Practical Titration: Training Manual For Titrimetric Volumetric Analysis

Practical Titration
Training Manual for Titrimetric Volumetric Analysis
Prof. Dr. Leo Gros

Europa Fachhochschule Fresenius
Limburger Strasse 2
DE-65510 Idstein/Taunus (Germany)
Peter A. Bruttel and Marcus von Kloeden

Metrohm Ltd.
Oberdorfstrasse 68
CH-9101 Herisau (Switzerland)
The authors would like to express their thanks to Ms. Kathrin Sager, Metrohm Ltd.,
and Messrs. Volker Beenders and Kevin Mller, Europa Fachhochschule Fresenius,
for carrying out the practical work.
All rights reserved, including those of translation.

Printed by Metrohm Ltd., CH-9101 Herisau, Switzerland
8.029.5003 2005-05
Titrimetric analysis with Titrino or Titrando
Practical of Titration
Preface
Recently a college lecturer was told that in the Geological Institute of a University the determinations of content were basically to be carried out by instrumental methods alone, for example atomic spectroscopy. The old-fashioned wet chemistry was no longer to be used.
How good it is that students with experience in industrial laboratories can inform their teachers during their courses about all the applications in which the old-fashioned but still young
titration method is being used in practice today.
This small book is based on the many years of experience gained by Metrohm in the development of instruments and applications. Peter Bruttel and Marcus von Kloeden have worked
out the applications and collected them. The Europa Fachhochschule Fresenius (EFF) Idstein, Germany, previously the Chemieschule Fresenius Wiesbaden, can look back on more
than 150 years of practice-oriented teaching. Students of the EFF have tried out the practical
examples. Since 1981 Leo Gros has taught analytical techniques at the EFF. Marcus von Kloeden was one of his students and became acquainted with Metrohm during a practical course
abroad. The authors would like to thank Jan Volker Geil, Vice President, Metrohm Ltd., and
himself a graduate of the EFF, for the many different ways in which he supported this project,
as well as the EFF students Kevin Mller and Volker Beenders, who carried out the titrations.
The authors would like to thank Heinz Gorbauch, their collegue of the Fresenius Institute and
graduate of the EFF for his critical reading and additional remarks.
This Tutorial is primarily intended for training purposes but can also, of course, be used to
advantage in any laboratory. It is intended to explain the theory in a simple manner and, by
using practical examples, demonstrate just how versatile and accurate titrimetric analyses
are. The individual methods and procedures also provide the reader with many useful tips
and explanations. This book is a practical manual not a detailed textbook and cannot and
will not replace textbooks (see list of literature references in the Appendix)! Nevertheless, in
order to be able to understand the practical applications better, some of the theory concerning types of reaction, substances and methods is briefly presented.
The titrations can be carried out with any Metrohm titrator (Titrando, Titrino, Titroprocessor)
as a matter of course.
Safety aspects
Please note that this manual contains no information about the dangers related to the toxicity of the chemicals used nor about their disposal and handling. Please obtain the necessary
knowledge from other sources. The chemicals used can be obtained from any qualified supplier. Any mention of manufacturers in the practical part is just meant to indicate with which
chemicals the experiments were carried out.
We hope that you will have a lot of pleasure and success with your work,
Your Metrohm Ltd. and Europa Fachhochschule Fresenius (EFF)
Table of contents
I.
Theoretical part
I.1
I.2
I.3
I.4
I.5
Introduction................................................................................................................... 7
Titration reactions ......................................................................................................... 9
Indication methods..................................................................................................... 25
Electrodes................................................................................................................... 36
Titrants: preparation and titer determination.............................................................. 44
II.
Practical part
II. 1
Acid-base titrations and methods, aqueous ............................................................
II. 1.1 Electrode calibration and electrode handling ............................................................ 55

II. 1.2 Titer determination of hydrochloric acid, c(HCl) = 0.1 mol/L with Tris ..................... 57
II. 1.3 Titer determination of hydrochloric acid, c(HCl) = 0.1 mol/L and validation
of the titrator ............................................................................................................... 58
II. 1 4 Titration of NaOH........................................................................................................ 59
II. 1.5 Titration of NaOH containing a small amount of Na2CO3 .......................................... 61
II. 1.6 Titration of sulfuric acid (H2SO4)................................................................................. 63
II. 1.7 Titration of acetic acid, DET and endpoint titration (SET) ......................................... 65
II. 1.8 Titration of phosphoric acid (H3PO4), DET and MET ................................................. 68
II. 1.9 Titration of boric acid (H3BO3) with and without addition of mannitol ....................... 71
II. 1.10 Titration of the acid and base capacity (p and m values) with fixed EPs and
calculation of the carbonate hardness....................................................................... 74
II. 1.11 Formol number in vegetable juices............................................................................ 77
II. 2
Acid-base titrations and methods, non-aqueous
II. 2.1
II. 2.2
II. 2.3
II. 2.4
II. 2.5
II. 2.6
II. 2.7
II. 2.8
II. 2.9
General and additional remarks about non-aqueous titrations................................. 79

Titer determination of perchloric acid, c(HClO4) = 0.1 mol/L in glacial acetic acid.. 80
Titer determination of alcoholic c(KOH) = 0.1 mol/L................................................. 82
Titration of nitrating acid (HNO3 / H2SO4 mixture)...................................................... 84
Acid number in petrochemical products with alcoholic KOH.................................... 86
Determining the ephedrine hydrochloride content according to Pharm. Europe..... 88
Determining the ephedrine hydrochloride content according to USP 24/25 ............ 90
Benzoic acid in H2O, ethanol, acetone, MIBK and acetonitrile.................................. 92
Aniline in H2O, ethanol, acetone, dioxan/IPA and acetonitrile ................................... 93
II. 3
Precipitation titrations...............................................................................................
II. 3.1
II. 3.2
II. 3.3
II. 3.4
II. 3.5
II. 3.6
II. 3.7
II. 3.8
Titer determination of c(AgNO3) = 0.1 mol/L............................................................. 95

Chloride (NaCl) in meat bouillon................................................................................ 97
Chloride in drinking water .......................................................................................... 99
Sulfide in wastewater................................................................................................ 100
Cyanide in wastewater ............................................................................................. 102
Mixture of chloride, bromide and iodide with and without added acetone............. 104
Cationic surfactant in mouth rinses.......................................................................... 106
Anionic surfactants and soaps in washing powder, potentiometric
two-phase titration .................................................................................................... 108
II. 3.9 Calibration factor for nonionic surfactants ............................................................... 111
II. 3.10 Nonionic surfactants in household cleaners............................................................ 113
II. 4
Redox titrations and methods
II. 4.1
II. 4.2
II. 4.3
II. 4.4
II. 4.5
II. 4.6
II. 4.7
II. 4.8
II. 4.9
II. 4.10
II. 4.11
Iodometry (iodine/thiosulfate) .................................................................................. 115

Chromatometry......................................................................................................... 118
Cerimetry .................................................................................................................. 120
Permanganatometry ................................................................................................. 122
Thiosulfate with iodine, potentiometric, biamperometric and bivoltametric
titration ...................................................................................................................... 124
Bromine index in petrochemical products ............................................................... 127
Free sulfurous acid (SO2) in wine............................................................................. 129
Oxygen content in water, Winkler method ............................................................... 130
Hydrogen peroxide (H2O2) in disinfectants, with KMnO4 ......................................... 134
Diazotization titration with NaNO2 ............................................................................ 136
Bromatometry........................................................................................................... 138
II. 5
Complexometric and chelometric methods
II. 5.1
II. 5.2
II. 5.3
II. 5.4
II. 5.5
II. 5.6
II. 5.7
II. 5.8
II. 5.9
Titer determination of c(Na2EDTA) = 0.1 mol/L with CaCO3 ................................... 141

Ca and sulfate content in tap water with the Ca ISE................................................ 143
Ca and Mg content (total hardness) in water with the Ca ISE................................. 145
Total hardness in drinking water with the Ca ISE .................................................... 147
Total hardness in drinking water with the Spectrosense 610 nm ............................ 149
Nickel in a nickel electroplating bath with the Cu ISE ............................................. 151
Calcium in milk with the Cu ISE ............................................................................... 153
Aluminum in antacids with the Spectrosense 610 nm............................................. 155
Iron in cement with the Spectrosense 610 nm ........................................................ 157
III.
Appendix
Further and/or cited literature standardized methods .......................................... 159
275 years the history of titrimetric analysis ........................................................... 162
I. 1 Introduction: titration means counting!

Together with gravimetry, titration is one of the oldest analytical methods. Both belong to a
group of analytical methods that is based on chemical reaction.
In a titration one determines the volume of a standard solution (titrant) that is necessary for
complete chemical reaction with the analyte. The titrant contains a known amount of a particular substance.
Since Loschmidt and Avogadro we know that one gram molecule of a substance contains a
defined number of particles. A standard solution is produced by dissolving a particular weight
of a substance in a solvent. Each volume fraction of this standard solution contains a defined
number of particles of the dissolved substance. This means that measuring the volume of a
standard solution is a method of counting particles: Titration means counting!
Despite many new, mainly physical instrumental analytical methods, titrimetry as a wetchemistry method still remains a standard procedure for quantitative analysis today. This is
because it has a number of specific advantages:
Titration is one of the absolute content determination methods, i.e. the result of the analysis provides direct information about the amount of substance to be determined, without
instrument or method-specific factors having to be calibrated (such as is normal in relative
methods, for example HPLC, atomic spectroscopy or UV/VIS photometry).
Titrations are easy to carry out: The equipment and the procedures to be performed are
simple. They are easy to understand the fundamentals of titrimetric methods are widely
known or can be learned in a short time.
Titrations are carried out rapidly: If the total time for setting up the workplace to obtaining the analytical result is taken into consideration, then titrimetric determinations require
much less time than other methods.
Titration is a versatile method: Numerous titration methods have been drawn up, these
range from the determination of inorganic ions up to the determination of complex organic
compounds. The analyte concentrations can range from 100% or virtually 100% (analysis
of ultrapure substances, purity determinations) down to the ppm range. Sample amounts
of a few micrograms are adequate, amounts in the gram range are also possible.
Titration supplies highly reproducible and correct results. A typical reproducibility is <1%.
In high-precision titrations values of 0.1% are demanded and also achieved. For such demands the accuracy should lie within the limits of the standard deviation.
Titrations can be automated: Titrimetric determinations can be automated to a high degree. This means that, for example, they are suitable for analyzing the content in routine
operation (e.g. active ingredient content in tablets).
Titrations are economical: Compared with other analytical methods, the costs are favorable the price/performance ratio is excellent. An example: pH and total acidity in fruit
juice; 20 titrations per day (or 4500 p.a.); Titrino complete with accessories, approx. Euro
4200. Investment costs per titration with one year pay-back time for the purchase = approx. 95 cts.
Important symbols used in the methods:

c (X)
Molar concentration of substance X in mol/L, often written as [X]
M (X)
Molar mass of substance or atomic mass (relative mass) of substance X in g/mol
w (X)
Mass fraction of substance X, e.g. w (NaOH) = 40%
(X)
Mass concentration of substance X, e.g. (NaCl) = 20 g/L
a (X)
Activity of substance X (only corresponds to the molar concentration in very dilute solutions; as the concentration increases, dissolved particles mutually influence each other so that their activity is lower than would be expected from the
concentration).
pKp
Autoprotolysis constant of a solvent
{}
In this monograph braces such as used in the formula {AgCl} indicate solid substances (precipitates) that do not consist of single molecules (in this case AgCl),
but whose ionic components form an extended ionic lattice.
I. 2 Titration reactions
I.2.1 Acid-base reactions
The term acid-base has been revised several times since the18th century in accordance with
the state of knowledge:
Acids contain oxygen (Lavoisier)
Acids contain hydrogen that can be replaced by a metal (Liebig)
Acids dissociate in aqueous solution to release protons and bases release hydroxide ions
(Arrhenius, Ostwald)
These theories can only partly explain chemical reactions. They refer to aqueous solutions;
ampholytes are not included. Examples are aqueous solutions of salts: KHSO4 reacts acidic,
Na2HPO4 alkaline.
Brnstedt defined the acid-base reaction as the exchange of protons. The acid acts as proton donor and the base as proton acceptor. A deprotonated acid is called the conjugate
base and a protonated base is called the conjugate acid. In this way the theory can also
be applied without any problem to ampholytes, salts and prototropes of non-aqueous solvents. The equilibrium constants of the reactions allow a quantitative reactivity series of acids and bases to be drawn up (see below).
Lewis extended the Brnstedt theory. A Lewis base has a free electron pair, a Lewis acid an
electron pair gap. Lewis acid and Lewis base react to form a covalent or coordinative compound. Examples:
2 CN + Ag+ [Ag(CN)2]
2 Cl + SnCl4 [SnCl6]2
Typical Lewis acids are molecules with an incomplete valency shell, cations as the central
atoms of complexes and molecules with multiple polar bonds (e.g. acid anhydrides). Typical Lewis bases are molecules and ions with free electron pairs, anions as complex ligands
and molecules with multiple bonds. The Lewis model can also be used to describe precipitation and complex-forming reactions. As no universal reference acid or base exists, there is no
practical quantitative reactivity series for Lewis acids and bases; however, the Lewis conception allows numerous chemical reactions to be systemized qualitatively.
Protolysis
Polar (prototropic, protic) solvents undergo self-dissociation, i.e. they form an acid-base pair
to a slight extent.
Example water: 2 H2O
H3O+ + OH
Neither free protons nor free electrons are found in a solution. For protons this means that H+
should not be used as an expression, but rather H3O+ to represent the clusters of protons and
water effectively present in an aqueous solution.
According to the law of mass action, the ionic product of water Kw is calculated as follows:
a(X+) a(Y) / a2(XY)
for H2O this means:
a(H3O+) a(OH) / a2(H2O) = KW = 1014
10
K is temperature-dependent. In tables it is usually given for 25 C (the values for H2O are 14.9
at 0 C, 14.2 at 20 C, 14.0 at 25 C, 13.5 at 40 C, etc.).
The relative strength of an acid or base in an aqueous solution are described by the equilibrium constants. These provide information about the extent to which an acid or base dissolved in water at equilibrium can accept or donate protons. Water is the reference base for
each acid and the reference acid for each base. These acidity and basicity constants are
known as Ka and Kb respectively. We have simplified their formulation here by using the molar concentration instead of the activities of the participating species. The molar concentration of water in a mixture is regarded as being constant for dilute solutions (55.5 mol/L) and
not included.
Ks = [H3O+] [S] / [HS]
Kb = [BH+] [OH] / [B]
The negative common logarithms of these values are, analogous to the pH definition, known
as pKa and pKb respectively. The higher the pK value, the weaker the acid or base.
The neutral point of a non-aqueous solvent is calculated in a similar manner to that for water.
Clearly, the pH term only applies to purely aqueous solutions!
H2O, neutral pH = - log
= - log
The following table shows a small selection of autoprotolysis constants of prototropic solvents (at 25 C).
Solvent
Autoprotolysis
Ethanol
Methanol
Acetic acid
Water
Formic acid
Sulfuric acid
2 C2H5OH
2 CH3OH
2 CH3COOH
2 H2O
2 HCOOH
2 H2SO4
pKp
C2H5OH2+ + C2H5O
CH3OH2+ + CH3O
CH3COOH2+ + CH3COO
H3O+ + OH
HCOOH2+ + HCOO
H3SO4+ + HSO4
19.1
16.7
14.5
14.0
6.2
3.6
Acid-base reactions with water

