photometric titration curve of magnesium with the Optrode at 610 nm 70
Figure 64 Potentiometric titration curve of manganese with the Cu-ISE 72
Figure 65 Example of a photometric titration curve of manganese with the Optrode 73
at 610 nm
Figure 66 Potentiometric titration curve of nickel with the Cu-ISE 75
Figure 67 Example of a photometric titration curve of nickel with the Optrode at 574 nm 76
Figure 68 Potentiometric titration curve of lead with the Cu-ISE 78
Figure 69 Example of a photometric titration curve of lead with the Optrode at 574 nm 79
Figure 70 Photometric titration curve of palladium with the Optrode at 610 nm 80
Figure 71 Example of a photometric titration curve of tin with the Optrode at 574 nm 82
Figure 72 Photometric titration curve of thorium with the Optrode at 574 nm 84
Figure 73 Potentiometric titration curve of thallium with the Cu-ISE 86
Figure 74 Example of a photometric titration curve of thallium with the Optrode at 86
610 nm
Figure 75 Potentiometric titration curve of zinc with the Cu-ISE 88
Figure 76 Example of a photometric titration curve of zinc with the Optrode at 610 nm 89
Figure 77 Example of a potentiometric titration curve of zirconium with the Cu-ISE 91
Figure 78 Photometric titration curve of zirconium with the Optrode at 520 nm 92
Subject to modifications
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