In aqueous solutions the protolysis reaction with water normally predominates (as an ampholyte H2O can act as a Brnstedt acid or a Brnstedt base):
acidic reaction of solvent
basic reaction of solvent
HB (s) + H2O (b)

B (b) + H2O (s)
H3O+ + B
HB + OH
Just as with the ionic product of water, a(solvent) is set = 1 for dilute solutions. The resulting
equilibrium constants are known as the acidity constant Ka and the basicity constant Kb.
K s Kb= Kw
pKs + pKb = pKw = 14 (25 0C)
The stronger the acid or base, the weaker the conjugate base or acid.
At the same time the pK values of the aqueous system limit the acidic or basic strength of protolytes in aqueous solution (differentiation).
11
Stronger acids and bases (pK <0 or pK >14 for the conjugate protolyte) are converted to oxonium ions (H3O+) and hydroxide ions (OH) in aqueous solution. Leveling occurs the separate determination of mixed very strong acids or mixed very strong bases in an aqueous solution is not possible by titration. (Only one endpoint is found in the titration of mixtures of e.g.
KOH/NaOH or HCl/H2SO4).
The known corresponding acid-base pairs are arranged according to increasing pKa (or decreasing pKb value) and normally divided into the following categories:
very strong
pKa <0
strong
pKa 04
weak
pKa 410
very weak
pKa 1014
extremely weak
pKa >14
Protolytes
As a result of the leveling effect of water, differences in the protolysis constants of strong protolytes can only be determined in non-aqueous solvents. In such solvents the relationship pKa
+ pKb = pKsolvent also applies for the conjugate acid-base pair. This means that the solvent cation (lyonium ion) and the solvent anion (lyate ion) are always the strongest acids and bases
in the affected system.
Whereas acetic acid behaves in water like a weak acid, in HClO4 it behaves like a base:
CH3COOH + H2O
HClO4 + CH3COOH
H3O+ + CH3COO
CH3COOH2+ + ClO4
In order to be able to achieve the separate determination of the components in an aqueous

solution by titration, the differences in their pK values should be approx. 5 units. In contrast,
in suitable non-aqueous solvents a difference of 2 to 3 pK units is normally sufficient.
12
pKa values of some selected acids
pKb values of some selected bases
Acids
pKa
Bases
pKb
Acetic acid
4.73
Acridine
9.89
Acrylic acid
4.26
Ammonia
4.75
Benzoic acid
4.20
Aniline
9.42
Boric acid
9.24
Benzylamine
4.62
Chloroacetic acid
2.81
Calcium hydroxide
1.30
Hydrobromic acid
approx. 6
Coffeine
13.39
Hydrochloric acid
approx. 3
Cyclohexylamine
3.36
Hydrocyanic acid
9.40
Diethanolamine
5.12
3.14
Ethanolamine
4.56
Hydrogen sulfide acid 1 stage
6.90
Ethylamine
3.33
Hydrogen sulfide acid 2nd stage
12.9
Imidazole
7.00
Lactic acid
3.86
Lithium hydroxide
0.10
Nitric acid
1.32
Magnesium hydroxide
3.36
Oxalic acid 1st stage
4.31
Naphthylamine
10.08
Oxalic acid 2nd stage
1.42
o-aminobenzoic acid
10.92
approx. 9
o-toluidine
9.61
9.95
2-Picoline
7.52
Phosphoric acid 1 stage
1.96
Piperidine
2.80
7.12
Pyridine
8.81
12.36
Triethanolamine
6.23
Salicylic acid
2.98
Triethylamine
3.28
Trimethylamine
4.20
Urea
13.8
Hydrofluoric acid
st
Perchloric acid
Phenol
st
nd
rd
Sulfuric acid 1 stage
approx. 3
Sulfuric acid 2 stage
1.92
st
nd
Source: see literature reference 8.

The strongest acid in the list is HClO4, the strongest base is lithium hydroxide.
The following empirical rules apply for the relative acid strength of inorganic acids:
Hydracids: the acidity increases as the atomic number increases, both within the group
and within the period. (This means that HI is the strongest acid.):
HF < HCl < HBr < HI
Oxyacids are stronger the fewer H atoms and more O atoms they contain. (The strongest
mono-oxyacid is HClO4).
HClO < HClO2 < HClO3 < HClO4
H2SiO4 < H3PO4 < H2SO4 < HClO4
13
Acid-base titrations
Acid-base reactions occur very rapidly (proton transfer takes far less then one millionth of a
second).
In mixtures of acids the titration is always carried out in the sequence of the relative acid
strengths. This means that the strongest acid is always titrated first, the weakest acid last.
Example:
The titration curve of a mixture of HCl and CH3COOH shows two equivalence points/
endpoints. The consumption up to EP1 corresponds to the molar concentration of HCl and
the consumption for the difference EP2 EP1 to the molar concentration of acetic acid.
a) Titration of strong protolytes (strong acid with strong base and vice versa)
The salts of strong acids with strong bases do not undergo protolysis with water, which
means that an equivalent amount of these acids and bases react neutrally. The equivalence
point in the titration of a strong acid with a strong base and vice versa is therefore identical
with the neutral point (pH = 7.0 in H2O).
The shape of the titration curve results from the fact that in order to increase the pH from 1 to
2 it is necessary to reduce the H3O+ concentration to 1/10 of the original value (or that 90% of
the equivalent base has already been added). From pH = 2 to pH = 3 it is then 9%, from pH
= 3 to pH = 4 then 0.9%, etc. With the excess base it is exactly the opposite; from pH = 7 to
pH = 8 0.0009% is necessary, from pH = 8 to pH = 9 requires 0.009%, from pH = 9 to pH =
10 it is 0.09% excess base, etc.
This is why typical symmetric titration curves with a steep jump region are obtained, whose
equivalence point (titration endpoint, corresponds to the point of inflection of the curve) lies
at pH = 7.0.
b) Titration of a weak acid with a strong base
Before the start of the titration it can be seen that the pH is acidic, which corresponds to the
weak acid not being completely dissociated in water. After the start of the titration a buffering range (10...90% of neutralization) can be observed in which the weak acid and its salt or
acid anion are both present. In this buffering range the addition of the base only alters the
pH slightly. The point of inflection of the buffering range corresponds to the semi-equivalence
point of the titration (half reaction) and therefore, according to the Henderson-Hasselbalch
equation, the pKa value of the weak acid is given by: pH = pKa + log [A] / [HA], where at half
reaction the molar concentrations of acid anion and acid are equal resulting in log 1, which
is equal to 0.
In the above case the equivalence point no longer lies at pH = 7, because the added base
competes with the conjugate base of the acid. At the equivalence point the salt solution present has an alkaline reaction, as the acid anions of a weak acid undergo protolysis with water
(hydrolysis). The equivalence point of such a titration lies depending on the relative strength
of the acid in the pH range 7.5...10.
The higher the concentration of acid and base in the solution, the wider the buffering range on
the volume axis. The pH value achieved by adding additional base beyond the equivalence
point finally approaches that of the base used as the titrant.
14
c) Titration of a weak base with a strong acid

Before the start of the titration an alkaline pH is measured that corresponds to that of the not
fully dissociated weak base in water. After the start of the titration a buffering range can also
be observed (10...90% of the neutralization), in which the weak base and its conjugated protonated form are both present. Addition of acid hardly alters the pH in this buffering range at
all. The point of inflection of the buffering range corresponds to the semi-equivalence point of
the titration (half reaction) and lies at that pH value which corresponds to the pKb value of the
base. The equivalence point is again no longer at pH = 7, because the added acid competes
with the conjugate acid of the base. The corresponding salt solution is acidic as the protonated base undergoes protolysis with water (hydrolysis). The equivalence point lies depending on the relative strength of the base in the pH range 6.5...4.
d) Titration of a weak acid with a weak base
This titration is unsuitable for quantitative determinations! There is no marked jump in the titration curve, and the slope of the curve in the equivalence region does not achieve a maximum
value. No suitable titration endpoint for a quantitative determination is reached. This means
that, when selecting a titrant for the titration of weak acids and bases, weak bases and acids
should not be chosen.
e) Titration curve
The following applies in general: The jump of a titration curve is more marked the higher
the Ka or Kb values of the two reaction partners and the higher the concentrations of both species.
I. 2.2 Precipitation reactions
Solubility and solubility product
The solubility of a dissociated sparingly soluble compound is determined by the maximum
ionic product or solubility product KL. This means that the product of the molar concentrations of the dissolved ions of a salt cannot be larger than the value KL. In equilibrium this value
becomes established when so much of the sparingly soluble compound is added to water
that a precipitate is formed. This value is not exceeded even when the amount of precipitate
is increased!
The solubility L is understood to be the total concentration of the substance in its saturated
solution. For a binary hardly soluble salt the following applies:
{ A + B }
A+ + B and, approximately,
c(A+) c(B) = KL (for the stoichiometric solubility product)

L = c(AB) dissolved = c(A+) = c(B)
L=
With AgCl as an example: KL = 1010 mol2/L2, L = 105 mol/L
Precipitation only begins when the product of the molar concentrations of the dissolved ions
A and B, the ionic product c(A+) c(B) >KL. Tables of solubility products show that the
known KL values of salts differ by many factors of ten and in aqueous solution for 1:1 electrolytes values between approx. 102 (e.g. NaOH) and 1052 (e.g. HgS) are achieved. (For HgS this
would mean that only 1026 mol/L Hg should dissolve. However, the actual solubility is consid-
15
erably higher precipitate aging, complex formation and other effects also play a role. Strictly
speaking, the molar concentrations should also be replaced by the activities.)
The equations mentioned above only apply when the dissolved ions A+ and B are in equilibrium with the precipitate. If one of the partners occurs in excess (isoionic addition), then the
solubility depends on the ion with the lower concentration. With isoionic addition the solubility decreases the solubility product is never exceeded. (This is why in gravimetry an excess
of the precipitation reagent is always used.)
If foreign ions are added (foreign ion addition) the opposite takes place the solubility increases. (In this case the coefficients of activity of all the ions present in solution the total
ionic strength play a role.)
The determination limit for precipitation titrations depends very strongly on the solubility product. Concentrations below the solubility (the precipitation) can no longer be titrated. In some
cases the solubility product can be reduced by the addition of an organic solvent (e.g. acetone or ethanol); this also results in a lower determination limit. (For chloride titration with
AgNO3 the determination limit in H2O is approx. 3.5 mg/L; in glacial acetic acid, for example
AOX determination, it is a few g/L.)
Many precipitates formed during the titration are voluminous and inclusions could occur
(sample ion and/or titrant). A more finely distributed precipitate, almost free from inclusions,
is obtained by the addition of protective colloids (e.g. polyvinyl alcohol) or organic solvents
(e.g. acetone or ethanol).
For AgNO3 titrations Ag electrodes (Ag Titrode) are usually used for indication of the titrations,
with ISEs usually being used for the determination of other ions.
In this monograph we are only concerned with substances that form sparingly soluble precipitates and can therefore be determined titrimetrically.
a) Inorganic compounds
Ion (analyte)
Titrant
Precipitation product
Ag+
KBr
AgBr
Ba
Na2SO4
BaSO4
Bromide
AgNO3
AgBr
Chloride
AgNO3
AgCl
Cyanide
AgNO3
AgCN
Fluoride
La(NO3)3
LaF3
2+
Iodide
AgNO3
AgI
Sulfate
BaCl2
BaSO4
Sulfide
AgNO3
Ag2S
Thiocyanate
AgNO3
AgSCN
In order to be able to titrate quantitatively the various ions present in a mixture, the differences between their solubility products must be at least three factors of ten. This means that
the determination of bromide/chloride mixtures is only possible at a ratio of 1:1. If this ratio
changes then problems occur or the ions can no longer be determined quantitatively in the
mixture. (In contrast, chloride and iodide mixtures can be separated titrimetrically without any
problems.)
16
The formation of precipitates from mixtures depends strictly on the solubility products of the
individual components. The most sparingly soluble product is always titrated first, e.g. in the
titration of halides with AgNO3 the sequence is always iodide bromide chloride.
Solubility products of some selected substances at 25 C *
Substance
KL
BaCO3
8.1 x 109 mol2/L2
BaSO4
1.08 x 1019 mol2/L2
CaF2
3.95 x 1011 mol3/L3
CaC2O4 x H2O
2.57 x 109 mol2/L2
PbCrO4
1.77 x 1014 mol2/L2
PbSO4
1.06 x 108 mol2/L2
PbS
3.4 x 1028 mol2/L2
AgBr
7.7 x 1013 mol2/L2
Ag2CO3
6.15 x 1012 mol3/L3
AgCl
1.56 x 1010 mol2/L2
Ag2CrO4
9 x 1012 mol3/L3
AgI
1.5 x 1016 mol2/L2
AgSCN
1.16 x 1012 mol2/L2
AgCN
2.2 x 1012 mol2/L2
Ag2S
1.6 x 1049 mol3/L3
HgS
1 x 1052 mol2/L2
Hg2S
1 x 1045 mol3/L3

* With most substances the solubility product increases as the temperature increases (more of the substance dissolves).
If a sensor (electrode) is used for the titration that responds to both the cation and the anion
(ISE) then the titration curve is similar to that obtained for the titration of a strong acid with a
strong base (pH electrode). This means that when the concentration changes by a factor of
ten the electrode potential changes by approx. 59 mV (29 mV for z = 2). z corresponds to the
valency, e.g. +2 for Ca. This also means that for the first 59 mV difference 90% of the ions to
be determined have been titrated, for the second 59 mV difference 99% of the ions have already been titrated, etc.
The resulting titration curves are symmetrical, and the point of inflection of the curve corresponds to the equivalence point/titration endpoint.
Self-dissociation/solubility product and dilution must be taken into account in order to obtain the true endpoint. In most cases, however, the resulting systematic error is so small that
it hardly affects the result. (The modern evaluation software of the Metrohm titrators at least
takes the dilution error into account.)
b) Titration of surfactants
Surfactants or surface-active substances are compounds that consist of a long-chain hydrophobic group (tail) and a hydrophilic head group. In sufficient concentration in water
they form aggregates (micelles), in whose hydrophobic interior lipophilic substances are
17
solubilized. Their effectiveness as detergents is based upon this fact, among others. Until
about 1995 surfactants were titrated manually by the classical Epton method. This is an extraction titration (two-phase titration) with visual endpoint recognition. A chloroform/ethanol
mixture is added to dissolve the sample, the pH adjusted to a particular value (usually with a
buffer solution) and the titrant is added step by step. After each addition of titrant the solution
is vigorously shaken and the ion associate formed (sample surfactant-titrant) is extracted in
the organic phase. As soon as the titration endpoint has been reached, the added colored indicator also changes to the organic phase and the titration is finished. From this brief description of the titration it is not difficult to recognize that automation would be both very difficult
and, if at all possible, unsatisfactory.
In the last few years Metrohm has concerned itself with this problem and can today offer complete solutions for anionic, cationic and nonionic surfactants. The solution to the problem is
the use of ion-selective electrodes (ISEs) for the potentiometric indication of these titrations.
It almost goes without saying that a single electrode is not sufficient to cover all the different
possibilities and requirements. This is why Metrohm offers five different surfactant ISEs. This
means that the customers can find custom-made solutions to their specific problems. The
methods can be automated and ever more important also be validated.
As will be seen later, in surfactants only the active group is titrated. This means that the titrimetric separation of different surfactants of the same class (e.g. those with different chain
lengths, such as are present in technical surfactants as a mixture of species of a homologous
series) is not possible. It is always the total amount of surfactant of a class in the sample solution that is determined.
Techniques such as TLC and liquid chromatography must be used for the detection and determination of individual surfactants or for the analysis of mixtures of surfactants in detergents
and hygiene products.
The main surfactant groups
a) Anionic surfactants and soaps (this is the largest and most frequently used of the main
groups).
Alkylbenzene sulfonates (LAS)

Fatty alcohol sulfates (FAS)
Fatty alcohol ether sulfates (FAES)
Secondary alkane sulfonates
-Olefin sulfonates
Isethionates
Sulfosuccinates (mono- and di-esters)
Taurides
Soaps (fatty acid salts), lauroyl sarcosinates, ether carboxylic acids
b) Cationic surfactants
ialkyldimethyl ammonium halides *

Benzalkonium halides *
Imidazolium quats **
Esterquats **
Fatty amines
Fatty amine ethoxylates
* usually chlorides or bromides

** quat = quaternary ammonium compound
18
c) Amphoteric surfactants
Amphoteric surfactants have both an anionic and a cationic functional group. Depending on
the pH value, one or the other becomes active. Amphoteric surfactants cannot be titrated at
least in formulations.
Betaines
Amphoglycinates
Lauryl aminopropionic acid
d) Nonionic surfactants
Alcohol ethoxylates
Fatty alcohol ethoxylates
Alkylphenol ethoxylates
Fatty acid polyglycol esters
Fatty acid alkanolamines
Fatty acid glycerides (cannot be titrated)
Sorbitan esters (cannot be titrated)
Alkylpolyglycosides sugar surfactants (cannot be titrated)
1. Ionic surfactants (anionic/cationic)

Anionic surfactants and cationic surfactants (and vice versa) form ion associates that are
sparingly soluble in aqueous solution and precipitate. The worse the solubility of these associates, the more pronounced and steeper the titration curve. This is why the choice of titrant is
very important. The pH of the solution to be titrated is also important as the surfactant-active
head groups are protonated or deprotonated; this influences their hydrophilicity.
The choice of the correct electrode is also crucial. Further information is provided below.
1.1 Anionic surfactants and soaps
In this case the titrant is a cationic surfactant. The best-known one for this purpose is Hyamine
1622 [N-benzyl-N,N-dimethyl-N-[4-(1,1,3,3-tetramethylbutyl)-phenoxy-ethoxyethyl] ammonium chloride. It is relatively cheap, but has the disadvantage that certain anionic surfactants
either cannot be titrated or the titration is not sufficiently accurate. (Chain lengths <C12, several ether side-chain ether groups result in flat titration curves.) However, we can recommend
the use of TEGOtrant A100 (Metrohm no. 6.2317.0X0) 1,3-didecyl-2-methyl-imidazolium
chloride. It is slightly more expensive than Hyamine 1622, but its use is worthwhile whenever
more accurate results are required or special surfactants have to be titrated.
The titrant is usually used at a concentration of c = 0.005 mol/L. With cationic surfactants it
must be remembered that they are strongly substantive i.e. they are attracted to surfaces
(Lenor-effect in fabric conditioners). This means that after the titrant has been filled into the
Exchange Unit it must be conditioned (preferably overnight) before its titer is determined.
The precipitating ion associates formed are 1:1 compounds (one anionic reacts with one cationic surfactant group).
For the aqueous titration of anionic surfactants we recommend the Ionic Surfactant Electrode
(6.0507.120), for the two-phase titration of anionic surfactants and soaps the 6.0507.140 Surfactrode Refill. (The 6.0726.107 Ag/AgCl electrode should be used as the reference electrode.)
19
Optimal pH ranges for the titration of anionic surfactants:
Sulfates and sulfonates

Carboxylates and soaps
Sulfosuccinates for the anionic sulfone group
Sulfosuccinates for the anionic sulfone group
and the carboxyl group, which is also anionic
pH = 24
pH = 10.512
pH = 13
pH = 810
1.2 Cationic surfactants

The titrant is an anionic surfactant. Sodium dodecylsulfate (sodium lauryl sulfate, SDS) is usually used at a concentration of c = 0.005 mol/L. The precipitating ion associates formed are
1:1 compounds (one cationic reacts with one anionic surfactant group).
For the aqueous titration of cationic surfactants we recommend the Cationic Surfactant Electrode (6.0507.150), for the two-phase titration of cationic surfactants 6.0507.130 Surfactrode
Resistant. (The 6.0726.100 Ag/AgCl electrode should be used as the reference electrode with
6.2320.000 electrolyte and 3.421.3720 ground glass diaphragm.).
Optimal pH ranges for the titration of cationic surfactants:
Quats
Esterquats
Fatty amines
pH = 9.510.5
pH = 12
pH = 34
pH = 34
2. Nonionic surfactants (NIO surfactants)

As their name says, nonionic surfactants have no reactive surfactant groups they therefore
neither react with anionic nor cationic surfactants. In order to still be able to titrate them we
must use a trick.
Nonionic surfactants based on polyoxyethylene (POE) adducts (these contain [R-CH2-CH2O-] groups) are converted to a pseudo-ionic form by the addition of barium ions that can be
titrated with Na tetraphenylborate. (The barium ions are inserted into a helix structure complex-like supramolecular compounds are formed in which the oxygen atoms in the helix coordinately bond with the barium ions to form a guest-host complex with the surfactant acting as the host and the barium ions as the guest.) The following points must be observed:
Complex formation depends largely on the chain length of the starter molecule. Short EO
chains are not able to bind the barium ions. Rule of thumb: in order to be able to be determined titrimetrically, at least 4 EO groups are required for ethylene oxide addition products
based on lipophilic starter molecules; for polyethylene glycols at least 11 to 12 POE groups
are required.
Experience has shown that approx. 11 EO groups form a barium complex with a double
positive charge. In order to precipitate this complex, two Na tetraphenylborate molecules
are required (this means that 1 consumed Na TPB particle corresponds to approx. 5.5 EO
groups).
- If a NIO surfactant (as a technical product) is known, for example, by the name POE-(20)stearyl alcohol, it cannot be assumed that this is a uniform product consisting exclusively
of stearyl alcohol with 20 POE groups. The number 20 rather represents a statistical mean
value, with POE distributions normally being encountered in the range between at least
POE 10 to POE 30.
20
For the above-mentioned reasons NIO surfactants do not react stoichiometrically on titration.
As in other analytical methods (e.g. HPLC) a calibration factor is determined for the titrant instead of a titer. Whenever possible, this determination of the calibration factor should be carried out with the NIO surfactant that is to be determined. Should this not be possible, or if a
mixture of NIO surfactants is to be analyzed then, for example, a mean molar mass can be
used for the calculation, or Triton X-100 or polyethylene glycol 1000 can be used for determining the calibration factor.
Nonionic surfactants cannot be determined with a two-phase titration.
For the titration of nonionic surfactants we recommend the 6.0507.010 NIO Surfactant Electrode with 6.0726.107 Ag/AgCl reference electrode (outer electrolyte NaCl, c = 1 mol/L, as
KCl is precipitated with NaTPB Kalignost; inner electrolyte KCl, c = 3 mol/L).
I.2.3 Redox reactions
In addition to acid-base reactions, redox processes form a further important group of exchange processes. In oxidation electrons are donated, in reduction electrons are accepted.
This means that an oxidizing agent is an electron acceptor and a reducing agent is an electron donor.
Ox + z e Red
//
Red z e Ox
Just like positive protons, negative electrons are also elementary particles but with a negative charge and, because of their high reaction potential (small particle radius), only exist
very briefly in concentrated materials (half-life value approx. 1 ms). Free electrons act as very
strong reducing agents and, for example, spontaneously decompose H2O:
H2O + e 12 H2 + OH
Many redox processes are inhibited, i.e., no conversion takes place even though it would be
thermodynamically possible. Example:
Fe3+ + 12 H2 Fe2+ + H+
In practice it is important that, in contrast to protons, in aqueous solution electrons cannot
migrate via water molecules. For example, they migrate via electron bridges using complex-forming partners such as chloride. This means that in some cases considerable activation enthalpies are necessary. Such reactions take place relatively slowly (e.g. Fe(III)/Sn(II)).
The same applies if the number of electrons accepted by the oxidizing agent is not the same
as the number donated by the reducing agent (e.g. permanganate/oxalate and dichromate/
iron(II) in this case a series of three single-electron steps is required to transfer chromium
to oxidation state III).
The time taken for complete conversion after mixing can amount to several seconds. Both
catalysts and heating can accelerate the reaction.
Oxidation and reduction of chemical compounds can also be described as an alteration in the
oxidation state. (Oxidation increases while reduction reduces the oxidation state.)
In a similar manner to the acid-base reaction, oxidation and reduction can only occur together (redox reaction). Most redox titrations are carried out under acidic conditions (excess protons).
21
Some examples of titrations:

Iodine Thiosulfate
I2 + 2 S2O32 S4O62 + 2 I
Sulfite Iodine
SO32 + I2 + 3 H2O SO42 + 2 H3O+ + 2 I
Arsenite Bromate
3 As3+ + BrO3 + 6 H3O+ Br + 3 As5+ + 9 H2O
Hydroxylamine Bromate
NH2OH + BrO3 NO3 + Br + H3O+
Bromate as titrant
BrO3 + 5 Br + 6 H3O+
9 H2O + 3 Br2
Bromine number
HC = CH + Br2 HBrC CBrH
electrophilic addition of bromine at the double bond)
Nitrite Cerium(IV)
NO2 + 2 Ce4+ + 3 H2O NO3 + 2 Ce3+ + 2 H3O+
Dichromate Iron(II)
Cr2O72 + 6 Fe2+ + 14 H3O+
2 Cr3+ + 6 Fe3+ + 21 H2O
Permanganate Oxalate
2 MnO4 + 5 C2O42 + 16 H3O+ 2 Mn2+ + 10 CO2 + 24 H2O
Permanganate hydrogen peroxide
2 MnO4 + 5 H2O2 + 6 H3O+
2 Mn2+ + 5 O2 + 14 H2O
Noble metal electrodes are used to indicate redox titrations. They are usually made of platinum; gold electrodes are used less frequently. We recommend the use of combined electrodes.
The redox potential is measured. The general formulation of the Nernst equation for the equilibrium Ox + z e
Red is
E = E0 + (0.059 / z) x log aox / ared (at 25 C)
Example:
Sn4+ + 2 e
Sn2+
E = E0 + (0.059 / 2) x log a (Sn4+) / a (Sn2+)

Example of a pH-dependent redox reaction for which the ion activities H+ or OH are used directly in the Nernst equation:
MnO4 + 8 H3O+ + 5 e
Mn2+ + 12 H2O
E = E0 + (0.059 / 5) x log [a (MnO4) x a8 (H3O+)] / a (Mn2+)

From this equation it can be clearly seen that the redox potential E is very pH-dependent.
22
Titration curve
In this case the electrode potential also represents a logarithmic function of the concentration,
just as in the other donor-acceptor reaction, the acid-base reaction. This means that the (potentiometric) curve appears similar to an (acid-base) neutralization curve. The height of the
potential jump is determined by the potential difference of the two redox systems and their
concentration in the solution. The further apart the two redox potentials (sample/titrant) and
the higher their concentration, the greater and steeper the potential jump.
At the point of inflection of the curve (the endpoint) a redox equilibrium exists, whereas before or after the endpoint one or the other component is present in excess. For a combined Pt
electrode the curve runs as follows:
titrant is oxidized to plus
titrant is reduced to minus
(For the Pt Titrode the reverse is true, as the glass electrode as reference electrode is connected to the high-impedance plus pole.)
Many reducing agents are sensitive to oxygen. This means that they are oxidized by atmospheric oxygen and are not determined (low-bias results). In this case we recommend that
the titration is carried out under an inert gas (N2 or CO2). In some cases the sample solution
is treated with an excess of the oxidizing or reducing agent and, after the conversion, the remaining fraction is back-titrated with a reducing or oxidizing agent. However, back-titrations
are more time-consuming than direct titrations and require two titers.
I.2.4 Complexometry / chelometry
All particles made up of individual ions or molecules and with the form [MLn] +/z are known
as complexes. In the stricter sense complexes are compounds that can easily be broken up
into simpler ions and molecules, e.g. dicyanoargentate: [Ag(CN)2] Ag+ + 2 CN(cyanide is
the ligand).
The coordination number of the central ion gives the number of monodentate ligands that
are bonded. In aqueous solutions cations are mostly present as aquacomplexes of the form
[M(OH2)4]z+ or M(OH2)6]z+.
Dentation is understood to be the number of possible or actually occupied coordination
sites of the ligand. Complexes with multi-dentate ligands are known as chelates.
Thermodynamic and kinetic factors determine the stability of complexes. A measure of the
thermodynamic stability is the complex formation constant KB, or the dissociation constant
K = 1/KB.
Derivatives of aminopolycarboxylic acids have proven to be best for titration. In addition to
their chemical names, protected brand names are often used, e.g.. Komplexon (Chemische
Fabrik Uetikon, Switzerland), Titriplex (Merck), Idranal (Riedel-de Han) etc.
For example, the stability of the metal complexes is given by the following simplified equation
(in this case using EDTA, ethylenediamine tetraacetic acid as the complexone):
KB = [MeEDTA2] x [ H3O+ ]2 / [Me2+] x [H2EDTA2]
The complex formation constant is usually given as log KB in tables. The larger that KB the
more stable the complex.
23
The effective complex formation constants are generally lowered by protons (acids), as these
react in competition to the metal ions with the complexing agent they protonate e.g. the carboxyl groups of the titrand. The following can be used as rule of thumb:
Metals with complex formation constants <10 are titrated under alkaline conditions, metals
with complex formation constant >15 under slightly acidic conditions (Fe3+ and Bi3+ can even
be titrated at pH = 2). The solutions are usually buffered (see below).
The table below lists some selected complex formation constants log KB for two common titrants (EDTA = ethylenediamine tetraacetic acid, NTA = nitrilotriacetic acid):
Metal ion
log KB EDTA
log KB NTA
Al(III)
16.1
Ba(II)
7.8
4.8
Bi(III)
27.9
Ca(II)
10.7
6.4
Cd(II)
16.5
9.8
Co(II)
16.3
10.4
Cu(II)
18.8
13.0
Fe(II)
14.3
8.8
Fe(III)
25.1
15.9
Hg(II)
21.8
Mg(II)
8.7
5.4
Mn(II)
13.8
7.4
Ni(II)
18.6
6.5
Pb(II)
18.0
11.4
Sr(II)
8.6
5.0
Zn(II)
16.5
10.7
Source: Metrohm Application Bulletin no. 101

From the above table the following conclusions can be drawn:
EDTA forms more stable complexes than NTA (ligand has more teeth).
Metal ions with a triple positive charge form more stable complexes than those with a double positive charge.
The most stable complex is formed by Bi(III) with EDTA, the least stable by Ba(II) with
NTA.
Titration curve
The curves of complex forming titrations are similar to those obtained with acids and bases or
in redox titrations as a logarithmic function of the titration. The jump is more marked the larger
the complex formation constant KB and the higher the concentrations of titrant and analyte.
Titration methods
As EDTA forms 1:1 complexes with all metal ions (their valency does not matter), the titrant
is usually used at a concentration of c = 0.1 mol/L. EDTA is practically insoluble in water, the
solution normally used is that of the disodium salt Na2EDTA (more correctly Na2H2EDTA).
24
Direct titration is possible if complexing takes place quickly and completely. Otherwise indirect titration (in this case back-titration) is used (an excess of EDTA is added, heated if necessary and back-titrated with Mg(II) or Zn(II)).
The separate determination of mixtures of different metal ions present in the same solution
is normally not possible by titration. For example, titration must be carried out at different pH
values, by recomplexing, by the addition of masking agents or by the use of a more selective
complexing agent (see also under 5.).
It is important to chose a suitable pH range for the titration. If the pH is too low then the carboxyl groups of the EDTA will be wholly or partially present as undissociated carboxylic acids
and cannot complex the metal ion. If the pH is too high then the metal could precipitate as a
hydroxide.
Titration is almost always carried out in a buffered solution as during complex formation protons are released and as we have seen the complex formation constant is pH-dependent.
Examples:
Ca2+ + Na2H2EDTA + 2 H2O
Al3+ + Na2H2EDTA + 2 H2O
Na2CaEDTA + 2 H3O+
NaAlEDTA + 2 H3O+ + Na+
The oxonium ions produced during the titration are neutralized by the buffer, which displaces
the equilibrium to the right.
25
I.3 Indication methods

General
The equivalence point is reached when titrant and analyte have reacted completely with each
other in the corresponding stoichiometric ratio. If titration is regarded as being counting molecules or ions, then this point must be detected as accurately as possible. This is done by
using the properties of the solution or an added indicator which, at the equivalence point,
changes as abruptly as possible and in a well-defined manner. The volume of titrant consumed up to the point that this change occurs is the endpoint volume. The endpoint should
be as close as possible to or identical with the equivalence point. This means that the indication method is very important. In addition to the accuracy of the titrant addition it makes
an important contribution to the reproducibility and, above all, the correctness of the results.
Details of the three most important indication methods are given in the following subsections
(less important ones such as conductometry/conductivity and calorimetry are not considered
here). These are:
Visual or photometric indication
Potentiometric indication
Indication with polarized electrodes (bivoltametry/biamperometry)
I.3.1 Visual or photometric indication
Visual indication with colored indicators is certainly the oldest method for recognizing the
endpoint of the titration; it is still frequently used today. It can be realized without any complicated instrumentation and at a low cost.
Colored indicators react
with the analyte: a small amount of indicator is added at the start of the titration and, together with the analyte, forms a species A. When the analyte has almost completely reacted
with the titrant the titrant displaces the indicator from species A which releases the indicator. This takes place with a change of color (in acid-base titrations phenolphthalein reacts
with protons to give a colorless substance. Under alkaline conditions the proton is split off
and the color changes to red-violet).
with the titrant: a small amount of indicator is added at the start of the titration. It does not
react with the analyte, and the color remains unchanged until the first excess titrant is present. The titrant then combines with the indicator. This takes place with a change in color
(e.g. chloride determination by MOHRs method, see below).
If the correct colored indicator is chosen then good results are obtained. The chief disadvantage of this method is that it cannot be automated and can hardly be validated. (The color
sensitivity differs from person to person and also depends on the lighting conditions. In addition, difficulties occur with colored and/or turbid solutions.)
Photometric indication can bring an improvement. The (individual) human eye is replaced by
a (neutral) sensor. The method can be automated and validated provided that the correct
colored indicator is chosen and that the solutions are not too turbid or no intense turbidity occurs during the titration.
In addition to added colored indicators, cases of self-indication also occur. An example of this
is the pink-violet colored KMnO4, which in redox titrations is converted into Mn(II), the latter
being colorless in dilute solutions.
26
Colored indicators do not have a transition point they have a transition range. This fact can
considerably influence the correctness of the results of titrations with visual endpoint recognition. An empirical rule is that the human eye recognizes a change in color when the concentration ratio of the two indicator species changes from a ratio of e.g. 1/10 to 10/1. For pH indicators this means that the pH must have altered by two units.
The size of the error that occurs (particularly with flat titration curves) must be known exactly.
It is often better to use mixed indicators with a smaller transition range.
The table shows a selection of frequently used colored indicators for aqueous acid-base titrations:
Indicator
Volume concentration
in solvent
Range of color change

(pH)
Color change*
Thymol blue, 1st change
0.04% in water
1.2...2.8
red yellow
M Cresol purple, 1st change 0.04% in water
1.2...2.8
red yellow
Bromophenol blue
0.05% in ethanol
3.0...4.6
yellow violet
Methyl orange
0.04% in water
3.1...4.4
red yellow orange
Bromocresol green
0.1% in 20% ethanol
3.8...5.4
yellow blue
Methyl red
0.1% in ethanol
4.4...6.2
red yellow
Litmus
0.2% in ethanol
5.0...8.0
red blue
Bromophenol red
0.1% in 20% ethanol
5.2...6.8
yellow crimson
Bromothymol blue
0.1% in 20% ethanol
6.0...7.6
yellow blue
Thymol blue, 2 change
0.04% in water
8.0...9.6
yellow blue
Phenolphthalein
0.1% in ethanol
8.2...9.8
colorless reddish violet
Alizarin yellow R
0.1% in water
10.0...12.1
light yellow reddish brown
Epsilon blue
0.1% in water
12.0...13.0
orange violet
nd
* First color mentioned refers to more acidic condition.

Titration example
H3PO4 with c(NaOH) = 0.1 mol/L:
Methyl orange
H3PO4 + NaOH NaH2PO4 + H2O (1st step)

1 mL c(NaOH) = 0.1 mol/L corresponds to 9.7995 mg H3PO4
Phenolphthalein
H3PO4 + 2 NaOH Na2HPO4 + 2 H2O (2nd step)

1 mL c(NaOH) = 0.1 mol/L corresponds to 4.8998 mg H3PO4
If both colored indicators are added then the solution will first change from red to yellow
1st step and then from yellow to red-violet 2nd step.
In precipitation titrations adsorption indicators can be used. They take their name from
the fact that they are adsorbed onto the surface of the precipitate. Precipitate surfaces carry charges. This means that you must remember that the behavior of adsorption indicators
greatly depends on the pH of the solution and that, in the presence of larger amounts of electrolytes, interference could occur as a result of flocculation (strong precipitate formation). In
such cases a protective colloid should be added in order to obtain a fine precipitate.
27
Examples of adsorption indicators are:

with excess silver ions.
Eosin for bromide and iodide; pink with excess halide, deep-pink with excess silver ions.
For special precipitation titrations two methods have been established for many years:
Chloride determination according to Mohr
For this determination potassium chromate is used as the indicator. The endpoint is obtained
when a slight excess of silver ions leads to the precipitation of brown-red silver chromate:
2 Ag+ + CrO4 2
{Ag2CrO4}
The pH must be between 6.5 and 9. Dichromate is formed under too acidic conditions which
does not form a sufficiently sparingly soluble silver precipitate. Under too alkaline conditions
silver hydroxide is formed which precipitates.
All determinations (including that of the titer) must be carried out under conditions that are as
identical as possible with respect to the halide and chromate ion concentrations so that the
silver ion excess necessary for the recognition of the brown-red color is always the same.
Silver determination according to Volhard
In this case the silver ions are titrated with thiocyanate. Excess thiocyanate ions are recognized with the aid of Fe(III) ions (red coloration). The simplified reaction equation is:
Fe3+ + 3 SCN
Fe(SCN)3
The titration is carried out in a solution of nitric acid (approx. c = 0.4 mol/L). The indicator is a
saturated solution of (NH4)Fe(SO4)2 x 12 H2O in water, which is treated with boiled nitric acid
until the brown coloration disappears. Acidification suppresses the hydrolysis of the iron(II)hexaquo complex according to [Fe(H2O)6]3+ + 3 H2O
{Fe(H2O)3(OH)3} + 3 H3O+ with
the formation of iron hydroxide precipitates.
Nitrous acid must be absent as it forms red nitrosyl thiocyanate (NOSCN) with thiocyanate.
Redox indicators are compounds whose reduced and oxidized forms differ in color. This
means that during a titration their color adapts itself in accordance with the prevailing redox
potential. Please note that the redox potential of the colored indicator is higher than that of
the corresponding titrant if an oxidizing titrant is used and lower than that of the corresponding titrant if a reducing titrant is used.
Redox titrations are usually carried out in strongly acidic solutions. The following table gives
a short overview of some redox indicators:
Indicator
Potential in V*
Color change**
Safranine O
0.24
blue violet colorless
Methylene blue
0.53
blue colorless
2,6-Dichlorophenolindophenol
0.67
red colorless
Variamine B blue
0.71
blue colorless
Diphenylamine
0.76
violet colorless
Diphenylamine-4-sulfonic acid
0.85
crimson colorless
* At pH = 0
** Oxidized / reduced form
28
It has been the development of colored indicators for complexometric/chelometric titrations that has made such titrations possible at all. Together with the metal ion to be determined these indicators form a colored complex whose color changes abruptly when all the
metal ions have been (re)complexed or titrated by the titrant. The following table contains a
small selection of colored indicators used for such titrations:
Indicator
Suitable for
Color change*
Pyrocatechol violet
Bi, Cd, Co, In, Mn, Ni, Zn
blue yellow
Dithizone
Zn
red green violet
Eriochrome T black
Ca, Cd, Hg, Mg, Pb, Zn
red blue
HHSNN**
Ca as well as Mg (pH = 12)
red blue
Murexide
Co, Cu, Ni
yellow violet
Phthalein purple
Ba, Ca, Sr
purple colorless
Tiron
Fe(III)
blue yellow
Xylenol orange
Al, Bi, La, Sc, Th, Zr
red yellow
* Metal excess EDTA

** 2-Hydroxy-1-(2-hydroxy-4-sulfo-1-naphthylazo)-3-naphthoic acid
Light guide sensors for photometric titrations

These consist of a light source, two glass fiber (light)
guides, a concave mirror and an amplifier.
Monochromatic light from the first light guide passes
through the solution where it is partially absorbed by the
color of the sample: it reaches the concave mirror where it
is reflected to the second light guide, again with part of the
light being absorbed by the sample solution. A potential
signal is finally produced in the amplifier and transmitted
to the titrator via the electrode input.
The light path through the solution to the mirror and back
from it determines the path length (l). For example, if the
mirror is mounted at a distance of 0.5 cm then l = 1 cm.
Schematic of light guide sensor
29
Curve shapes of photometrically indicated titrations

Photometrically indicated titration curves can have different shapes; these depend on:
the type of indication: self-indication or external indication (indicator)
the stability constant of the indicator with the educt or product of the titration reaction (with
externally indicated titrations).
Externally indicated titrations produce three basic structures whose titration curves (or their
endpoint) can be evaluated in different ways:
Fig. 1 The indicator only changes its color after the

endpoint of the titration break-point evaluation
Fig. 2 The indicator changes its color in the region of

the endpoint of the titration reaction potentiometric
inflection point evaluation.
For the type of curve shown in Fig. 2 a potentiometric inflection point / endpoint evaluation is advisable and correct. This evaluation is preprogrammed in the Titrino as
standard.
The curve types shown in Figs. 1 and 3 must
be evaluated by the break-point method,
e.g. with Metrodata VESUV or TiNet (preprogrammed) or in the Metrohm Titrando.
Fig. 3 The indicator stops changing its color after the

endpoint of the titration reaction break-point evaluation.
30
I.3.2 Potentiometric indication

General
In addition to visual/photometric methods, potentiometry is one of the most frequently used
methods for the endpoint indication of titrimetric analyses. Numerous sensors are available
(some of which have been specially developed for a particular application). They cover the
whole wide range of titrations aqueous and non-aqueous acid-base titrations, redox titrations, precipitation titrations and chelometric/complexometric titrations.
The principle of potentiometric measurements
The measuring arrangement for potentiometric measurements always consists of two electrodes an indicator electrode and a reference electrode. The quantities measured are not
potentials (also known as Galvani potentials), but differences in potential (voltages).
The indicator electrode (e.g. pH, ISE, redox, Ag) provides an electrode potential that depends
upon the composition of the solution.
The reference electrode (e.g. Ag/AgCl, Hg/Hg2Cl2) has the job of supplying an electrode potential that is as independent as possible of the solution to be measured (reference potential).
The potential is measured practically current-free with a voltmeter (e.g. Titrino) having a
high-impedance measuring input. This is important as any potential drops should be avoided.
The measured potential U is made up of the individual potentials given by the indicator and
reference electrodes. Fig. 1 shows a schematic setup with a separate pH glass electrode (left)
and a reference electrode (right).
Fig. 1
U1: Galvani potential between measuring electrode
and solution
U2: Galvani potential between inner buffer and glass
membrane
U3: Galvani potential between inner bleeder electrode
and inner buffer
U4: Galvani potential of reference electrode
U5: Diffusion potential at diaphragm
31
The individual potentials U2, U3 and U4 are determined by the construction of the electrode;
they are therefore constant for a particular electrode pair. The diffusion potential U5 should
be kept relatively constant and small by taking suitable measures (optimal and clean diaphragm, constant stirring speed during the measurements, suitable reference electrolyte solution whose anions and cations have similar ionic mobilities e.g. KCl). In this way the potential U1 measured between the two electrodes depends on the measuring solution alone.
This potential is again dependent on the activity ai of the measuring ion (only active, dissociated ions are measured). For pH and ISE measurements this relationship is described by the
Nernst equation:
1) U = U0 + 2.303 RT loga ; = U0 + UN loga ;

zi F
U:
U0:
R:
T:
zi:
F:
ai:
UN:
2.303
measured potential between indicator and reference electrodes

standard potential of the electrode (depends on its construction)
gas constant (8.31441 J/K/mol)
absolute temperature in K (273.15 + t C)
charge of measuring ion i including its sign (e.g. +1 for H3O+, 2 for S2)
Faraday constant (96484.56 C/mol)
activity of measuring ion
Nernst slope (59.16 mV at 25 C and z = 1, or 29.58 mV at 25 C and z = 2)
conversion factor from natural to common logarithm
The Nernst slope UN gives the theoretical electrode slope and corresponds to
the change in potential that results when ai
changes by a factor of 10. It depends on the
temperature and the charge z of the measuring ion. UN and not the pH value of the solution is temperature-compensated by the instrument! In the following table these values
are summarized (UN versus t in C for z = 1):
Temperature C
U/mV
54.20
10
56.18
20
58.17
25
59.16
30
60.15
38
61.74
40
62.14
50
64.12
60
66.10
70
68.09
80
70.07
90
72.06
For redox potential measurements for which inert noble metal electrodes (e.g. Pt or Au) are
used the following applies:
U0:
UN:
aox:
ared:
standard potential
Nernst slope
activity of oxidized form
activity of reduced form (of the redox pair)
32
Redox reactions are pH-dependent. They often occur with the participation of hydrogen ions,
as can be seen in the following example. The equation indicates that the pH must be taken
into account in redox titrations. In extreme cases, for example, an alkaline pH value for the
below reaction could lead to the manganese only being reduced to Mn(VI) or Mn(V), or being
precipitated as manganese hydroxide.
MnO4 + 8 H3O+ + 5 e Mn2+ + 12 H2O
The associated Peters equation describes the pH dependency of the potential U and is:
3) U = U0 + UN log
a MnO4 U 8 pH
N
a Mn2+
with a Nernst slope of UN = 1/5 x 59.16 mV = 11.83 at 25 C.

Electrodes for potentiometry
As mentioned earlier in this section, potentiometric electrodes always consist of two electrodes an indicator electrode and a reference electrode. In such a combined electrode the
indicator and reference electrodes are constructed together to form a so-called single-rod
electrode. This has the advantage that measurements can be simplified and can also be
made in small volumes. Combined electrodes are primarily used for pH and redox measurements and precipitation titrations.
The measuring electrode depends upon the ion or species to be measured and the titrant
(e.g. pH glass electrode, ISE, Pt electrode, Ag electrode).
With reference electrodes the type of electrolyte filling plays a large role. This electrolyte
should have an adequate conductivity and must not take part in the reaction, nor should it interfere with the determination. The following table shows some applications:
Titration
Electrolyte solution
Acid-base, aqueous
3 mol/L KCl in water
Acid-base, non-aqueous, alkaline titrant
0.4 mol/L TEABr in ethylene glycol
Acid-base, non-aqueous, more acid titrant
1...2 mol/L LiCl in ethanol
Redox, general
Redox. very acid, hot
sat. K2SO4 in water
Precipitations with Ag
sat. KNO3 in water
Precipitations of surfactants, general
Precipitations of surfactants, with STPB
1 mol/L NaCl in water
TEABr
STPB
sat.
tetraethylammonium bromide
sodium tetraphenylborate
saturated
When recording the whole titration curve the electrodes do not need to be calibrated in order
to determine the content. However, the situation is different when an endpoint titration has to
be carried out to a particular pH value. In this case it is essential to calibrate the electrodes
used. A two-point calibration is normally carried out with buffer solution pH = 7 for the electrode zero point and buffer solution pH = 4 (EP on the acidic side) or buffer solution pH = 9
(EP on the alkaline side) in order to correct the electrode slope.
33
A theoretical pH glass electrode has a slope of 1 (100% of the Nernst slope, 59.16 mV per 1
pH at 25 C) and an electrode zero point pHas / pH(0) of 7.0 or Uas of 0 mV. In practice the situation is different. The electrode zero point Uas should be within 15 mV (pHas 6.75...7.25) and
the slope >0.95 (>56.2 mV per 1 pH at 25 C).
pHas and Uas are used to describe the real values by which the variations/asymmetries of the
pH glass electrode differ from the theoretical values pHas = 7.00 and Uas = 0.0 mV. As the
two sides of the glass electrode are never fully identical, a small potential known as the
asymmetry potential occurs across the glass membrane.
In order to inform the instrument about the real electrode data the electrode has to be calibrated. Buffer solutions have a defined pH value that is temperature-dependent. The temperature profile of the buffer solution can be compensated on the instrument! The appropriate
data for the buffer solutions is entered during calibration or, as with Metrohm pH meters / Titrandos, is already stored in the instrument. The temperature profile of the measuring solution cannot be compensated. This means that the instrument shows the correct value for the
actual measuring temperature. The following table shows the temperature-dependent values
for Metrohm buffer solutions:
Temperature t / C
pH = 4.00 0.02
pH = 7.00 0.02
pH = 9.00 0.02
10
3.99
7.06
9.13
20
3.99
7.02
9.04
25
4.00
7.00
9.00
30
4.00
6.99
8.96
38
4.02
6.98
8.91
40
4.02
6.98
8.90
50
4.04
6.97
8.84
60
4.07
6.97
8.79
70
4.11
6.98
8.74
80
4.15
7.00
8.71
90
4.20
7.01
8.68
Buffer solutions are not stable. They can be decomposed by bacteria and/or molds, while the
pH of alkaline buffer solutions can change as a result of CO2 absorption from the atmosphere.
This is why you should always use fresh buffer solutions and never pour used buffers back
into the storage bottle!
34
I.3.3 Indication with polarized electrodes

General
These methods are primarily used for redox titrations in dilute solutions or if dilute titrants are
used, as in such cases potentiometric indication is not longer satisfactory (titration curves are
too flat loss in precision).
Terminology:
Amperometry:
potential polarization/current measurement with one polarizable electrode

Upol
Biamperometry:
potential polarization/current measurement with two polarizable electrodes Upol
Voltametry:
current polarization/potential measurement with one polarizable electrode

Ipol
Bivoltametry:
current polarization/potential measurement with two polarizable electrodes Ipol
Upol and Ipol are included in the Titrino as so-called polarizers and can be set throughout a wide
range. Never connect pH glass electrodes and ISEs to a polarizer they will be destroyed!
Amperometric indication
The use of amperometric indication (as well as polarimetric indication) for titration originated in polarography. A dropping mercury electrode (DME) is used as the indicator electrode
(switched as the cathode) and an Ag/AgCl electrode as the reference electrode. A constant
potential is applied between the two electrodes that is so high that at least one of the reaction partners (sample ion or titrant) is reduced at the cathode. This causes a diffusion current,
which is evaluated. The method is very sensitive and can be used for concentrations down to
c = 106 mol/L. However, this method has never been able to become properly established
because of the indicator electrode (DME). The resulting titration curves are T-shaped (one active reaction partner) or V-shaped (both reaction partners active).
Biamperometric (dead-stop) indication
In this case both the electrodes (usually double-Pt electrodes) are polarizable. A constant potential is also applied to the electrodes, but this is considerably lower (max. 250 mV) than in
amperometric indication. This method is chiefly used for iodometric determinations. The following reactions occur at the electrodes:
Cathode: I2 + 2 e 2 I (reduction)
Anode:
2 I 2 e I2 (oxidation)
This means that a current flows for as long as
iodine is present. When the iodine has been
consumed (e.g. by titration with thiosulfate)
the current drops to zero (dead-stop); the
resistance between the electrodes increases greatly and the electrodes are again polarized.
Example of a biamperometric titration curve
35
Voltametric indication
As in amperometry, only one electrode (the indicator electrode) is polarizable. In contrast to
amperometry the current polarization takes place with only a few A, i.e. 1...5 A. If Ipol has
the correct sign (plus for oxidizing titrants, minus for reducing titrants) then the resulting titration curves are similar to those for potentiometric indication. However, the curves are
steeper and cover a larger potential range. An example of the use of this method is the titration of free chlorine in drinking water with c(As2O3) = 0.005 mol/L using a combined Pt electrode, Ipol = 1 A.
Bivoltametric indication
Again two electrodes (usually double-Pt electrodes) are polarized by applying a small DC or
AC current (AC is considerably more sensitive than DC) between the electrodes and measuring the resulting potential. The titration curves obtained are similar to those found in biamperometry, but are usually more pronounced and larger. If both the sample and titrant are
electrochemically active then peak-shaped titration curves are produced (Fig. 1). If only one
partner is electrochemically active then L-shaped curves are produced (Fig. 2).
Examples:
Fig. 1
This indication method is used very frequently in the Karl Fischer titration for water determination. The resulting potentials for iodine or excess water are, of course, dependent on the applied current (Ipol). Three examples (separate double Pt-sheet electrode):
Ipol = 50 A, U approx. 100 mV for excess iodine, approx. 680 mV for excess water
36
I. 4 Electrodes
General
One of the most important criteria for volumetric analysis is to find the equivalence point (the
point in the titration at which it is indicated that the species of the sample has been completely titrated stoichiometrically converted and at which there is not yet an excess of titrant).
The associated value for the volume or endpoint shown by the instrument must be as close
as possible to the equivalence point. Even the most modern analytical instruments, with their
high resolution on the volume axis (of the titrant), are of little use if unsuitable sensors are
used or if they have a poor response. In Section I.3 Indication methods the theory behind
the various possibilities has already been mentioned. In this section we are concerned with
providing details of the most important electrodes for the methods described in the practical
section and passing on information and recommendations to the users.
1. Acid-base titrations, aqueous
The choice of electrode depends mainly on the matrix (type of sample) in which the titration
is to be carried out. The sample solution could influence both the glass membrane and the
diaphragm and therefore affect the reference electrode. Combined electrodes are normally
used measuring electrode and reference electrode (possibly with an additional temperature
sensor) are contained in a single electrode.
1.1 For general use
Contents of uncontaminated acids and bases are best deermined with the 6.0232.100 Ecotrode LL combined pH glass electrode with ceramic pin diaphragm.
1.2 For beverages (fruit or vegetable juice, wine, beer) and pharmaceutical ingredients
according to USP and Pharm. Europe and for solutions containing phosphates
Recommended electrode: 6.0259.100 LL Unitrode. This electrode has a fixed ground-joint diaphragm that is not easily blocked and ensures a stable, rapid response.
1.3 Water and ion-deficient solutions
Recommended electrode: 6.0253.100 LL Aquatrode Plus. It has been developed specially for
such applications and has a fixed ground-joint diaphragm, which ensures that the total resistance remains low. A special glass combining a low membrane resistance with the greatest
possible robustness is also used for this electrode.
1.4 Products containing proteins (dairy products, nutrient solutions)
Recommended electrode: 6.0235.100 LL Porotrode. It has special diaphragms (two capillaries) and a special electrolyte that prevents proteins from being precipitated at or on the diaphragm and negatively affecting the electrode response.
1.5 Acidic solutions containing fluoride
Recommended electrode: 6.0421.100 combined Sb electrode. No pH glass electrode can be
used in such solutions as glass is attacked by hydrofluoric acid the electrode would only respond slowly and would lose its slope.
37
1.6 Electroplating baths, dye baths, Bayer caustic solution (strongly alkaline digestion
mixtures used in aluminum production from bauxite), amine-containing absorption solutions, dispersions, liquid manure, wastewater containing sulfides
Recommended electrode: 6.0255.100 LL combined pH glass electrode with ground-joint diaphragm, double junction. In order to prevent sample solution or sample constituents from entering the reference electrolyte (this would destroy the Ag/AgCl reference system and make
the electrode unusable) an electrode with a double electrolyte chamber (double junction) is
used. The outer electrode chamber can be filled with any electrolyte solution, which can be
easily exchanged. The electrode has a separable ground-joint glass diaphragm that is almost
impossible to block.
2. Acid-base titrations, non-aqueous
General
The choice of electrode system depends primarily upon the solvent (mixture) that is to be titrated and the titrant used. In principle, a differentiation can be made between more or less
polar and completely nonpolar solvents. Nonpolar solvents (e.g. pure hydrocarbons or chlorinated hydrocarbons) have a very high electrical resistance. Although they are easily able to
dissolve oils and fats (as well as paraffins), ionic compounds are only poorly soluble. If the total resistance (solvent plus sample) is too high then potentiometric indication of the titration is
no longer possible. Massive interference occurs as a result of electrostatic charges in such
cases the titration curve can no longer be evaluated.
2.1 In solvents with a moderate electrical resistance
Recommended electrode: 6.0229.100 LL Solvotrode. This electrode has been specially developed for titrations in non-aqueous solvents and has the following advantages:
Large membrane glass surface with comparatively low resistance and good response
Electric shielding of the whole electrode up to the connection plug
Separable ground-joint diaphragm with good electrolyte flow almost never becomes
blocked
Single-rod (combined) electrode
Easy to exchange the electrolyte solution
We recommend the use of the following electrolyte solutions:
a) Titrant is an acid
c(LiCl) = approx. 2 mol/L in ethanol. Dilute saturated solution of LiCl (Metrohm no. 6.2312.000)
1:1 with ethanol.
b) Titrant is an base
c(TEABr) = 0.4 mol/L in ethylene glycol (Metrohm no. 6.2320.000)
TAEBr = tetraethylammonium bromide
2.2 In solutions with a relatively high electrical resistance
Recommended electrodes: 6.0431.100 Pt Titrode plus 6.0729.100 Ag/AgCl reference electrode, shielded, with double junction and ground-joint diaphragm. Electrolyte filling differs depending on whether the titrant is acidic or basic. See also remarks under a) and b) in 2.1.
38
The higher the electrical resistance of the solution to be titrated, the greater the interference
by electrostatic charges. If this interference is so large that the Solvotrode can no longer be
used then work must be carried out with the so-called three-electrode technique and the differential amplifier input (diff) of the Titrino. The specially shielded Ag/AgCl electrode is used
as the reference electrode, the pH glass membrane of the Pt Titrode as the measuring electrode and the platinum ring of the Pt Titrode as auxiliary/bleeder electrode.
If this electrode combination does not help (too strong interference is still present) then the
titration cannot be indicated potentiometrically. In such cases we recommend the use of a different solvent or the addition of approx. 5...10% V/V acetone or IPA (isopropanol) to the solution. (In pure aprotic solvents it is often only possible to titrate photometrically using a colored indicator.)
3. Precipitation titrations
General
By far the most frequent titrations of this type are precipitations with silver nitrate. Many anions
produce sparingly soluble silver compounds that can be used for the determination of these
anions. In mixtures it is always the most sparingly soluble compound that is titrated (smallest
solubility product). In order to achieve a good separation the solubility products must differ
sufficiently from each other. The following are titrated with silver nitrate: chloride, bromide, iodide, cyanide, sulfide, mercaptans and thiocyanate (the anions of other sparingly soluble Ag
compounds e.g. chromate or thiosulfate are determined better by redox titrations).
Further precipitation titrations are, for example, sulfate determination (with barium chloride or
acetate or perchlorate), fluoride determination (with lanthanum nitrate) and naturally the determination of the purity of silver (with potassium bromide).
In recent years the potentiometric titration of surfactants has greatly increased and is replacing more and more the complicated visual Epton titration, which is either difficult to automate
or cannot be automated at all. More details about electrodes for surfactant titrations are given
under 3.2.
3.1 Titrations with AgNO3
Recommended electrodes: 6.0430.100 Ag Titrode and/or 6.0450.100 combined Ag-ring
electrode.
Bright silver electrodes do not always stabilize quickly (independent of the construction). This
applies in particular whenever titrations are carried out in dilute solutions or solutions with a
high ionic strength (examples are traces of chloride in drinking water, in salts, or in NaOH or
Na2CO3 after neutralization). The electrode does not remain bright, as the corresponding
Ag salt is formed little by little on its surface. For this reason we recommend giving the electrode an Ag2S coating right from the start. This provides it with a rapid response with usually
large potential jumps; the reproducibility of the results is also improved. The electrode behaves like an ion-selective electrode (ISE), i.e. it responds both to Ag+ and the corresponding anion.
However, the Ag Titrode should be preferred. Its glass membrane acts as a reference electrode and hardly alters its potential at all if the titration is carried out in buffered solutions
(acidic or alkaline). As this glass electrode is connected to the high-impedance input of the
Titrino (measuring electrode input), the titration curves are produced in the opposite (and unusual) direction compared with a titration with a combined Ag electrode. The Ag Titrode has
the advantage that no diaphragm is present (and therefore cannot be blocked) and no elec-
39
trolyte solution needs to be refilled. It can be stored in dist. H2O. With combined Ag electrodes
it is, of course, not possible to use electrolyte solutions containing chloride (formation of AgCl
which influences the result and blocks the diaphragm). KNO3 solutions are normally used.
In acidic solution (pH <4, in order to avoid possible precipitation of Ag2CO3) the following are
titrated: chloride, bromide, iodide and thiocyanate
In alkaline solution (pH >11) the following are titrated: cyanide, sulfide and (usually) mercaptans.
3.2 Surfactant titrations
General
Surfactants are divided into the following classes (see also I.2.):
Anionic (anion-active) surfactants and soaps
Cationic (cation-active) surfactants
Amphoteric surfactants (can be either anionic or cationic depending on the pH)
Nonionic surfactants (NIOs)
The anionic, cationic and the largest group of nonionic surfactants the polyoxyethylene
(POE) adducts can be titrated potentiometrically.
Anionic surfactants react with cationic surfactants and vice versa. In aqueous solutions the
corresponding ion association is precipitated (in the two-phase titration it is extracted into the
organic phase).
As their name says, nonionic surfactants have no groups that can react and therefore cannot
be titrated directly. Barium ions are added to their solutions. A Ba pseudo-complex is formed
that can be precipitated and thus titrated with sodium tetraphenylborate.
Single-rod electrodes (combined electrodes) are difficult to handle in surfactant analysis.
Changes in the diffusion potential occur at the diaphragm during the titration; these may falsify the titration curve and therefore produce incorrect results. This is why Metrohm in principle uses only separate electrodes: on one side is the measuring electrode (surfactant ISE),
on the other side is the Ag/AgCl reference electrode with double junction and a ground-joint
diaphragm.
Recommended reference electrode: 6.0726.107 (electrolyte solution for ionic surfactants is
KCl, c = 3 mol/L, for nonionic surfactants NaCl, c = 1 mol/L at least in the outer electrolyte
vessel). We recommend the use of the 3.421.3720 ground-joint glass sleeve for cationic surfactants.
3.2.1 Anionic surfactants, aqueous
Recommended electrode: 6.0507.120 Ionic Surfactant Electrode
3.2.2 Cationic surfactants, aqueous
Recommended electrode: 6.0507.150 Cationic Surfactant Electrode
3.2.3 Nonionic surfactants (aqueous only)
Recommended electrode: 6.0507.010 NIO Surfactant Electrode
3.2.4 Two-phase titration, anionic and cationic surfactants, pH <10, organic medium chloroform or MIBK
Recommended electrode: 6.0507.130 Surfactrode Resistant
40
3.2.5 Two-phase titration, anionic surfactants and soaps, cationic surfactants, pH >10, organic
medium MIBK
Recommended electrode: 6.0507.140 Surfactrode Refill
The surfactant ISEs for aqueous titrations are polymer membrane (PVC) ISEs and are either
not resistant to solvents or have a limited resistance. Metrohm (in contrast to other suppliers)
offers five different surfactant electrodes. Among them you will find the optimal electrode for
your application and do not have to try to solve all your problems (usually unsatisfactorily)
with a single electrode.
4. Redox titrations
General
Probably the most frequently carried out redox titrations are iodometric titrations using iodine
as the titrant (in the form of the water-soluble triiodide, KI3) and thiosulfate. Other titrants are
KMnO4, Ce(IV), KBrO3, Fe(II) and As(III), which latter, because of its toxicity, is relatively seldom used.
Noble metal electrodes must be used for indicating these titrations. Silver is unsuitable, as it
oxidizes rapidly or forms silver halide or silver sulfide coatings. These damage the electrode
the potential stabilization takes longer. Gold is only used for a few special applications. Platinum electrodes are normally used.
But even the surfaces of platinum electrodes are not immune to oxidation. Oxidized Pt electrodes only become stabilized very slowly, the titration curves are flat and the potential jumps
are small. In order to obtain a perfectly functioning and quick electrode it must be regenerated. This is best carried out by electrolytic hydrogen evolution on its surface:
The Pt electrode to be treated is connected to the minus pole (cathode) of a DC source of
4.5...6 V (e.g. a battery). A further platinum (wire) electrode or an iron nail is connected to the
plus pole (anode). Do not use copper as anode as this would copper-plate the Pt!
Both electrodes are immersed in a stirred solution of c(H2SO4) = approx. 2 mol/L under voltage. Hydrogen should be produced at the cathode (and accordingly oxygen at the anode)
this can be recognized by the formation of bubbles. After approx. 5 min the electrodes still
under voltage are removed from the solution and rinsed thoroughly with dist. H2O.
4. 1 Potentiometric indication
Recommended electrodes: 6.0431.100 Pt Titrode and/or 6.0451.100 LL combined Pt-ring
electrode.
The Pt Titrode is to be preferred. Its glass membrane acts as the reference electrode and
hardly changes its potential at all if the titration is carried out in buffered solutions (usually
acidic). As the glass electrode is connected to the high-impedance input of the Titrino (measuring electrode input) the titration curves are produced in the opposite (and unusual) direction compared with a titration with a combined Pt electrode. The Titrode has the advantage
that no diaphragm is present (and therefore cannot be blocked) and no electrolyte solution
needs to be refilled. It can be stored in dist. H2O.
4.2 Bivoltametric and/or biamperometric (dead stop) indication
Recommended electrodes: 6.0341.100 double Pt-wire electrode or 6.0309.100 double Ptsheet electrode.
41
The double-wire electrode is suitable for general applications (e.g. iodometry); the doublesheet electrode is mainly used with dilute titrants (examples are SO2 in wine or vitamin C with
dichlorophenolindophenol).
5. Complexometric / chelometric titrations
General
Apart from acid-base titrations, complexometric titrations are probably the most frequently
used volumetric titrations throughout the world. In more than 90% of the cases the disodium salt of ethylenediamine tetraacetic acid (EDTA) is used. In earlier days nitrilotriacetic acid
(NTA) was frequently used today its use is no longer so important. For special, more selective titrations the sodium salts of the following complexing agents are still used:
DCTA trans-diaminocyclohexane tetraacetic acid
DIGITA bis-(aminoethyl)-glycol ether tetraacetic acid
DTPA diethylenetriamine pentaacetic acid
EGTA ethylene glycol-bis-(2-aminoethyl)-tetraacetic acid
One thing that all of these have in common is that they form 1:1 complexes with metal ions,
no matter whether the metal ions have a double or triple positive charge. This means that, for
example, 1 mL c(Na2EDTA) = 0.1 mol/L corresponds to 4.008 mg Ca, 2.431 mg Mg, 2.698 mg
Al, 5.585 mg Fe(II) or Fe(III), etc. Using Na2EDTA as an example this appears as follows:
Ca2+ + Na2H2EDTA + 2 H2O
Al3+ + Na2H2EDTA + 2 H2O
Na2CaEDTA + 2 H3O+
NaAlEDTA + 2 H3O+ + Na+
The acids of the complexing agents are hardly soluble in water. For this reason their sodium
salts are generally used.
values, by recomplexing or by the addition of masking agents. Examples:
Ca/Mg mixtures:
addition of acetylacetone (recomplexing)
Ca/Al mixtures:
titrate Ca alkaline, titrate Al acidic
KCN addition:
masks Ag, Cd, Co, Cu, Hg, Ni and Zn
Triethanolamine addition:
masks Al and Fe
42
5.1 Titrations with photometric indication

Recommended electrodes: 6.1109.110 Spectrosense 610 nm or 6.1109.100 Spectrosense
523 nm.
The oldest and still the most widespread method for endpoint recognition in complexometric titrations is the use of suitable colored indicators. Together with the metal ion to be determined these form a colored complex, whose structure and color changes abruptly when all
the metal ions have been (re)complexed or titrated, e.g. by EDTA. Here is a small selection
of frequently used colored indicators (the metals whose ions are determined are shown in
brackets):
Eriochrome black T (Mg, Zn, Cd, Pb, Hg)

Murexide (Co, Ni, Cu)
Tiron (Fe)
Phthalein purple (Ca, Sr, Ba)
Pyrocatechol violet ( Bi, Co, Ni, Mn, In, Zn, Cd)
Xylenol orange (Al, La, Th, Bi, Sc, Zn)
HHSNN (Ca in the presence of a large amount of Mg at pH = approx. 12)
HHSNN is 2-hydroxy-1-(2-hydroxy-4-sulfo-1-naphthylazo)-3-naphthoic acid
Colored indicators for complexometric titrations are also complexing agents. However, their
complex formation constants must be smaller than those of the titrants. In addition, the indicator complex must also have a different color from that of the free indicator and have a more
intensive color than that of the titrant complex. As these colored indicators are usually multivalent acids, it must be remembered that their color-change range is pH-dependent. As already
mentioned in Section I.2., the titration is carried out in a buffered solution.
At the start of the titration the color of the solution is determined by the metal-indicator complex. The titrant reacts first with the free metal ions and towards the end of the titration it also
extracts the metal ion from the weaker indicator complex. The endpoint/point of inflection is
reached when 50% of the indicator has been released (mixed color). A sharper color change
can often be achieved if an organic solvent (e.g. acetone or ethanol) is added to the solution.
Of course, titrations can also be carried out with visual endpoint recognition. However, these
methods cannot be automated and, above all, are virtually impossible to validate as each analyst sees the color change differently depending on the lighting conditions. This is the reason behind the use of photometric sensors, such as are built into the Spectrosense 523 nm
and 610 nm.
43
5.2 Indication with the Cu ISE

Recommended electrode: 6.0502.140 Cu ISE (do not forget the reference electrode, e.g.
Metrohm 6.0726.107).
The Cu ISE is a crystal membrane electrode.
The Cu ISE responds (only) to Cu(II) ions (otherwise it would not be an ion-selective electrode). In order to be able to indicate the titration of other metal ions a trick has to be used.
Some CuEDTA is added to the solution to be titrated. CuEDTA is a very stable complex and
only releases a very small amount of Cu(II) ions. However, in alkaline solution and in the presence of e.g. Ca(II) ions all the Cu(II) ions are released and the Ca-EDTA complex is formed.
This means that during the titration the concentration of Cu(II) ions is continuously reduced
until at the endpoint the very small initial value is again reached. A typical potentiometric titration curve is obtained. The following equations symbolize the three steps:
CuEDTA Cu(II) + EDTA
CuEDTA + Ca(II) CaEDTA + Cu(II)
Cu(II) + EDTA CuEDTA
5.3 Indication with the Ca ISE
Recommended electrode: 6.0508.110 Ca ISE (do not forget the reference electrode, e.g.
Metrohm 6.0726.107).
The Ca ISE is a polymer membrane electrode.
This electrode is used especially for the complexometric titration of calcium. In many cases
the Mg(II) content of the sample is also to be determined at the same time as the Ca(II) content. A typical and frequently used example is the titration of water hardness. This is also done
by using a trick. An auxiliary complexing agent (acetylacetone in Tris buffer) is added to the
solution.
If the titration is now carried out with EDTA the Ca(II) reacts first. If Ca(II) is no longer present the auxiliary complexing agent enters the picture. Mg(II) reacts with CaEDTA to form
MgEDTA, the corresponding amount of Ca(II) is again released and can be titrated again with
EDTA. A potentiometric titration curve with two endpoints is obtained. EP1 (flat) corresponds
to Ca(II) and EP2 EP1 to the Mg(II).
44
I. 5 Titrants: preparation and titer determination

General
Titrants are standard solutions, i.e. solutions that contain a defined content of a reactant. This
content is given as the molar concentration c in mol/L. The term normality (mol/L divided by
the valency), which was frequently used in earlier days, is no longer valid and should therefore no longer be used. Examples:
0.1 N HCl
0.1 N H2SO4
0.1 N iodine solution
0.1 N KMnO4
c(HCl)
c(H2SO4)
c(I2)
c(KMnO4)
= 0.1 mol/L
= 0.05 mol/L
= 0.05 mol/L
= 0.02 mol/L
Not all titrants have a stable titer, i.e. the molar concentration of the dissolved reactant can
change with time. Examples:
Bases absorb CO2 from the atmosphere, the pH drops
Iodine solutions release iodine
Arsenite solutions are oxidized to arsenates by atmospheric oxygen
Thiosulfate solutions decompose as a result of CO2 absorption with the deposition of sulfur
Potassium permanganate solutions in the presence of organic substances (e.g. dust particles) deposit MnO2 (permanganate oxidizes such foreign bodies and is itself reduced).
Titrants in organic solvents can be concentrated by evaporation.
This means that the titer of such a solution is constantly changing. Titer determinations are
carried out in order to know the correct molar concentration so that correct calculations can
be carried out.
The titer is determined by comparison with so-called standard titrimetric substances. These
hardly change in content, are available at a defined degree of purity, can be dried and are directly traceable to standard reference materials (e.g. National Institute of Standards and Technology NIST, USA).
Such standard titrimetric substances or secondary standards are:
For bases
potassium hydrogen phthalate
M = 204.23 g/mol
For acids
tris(hydroxymethyl)-aminomethane
M = 121.14 g/mol
For iodine solution
arsenic trioxide
M = 197.841 g/mol
For thiosulfate
potassium iodate
M = 214.001 g/mol
For cerium(IV):
disodium oxalate
M = 133.999 g/mol
For KMnO4
disodium oxalate
M = 133.999 g/mol
For silver nitrate
sodium chloride
M = 58.443 g/mol
For Na2EDTA
calcium carbonate
M = 100.09 g/mol
For potassium dichromate
this is itself a standard titrimetric substance; its solutions have M = 294.184

a stable titer
For potassium bromate
this is itself a standard titrimetric substance; its solutions have M = 167.001

a stable titer
Most standard solutions and titrants are commercially available in the form of ready-to-use
solutions or concentrates; their titer has been adjusted by the manufacturer to 1.000 at 20 C.
45
However, we nevertheless strongly urge you to carry out a titer determination! This provides
you with more security, and it could mean that you avoid serious errors.
In principle titer determinations should always be carried out at the same temperature as that
used for the subsequent titrations. As the temperature increases the titrants expand aqueous solutions not as much as non-aqueous ones.
Thus, for a temperature difference of 5 C and a theoretical consumption of 10.00 mL, the
consumption will be higher by 12.5 L for aqueous and about 50 L for non-aqueous titrants.
Accordingly, a titer of 1.000 at 20 C becomes 0.9988 and 0.9950 at 25 C, respectively.
Examples
I.5.1 c(NaOH) = 0.1 mol/L
NaOH solutions do not have a stable titer. They can absorb CO2 from the atmosphere to form
sodium carbonate:
2 NaOH + CO2 Na2CO3 + H2O
This means that not only the titer decreases. As NaOH and Na2CO3 have different base
strengths this will affect the titration curve and therefore the results. In order to largely avoid
CO2 absorption from the atmosphere the drying or absorber tube of the Exchange Unit is filled
with soda lime (CO2 absorber). As strong bases attack glass the Exchange Unit should be
provided with a plastic storage bottle.
Preparation
Approx. 4.4 g NaOH pellets are weighed out into a beaker, treated with a little dist. H2O and
swirled briefly in order to dissolve any Na2CO3 present on the surfaces. This solution is rejected and the remaining NaOH is dissolved in CO2-free dist. H2O, transferred to a 1000 mL volumetric flask, made up to the mark and mixed. Carbon dioxide is removed from the dist. H2O
by boiling or by passing a stream of e.g. nitrogen through it.
Titer determination
Potassium hydrogen phthalate is dried overnight in a drying oven at 105 C and allowed to
cool down in a desiccator for at least 1 h. Care must be taken that the titrations are carried out
at a constant temperature.
Normally the titer determination is carried out three times and the mean value is used. The
mean value of the titer can be stored in the titrator as a common variable.
Approx. 200 mg potassium hydrogen phthalate is accurately weighed out into the titration
beaker to the nearest 0.1 mg and dissolved in approx. 50 mL CO2-free dist. H2O. It is immediately titrated with c(NaOH) = 0.1 mol/L to after the first endpoint (combined pH glass electrode).
Calculating the titer
1 mL c(NaOH) = 0.1 mol/L corresponds to 20.423 mg KH phtalate
Titer = C00 / C01 / EP1 (formula entered in the Titrino)
EP1 = mL NaOH up to endpoint
C00 = weight of KH phthalate in mg
C01 = 20.423
Result to be given to four decimal places.
46
I.5.2 c(HCl) = 0.1 mol/L

Preparation
Approx. 800 mL dist. H2O is placed in a 1000 mL volumetric flask. 9.8 mL hydrochloric acid,
w(HCl) = 32% is added, made up to the mark with dist. H2O and mixed.
Titer determination
Tris(hydroxymethyl)-aminomethane (Tris) is dried overnight in a drying oven at 105 C and allowed to cool down in a desiccator for at least 1 h. Care must be taken that the titrations are
carried out at a constant temperature.
mean value of the titer can be stored in the Titrino as a common variable.
Approx. 100 mg Tris is accurately weighed out into the titration beaker to the nearest 0.1 mg
and dissolved in approx. 50 mL CO2-free dist. H2O. It is immediately titrated with c(HCl) = 0.1
mol/L to after the first endpoint (combined pH glass electrode).
1 mL c(HCl) = 0.1 mol/L corresponds to 12.114 mg Tris
Titer = C00 / C01 / EP1
EP1 = mL HCl up to endpoint
C00 = weight of Tris in mg
C01 = 12.114
I.5.3 c(I2) = 0.05 mol/L

Iodine solutions do not have a stable titer. Iodine escapes from the solution by sublimation
the molar concentration decreases.
Preparation
25 g pure, iodate-free potassium iodide is weighed out into a 1000 mL volumetric flask and
dissolved in 40 mL dist. H2O. 12.8 g iodine is added and the flask is sealed and then shaken
until all the iodine has dissolved (as KI3). It is then made up to the mark with dist. H2O and
mixed. Do not dilute with dist. H2O too soon as otherwise the iodine will no longer dissolve.
Titer determination
Arsenic trioxide is dried overnight in a drying oven at 105 C and allowed to cool down in a
desiccator for at least 1 h. Care must be taken that the titrations are carried out at a constant
temperature.
Approx. 60 mg As2O3 is accurately weighed out into the titration beaker to the nearest 0.1 mg
and quickly dissolved in approx. 10 mL c(NaOH) = 0.1 mol/L. 12 mL c(HCl) = 0.1 mol/L is
added immediately followed by approx. 2 g NaHCO3 and then diluted to approx. 80 mL with
dist. H2O (the solutions used should be free from oxygen). Titrate with c(I2) = 0.05 mol/L to
after the first endpoint (Pt Titrode or combined Pt-ring electrode).
Na3AsO3 + I2 + H2O
Na3AsO4 + 2 HI
47

1 mL c(I2) = 0.05 mol/L corresponds to 4.946 mg As2O3
Titer = C00 / C01 / EP1
EP1 = mL iodine solution up to endpoint
C00 = weight of As2O3 in mg
C01 = 4.946
I.5.4 c(Na2S2O3) = 0.1 mol/L

Thiosulfate solutions do not always have a stable titer. They can be decomposed due to catalysis by traces of heavy metals, be oxidized by microorganisms or undergo CO2 absorption. This reduces the molar concentration. It is best to use boiled ultrapure water to prepare
the solution.
Preparation
25 g Na2S2O3 x 5 H2O is weighed out into a 1000 mL volumetric flask, dissolved in CO2-free
dist. H2O, made up to the mark and mixed.
Titer determination
Potassium iodate is dried overnight in a drying oven at 180 C and allowed to cool down in a
temperature.
Approx. 50 mg KIO3 is accurately weighed out into the titration beaker to the nearest 0.1 mg
and dissolved in approx. 100 mL dist. H2O. Approx. 1 g potassium iodide and 10 mL sulfuric
acid w(H2SO4) = 25% are added and immediately titrated with c(Na2S2O3) = 0.1 mol/L to after
the first endpoint (Pt Titrode or combined Pt-ring electrode).
KIO3 + 5 KI + 3 H2SO4 3 I2 + 3 K2SO4 + 3 H2O
2 Na2S2O3 + I2 Na2S4O6 (Na tetrathionate) + 2 NaI
1 mL c(Na2S2O3) = 0.1 mol/L corresponds to 3.567 mg KIO3
Titer = C00 / C01 / EP1
EP1 = mL thiosulfate solution up to endpoint
C00 = weight of KIO3 in mg
C01 = 3.567
I.5.5 c(Na2EDTA) = 0.1 mol/L

EDTA solutions have a stable titer. They always form 1:1 complexes with metal ions, irrespective of their charge number:
Me2+ + Na2H2EDTA + 2 H2O
Me3+ + Na2H2EDTA + 2 H2O
Na2MeEDTA + 2 H3O+
NaMeEDTA + 2 H3O + + Na+
values or after the addition of masking agents.
48
The endpoint of the titration can be indicated in different ways. The oldest and still the most
widespread method is the use of suitable colored indicators (photometric titration). For potentiometric indication ion-selective electrodes are usually used (e.g. Cu ISE, Ca ISE). Explanations are given for the individual determinations in Section II.5.
Preparation
37.224 g Na2EDTA x 2 H2O is weighed out into a 1000 mL volumetric flask, dissolved in dist.
H2O, made up to the mark and mixed.
Additional reagents
Buffer solution pH = 10:
54 g NH4Cl and 350 mL ammonia solution, w(NH3) = 25%,

are dissolved in dist. H2O and made up to 1 liter.
Auxiliary solution:
Cu(NH4)2EDTA, c = 0.1 mol/L (e.g. Merck no. 105217)
Titer determination
Calcium carbonate is dried overnight in a drying oven at 140 C and allowed to cool down in
a desiccator for at least 2 h. Care must be taken that the titrations are carried out at a constant temperature.
Approx. 100 mg CaCO3 is accurately weighed out into the titration beaker to the nearest 0.1
mg and suspended in approx. 20 mL dist. H2O. Hydrochloric acid c(HCl) = 5 mol/L is added
drop by drop under stirring until everything has dissolved (as CaCl2). After the addition of approx. 30 mL dist. H2O, 5 mL buffer solution pH = 10 and 0.5 mL auxiliary solution it is titrated
with c(Na2EDTA) = 0.1 mol/L to after the first endpoint (Cu ISE/reference electrode).
1 mL c(Na2EDTA) = 0.1 mol/L corresponds to 10.009 mg CaCO3
Titer = C00 / C01 / EP1
EP1 = mL Na2EDTA solution up to endpoint
C00 = weight of CaCO3 in mg
C01 = 10.009
I.5.6 c(AgNO3) = 0.1 mol/L

Silver nitrate solutions are sensitive to light. After they have been placed in the Exchange Unit
they are automatically protected against light.
Precipitation titrations with silver nitrate are normally carried out in acidified solutions (with
the exception of cyanide) in order to prevent the formation of interfering AgOH or Ag2CO3.
For potentiometric indication we recommend the use of an Ag electrode with an Ag2S coating. In comparison to a bright Ag electrode it has a more stable potential and a quicker response. Metrohm Application Bulletin no. 25 describes the preparation of the coating on Ag
electrodes.
Preparation
16.99 g AgNO3 is weighed out into a 1000 mL volumetric flask and dissolved in approx. 200
mL dist. H2O. After the addition of 0.1 mL nitric acid, c(HNO3) = 2 mol/L, it is made up to the
mark with dist. H2O and mixed.
49
Titer determination
Sodium chloride is dried overnight in a drying oven at 140 C and allowed to cool down in a
temperature.
Approx. 60 mg NaCl is accurately weighed out into the titration beaker to the nearest 0.1 mg
and dissolved in approx. 50 mL dist. H2O. After the addition of 1 mL c(HNO3) = 2 mol/L it is titrated with c(AgNO3) = 0.1 mol/L to after the first endpoint (Ag Titrode with Ag2S coating).
1 mL c(AgNO3) = 0.1 mol/L corresponds to 5.844 mg NaCl
Titer = C00 / C01 / EP1
EP1 = mL AgNO3 solution up to endpoint
C00 = weight of NaCl in mg
C01 = 5.844
I.5.7 c(KMnO4) = 0.02 mol/L

Permanganate solutions have if pretreated correctly and stored protected against light a
relatively stable titer. However, traces of ammonium salts and organic substances (e.g. dust
particles) have the effect of reducing KMnO4 to MnO2. If this is not removed from the solution
it acts as a catalyst and the titer continuously decreases:
MnO4 + 4 H3O+ + 3 e {MnO2} + 6 H2O
Preparation
3.2 g KMnO4 is weighed out into a beaker and dissolved in approx. 950 mL dist. H2O. The solution is heated to boiling and kept boiling for approx. 15 min. After cooling down it is filtered
through a glass filter crucible (not a paper filter! permanganate oxidizes paper constituents
and is reduced to MnO2!) into a thoroughly cleaned 1000 mL volumetric flask, made up to the
mark with dist. H2O and mixed. (If the solution is prepared directly without heating then the
MnO2 formed must be filtered off after approx. 2 weeks.)
Titer determination
Disodium oxalate is dried overnight in a drying oven at 240 C and allowed to cool down in a
temperature.
Approx. 70 mg Na2C2O4 is accurately weighed out into the titration beaker to the nearest 0.1
mg and dissolved in approx. 50 mL dist. H2O. It is treated with 0.5 to 1 g MnSO4*, 5 mL sulfuric acid w(H2SO4) = 25% is added and then titrated with c(KMnO4) = 0.02 mol/L to after the
first endpoint (Pt Titrode or combined Pt-ring electrode).
* Manganese sulfate acts as a catalyst and accelerates the oxidation of the oxalate so that the titration does not
have to be carried out in a hot solution.
2 KMnO4 + 5 Na2C2O4 + 8 H2SO4 2 MnSO4 + 5 Na2SO4 + K2SO4 +10 CO2 + 8 H2O
50

1 mL c(KMnO4) = 0.02 mol/L corresponds to 6.700 mg Na2C2O4
Titer = C00 / C01 / EP1
EP1 = mL KMnO4 solution up to endpoint
C00 = weight of Na2C2O4 in mg
C01 = 6.7
I.5.8 Cer(IV), c = 0.1 mol/L

Cerium(IV) solutions are strong oxidizing agents with a stable titer; titrations with them are
only carried out under strongly acidic conditions. In comparison to KMnO4 they have the advantage that titrations can also be carried out in solutions containing chlorides (chloride ions
interfere with the KMnO4 titration KMnO4 oxidizes them to chlorine / chlorine dioxide).
Preparation
41 g Ce(SO4)2 x 4 H2O is weighed out into a beaker and dissolved in approx. 500 mL sulfuric
acid, c(H2SO4) = 1 mol/L under moderate heat. After cooling down the solution is transferred
to a 1000 mL volumetric flask using dist. H2O, made up to the mark and mixed.
Titer determination
Disodium oxalate is dried overnight in a drying oven at 240 C and allowed to cool down in a
temperature.
Approx. 70 mg Na2C2O4 is accurately weighed out into the titration beaker to the nearest
0.1 mg and dissolved in approx. 50 mL dist. H2O. After the addition of 10 mL sulfuric acid,
w(H2SO4) = 25%, the solution is heated to approx. 40 to 50 C and titrated with Ce(IV), c =
0.1 mol/L to after the first endpoint (Pt Titrode or combined Pt-ring electrode). The reaction
can be described by the following simplified equation:
2 Ce(IV) + C2O4 2 2 Ce(III) + 2 CO2
1 mL Ce(IV), c = 0.1 mol/L corresponds to 6.700 mg Na2C2O4
Titer = C00 / C01 / EP1
EP1 = mL cerium(IV) solution up to endpoint
C00 = weight of Na2C2O4 in mg
C01 = 6.7
I.5.9 Alcoholic solution c(KOH) = 0.1 mol/L

KOH solutions do not have a stable titer. They can absorb CO2 from the air to form potassium carbonate. This means that not only the titer becomes reduced. As KOH and K2CO3
have different base strengths this will affect the titration curve and therefore the results. In order to largely avoid CO2 absorption from the atmosphere the drying or absorber tube of the
Exchange Unit is filled with soda lime (CO2 absorber). As strong bases attack glass the Exchange Unit should be provided with a plastic storage bottle.
51
Please also note that non-aqueous titrants have a coefficient of expansion that is higher than
that of water by a factor of 4!
Preparation
6 g KOH is weighed out into a beaker, treated with a little dist. H2O and swirled about briefly
in order to dissolve any K2CO3 on the surface. This solution is rejected. 20 mL CO2-free dist.
H2O is added and the KOH is completely dissolved. The solution is transferred to a 1000 mL
volumetric flask using CO2-free ethanol or isopropanol (isopropyl alcohol, IPA), made up to
the mark with this solvent and mixed.
Titer determination
Benzoic acid is dried overnight in a drying oven at 105 C and allowed to cool down in a desiccator for at least 1 h. Care must be taken that the titrations are carried out at a constant temperature.
Approx. 120 mg benzoic acid is accurately weighed out into the titration beaker to the nearest 0.1 mg and dissolved in approx. 50 mL ethanol. It is immediately titrated with alcoholic
c(KOH) = 0.1 mol/L to after the first endpoint (Solvotrode).
1 mL alcoholic potassium hydroxide, c(KOH) = 0.1 mol/L corresponds to 12.212 mg benzoic
acid (C7H6O2)
Titer = C00 / C01 / EP1
EP1 = mL alcoholic KOH up to endpoint
C00 = weight of benzoic acid in mg
C01 = 12.212
I.5.10 c(HClO4) = 0.1 mol/L in glacial acetic acid

The strongest acid for non-aqueous media is HClO4 in glacial acetic acid (concentrated acetic acid). It is particularly suitable for the titration of weak bases that can no longer be titrated
in purely aqueous solution.
Please also note that non-aqueous titrants have a coefficient of expansion that is higher than
that of water by a factor of 4!
Preparation
8.5 mL perchloric acid, w(HClO4) = 70% (1.68 g/mL), is measured out into a 1000 mL volumetric flask, made up to the mark with concentrated acetic acid (w = 96...100%) and mixed.
Titer determination
Potassium hydrogen phthalate is dried overnight in a drying oven at 105 C and allowed to
cool down in a desiccator for at least 1 h. Care must be taken that the titrations are carried out
at a constant temperature.
Approx. 200 mg KH phthalate is accurately weighed out into the titration beaker to the nearest 0.1 mg. It is treated with 50 mL glacial acetic acid and stirred at room temperature until
52
everything has dissolved (5 to 10 min). It is then titrated with perchloric acid, c(HClO4) = 0.1
mol/L, to after the first endpoint (Solvotrode).
1 mL perchloric acid c(HClO4) = 0.1 mol/L corresponds to 20.423 mg KH phthalate
Titer = C00 / C01 / EP1
EP1 = mL HClO4 solution up to endpoint
C00 = weight of KH phthalate in mg
C01 = 20.423
53
II. Practical part

Preliminary remarks
What must a modern titrator be able to do in order to meet market demands?
This is a question that Metrohm always has to face, no matter whether for new developments
or the further development of existing instruments.
The basis can be assumed to be the knowledge about titrations that has been acquired by
a qualified laboratory technician, i.e. the correct working procedure for each type of titration.
This includes the titration speed (as fast as possible but always waiting for the equilibrium
to be established), as accurate as possible (volume increments that are as small as possible
toward the end of the titration) and recognition of the true titration endpoint.
In addition there are such matter-of-course things as PC and balance connections, flexible
calculation possibilities, automation possibilities, compliance with regulations, etc.
Titration endpoint
The simplest way of finding the endpoint of an S-shaped potentiometric titration curve (U/mL)
is the differentiation U/mL. Peak-shaped curves are produced whose peak maximum contains two pieces of information:
on the volume axis (mL) the titration endpoint (EP)
on the potential axis (U) the shape of the curve (steep, flat, symmetrical, asymmetrical)
and, with Metrohm, an endpoint criterion (EPC) with whose help endpoints can be selected deliberately (e.g. filter functions).
However, this possibility for evaluation only applies to ideal and symmetrical single curves.
For mixtures (several endpoints) or with asymmetrical curves Metrohm has developed its own
algorithm (polynomial of the nth degree), with which these possibilities can also be taken into
account.
Further information about the titration modes used by Metrohm:
SET (Set Endpoint Titration)
Titration to a predefined endpoint. For quick, quantitative determinations when the EP does
not become displaced during a series of determinations or for titrations in which an excess
of titrant has to be avoided. In this mode there is no point in printing out titration curves (they
contain no useful information).
MET (Monotonic Equivalence point Titration)
Constant volume increment dosing, not dependent on the slope of the curve. Measured value acceptance can be either drift-controlled (equilibrium titration) and/or after a predefined
waiting period. For slow titration reactions (e.g. diazotization, bromination) and/or slowly responding sensors (electrodes).
DET (Dynamic Equivalence point Titration)
Reagent (titrant) dosing with variable volume increments, depending on the slope of the titration curve (large in the flat parts and small in the steep parts of the curve). Measured value acceptance can also be either drift-controlled and/or after a predefined waiting period. Suitable
for most titrations. This method recognizes jumps that are close together or relatively flat.
54
TIP (Titration Procedure)

Combination of different commands to give a titration sequence. This is a first step toward
automation, e.g. different additions (auxiliary reagents), measurements and titrations can be
linked together and printed out as a results block.
55
II.1 Acid-base titrations and methods, aqueous

II.1.1
Electrode calibration and electrode

handling
As mentioned in Electrodes for potentiometry, the pH of the buffer and sample solutions is temperature-dependent and cannot
be compensated by the instrument.
We would also like to remind you again that
buffer solutions are not stable and should always be disposed of after use.
We recommend the following procedure for
calibrating a pH glass electrode:
Remove the electrode from its storage
vessel, attach the cable and connect it to
the instrument.
Open the filling opening (electrolyte), top
up the electrolyte solution if necessary.
Thoroughly rinse the electrode with dist.
H2O and dab dry with a soft paper tissue
(do not rub).
Fill buffer solution pH = 7.0 into a beaker
and add a magnetic stirrer bar.
Immerse the electrode in the buffer solution and stir for approx. 1 min. Measure
the buffer solution temperature and enter
it in the instrument (a Pt 1000 temperature
sensor can also be connected).
Enter the pH value (for the corresponding

temperature) and start the calibration with
buffer 1 under stirring.
As soon as the measurement has been
accepted, remove the electrode from the
solution, thoroughly rinse it with dist. H2O
and dab dry with a soft paper tissue.
Fill buffer solution pH = 4.0 or pH = 9.0
into a second beaker, add a magnetic stirrer bar, immerse the electrode and stir for
1 min (the second buffer solution must be
at the same temperature as the first buffer
solution).
Enter the pH value of the second buffer
solution (for the corresponding temperature) and continue the calibration under
stirring.
When the measurement has been accepted, end the calibration, rinse the electrode
with dist. H2O and dab dry with a soft paper tissue.
What takes place in the instrument during
calibration can be seen in the following diagram:
56
Handling the combined pH glass electrode

The working life of electrodes used in the laboratory should be as long as possible. Their
characteristic data must lie within the given
criteria (slope, pHas and Uas) and they should
have a rapid response behavior. In order to
ensure that these targets are met, a few basic rules must be observed.
A) Purchase and use of the correct electrode
This is the first decisive step that you can
take. Selecting the correct electrode will
save you a lot of trouble. Information is provided in the Metrohm catalogue Metrosensor Electrodes under chapter Which electrode for which application?.
In which samples will my electrode be used?
What influence do these samples have on
my electrode? These questions primarily
concern the diaphragm, the electrolyte solution and the Ag/AgCl reference system.
In older Ag/AgCl reference electrodes the
electrolyte solution becomes saturated with
complexed silver ions. AgCl can precipitate
in the diaphragm as AgCl or, in the presence of sulfide ions, as Ag2S and block the
diaphragm this mainly affects ceramic diaphragms.
With LL electrodes this occurs less frequently as only traces of AgCl can enter the electrolyte solution. The glass membrane is also
affected less frequently (drying out, abrasion
or aging of the gel layer).
B) Electrode storage and maintenance
After use rinse the electrode thoroughly with
dist. H2O and dab it dry with a soft paper tissue. Close the filling opening (electrolyte)
and store the electrode by immersing it to
a sufficient depth in the electrolyte solution
usually c(KCl) = 3 mol/L.
Caution: Dry storage leads to a delayed and
poor response. The electrolyte could become more concentrated and pHas/Uas could
change. Storage in dist. H2O could block the
diaphragm.
C) Troubleshooting
For blocked diaphragms please consult
the electrode data sheet that accompanies
each electrode. Remedying a blocked diaphragm is complicated; it is better to send
the electrode to your local Metrohm agency for repair.
Contamination by fats, paints, lacquers,
etc.: Remove the contamination with an
organic solvent (acetone, benzine, toluene), then rinse it thoroughly with ethanol
and dist. H2O and immerse the electrode
in electrolyte solution.
Contamination by proteins: Immerse the
electrode for several hours in a solution of
5% pepsin in hydrochloric acid, c(HCl) =
0.1 mol/L. Then rinse thoroughly with dist.
H2O.
If the measured value is slow to stabilize
and/or the slope is unsatisfactory then the
electrode requires etching. This is done by
immersing the electrode for 10 s in a solution of ammonium difluoride (NH4HF2, w =
10%, plastic beaker), then swirling it in hydrochloric acid, c(HCl) = 5 mol/L, for approx. 10 s, rinsing it with dist. H2O, removing silicate residues with a moist tissue
and immersing the electrode in c(KCl) = 3
mol/L for 24 h (or 5 h at 50 C).
57
II.1.2 Titer determination of hydrochloric acid, c(HCl) = 0.1 mol/L with Tris
Procedure
Learning topics
Use of standard titrimetric substances.
Clean working practices.
Titration of a weak base with a strong
acid.
Titration curve and position of endpoint.
Titer determination of HCl
Principles
As a dilute HCl standard solution frequently is
not adjusted exactly to a particular concentration, but only has an approximate concentration of e.g. 0.1 mol/L, its accurate concentration must be determined by using a standard
titrimetric substance. The titer of HCl is determined by using tris(hydroxymethyl)-aminomethane (Tris) as the standard titrimetric
substance. As Tris is a weak base, the equivalence point of the titration is at approx. pH
5.2, i.e. on the acidic side. The broad plateau
that lies before it demonstrates the buffering properties of the Tris/Tris hydrochloride
mixture formed during the titration. The true
concentration of the HCl is obtained from the
product of the approximate concentration
and the titer.
Reaction equation
(CH2OH)3CNH2 + HCl
(CH2OH)3CNH x HCl
Materials and apparatus
Analytical balance 5-digit
Exchange Unit
Ecotrode
Sartorius 1702
20 mL
6.0232.100
Reagents and chemicals

HClaq c = 0.1 mol/L
Tris
Riedel-de Han 35335

Fluka 93350
Tris is placed in a weighing bottle and dried

in a drying oven at 105 C for 2 h, then cooled
down and stored in a desiccator. 10 samples
between 100 and 150 mg are then weighed
out with an accuracy of 0.1 mg and each is
placed in a 100 mL beaker. 60 mL dist. H2O is
added and the titration is carried out with the
following parameters:
DET pH
>titration parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
abs.
start V
0 ml
dos.rate
max. ml/min
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
ON
mean
n=
10
res.tab:
original
>evaluation
EPC
5
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
58
Example of a titration curve

Calculation
In order to obtain the titer of
hydrochloric acid the following formula must be entered
in the instrument:
Titer = C00 x C01 /C02 /
EP1;4;
The individual variables are:
EP1 = added volume up to first
equivalence point [mL]
C00 = weight of standard titrimetric substance [g]
C01 = correction factor (c = 0.1
mol/L 10000 mL/mol)
Measured values and statistics

Sample size Tris
(g)
Consumption of
HCl (mL)
Titer
C02 = molar mass of Tris (121.17

g/mol)
0.08973
7.422
0.9980
The titer has no unit and should be

given to 4 decimal places.
0.11924
9.867
0.9976
0.09025
7.454
0.9995
0.08714
7.216
0.9969
0.08699
7.205
0.9967
0.07515
6.213
0.9985
0.09383
7.763
0.9978
0.07066
5.850
0.9971
0.79730
6.591
0.9986
10
0.11616
9.596
0.9993
Measured value
0.9980
0.0001
Srel %
0.1
II.1.3 Titer determination of hydrochloric acid, c(HCl) = 0.1 mol/L and validation of the titrator
Principles: see II.1.2.
Learning topics
Temperature coefficient of the titrant.
Systematic errors and their correction.
Achievable precision. Validation of
the titrator as a complete system
and not as individual components.
For texts and calculations please refer to Application Bulletin no. 252.
Work is carried out with different sample

weights so that between 20% and 80% of the
cylinder volume is consumed up to the endpoint. Procedure otherwise as under 1.2.
59
Possible sources of error

The greatest source of error lies in weighing
out the standard titrimetric substance. It is
important that the balance and standard titrimetric substance have the same temperature, and that the balance is not exposed to
drafts. If the weights are not accurate enough
the accuracy can be improved by making a
relative measurement. The weighing boat
is tared and then reweighed after the standard titrimetric substance has been added.
This allows the weight of added substance to
be read off directly and very accurately. Before the start of the titration it is essential that
the standard titrimetric substance has been
completely dissolved, as only solvated and,
if applicable, dissociated molecules can take
part in the reaction.
II.1.4 Titration of NaOH

Learning topics
is to be titrated immediately. In this way the

carbonate error is kept as small as possible.
Titration of a strong base with a

strong acid.
The titration is carried out with the following

parameters:
Titration curve and position of the

endpoint.
Titer adjustment can be avoided by using a
ready-to-use standard solution. If the titer is
to be determined then Tris is used; this must
have been dried for approx. 2 h at 105 C.
Reaction equations
1. NaOH Na+ + OH
dissociation of
base
2. OH + H3O+ 2 H2O neutralization

Exchange Unit
Ecotrode
20 mL
6.0232.100

c(HCl) = 0.1 mol/L
Riedel-de Han
35335
c(NaOH) = 0.1 mol/L
CO2-free
Procedure
15 mL c(NaOH) = 0.1 mol/L is pipetted into
10 beakers (100 mL) and made up to 60 mL
with dist. H2O. It is essential that the NaOH is
carbonate-free, as otherwise 2 equivalence
points will be found, one the equivalence
point of NaOH and the other the equivalence
point of the carbonate. In order to achieve results that are as good as possible we recommend that only that beaker is prepared which
DET pH
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
abs.
start V
0 ml
dos.rate
max. ml/min
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
ON
mean
n=
10
res.tab:
original
>evaluation
EPC
8
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
60

Calculation
In order to obtain the titer of
the NaOH solution, the following formula must be entered in the instrument:
c(NaOH) = EP1 x C01 x C02
/ C00;3;mol/L
C00 = volume of NaOH solution
[mL]
C01 = concentration of HCl solution (1) [mol/L]

Measured value
Sample size
NaOH (mL)
Consumption of
HCl (mL)
c (NaOH) in
mol/L
15.000
15.115
1.0098
15.000
15.055
1.0058
15.000
15.101
1.0088
15.000
15.082
1.0076
15.000
15.124
1.0103
15.000
15.055
1.0058
15.000
15.089
1.0081
15.000
15.059
1.0060
15.000
15.049
1.0054
10
15.000
15.097
1.0086
1.0076
0.0018
Srel %
0.18

Possible sources of error in the titration could be, for example, pipetting errors, or an HCl solution with an inaccurate
titer. We recommend that pipetting is carried out with great
care and that the titer of the standard solution is checked.
If two equivalence points are found in the titration the possible cause could be dissolved CO2. In this case freshly-made
NaOH should provide help.
C02 = titer (1.0021) []
This results in c(NaOH)

having the unit [mol/L]; the
concentration of the base
should be given to 4 decimal
places.
61
II.1.5 Titration of NaOH containing a small amount of Na2CO3

Learning topics
Absorption of CO2 from the air.
Titration curve and position / displacement of the endpoints.
Titration sequence according to
base strength.
Calculating the CO2 content.
Principles
The sodium hydroxide solution containing
the carbonate is titrated against a strong acid
of known concentration. The sodium hydroxide is titrated first, followed by the carbonate.
The titration curve has 2 equivalence points;
the first equivalence point is produced by
NaOH, the second by the carbonate.
Titer adjustment can be avoided by using a
ready-to-use standard solution. If the titer is
to be determined then Tris is used; this must
have been dried for approx. 2 h at 105 C.
Reaction equations
1. NaOH Na+ + OH
dissociation of base
2. OH + H3O+ 2 H2O
titration of NaOH
3. CO32 + 2 H3O+ CO2 + 3 H2O
titration of carbonate
Exchange Unit
Ecotrode
20 mL
6.0232.100

HClaq
c = 0.1 mol/L
Riedel-de Han 35335
NaOHaq c = 0.1 mol/L
Procedure
15 mL c(NaOH) = 0.1 mol/L is pipetted into
10 beakers (100 mL) and made up to 60 mL
with dist. H2O. In order to achieve results that
are as good as possible we recommend that
only that beaker is prepared which is to be titrated immediately.
parameters:
DET pH
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
abs.
start V
0.0 ml
dos.rate
max. ml/min
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
ON
mean
n=
10
res.tab:
original
>evaluation
EPC
10
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
62

Calculation
Two formulas are entered in
the instrument:
1. To obtain the concentration of the NaOH solution:
c(NaOH) = EP1 x C01 x
C02 / C00;3;mol/L
2. To obtain the carbonat
concentration of the solution:
c(carb.) = (EP2 EP1) x
C01 x C02 / C00=;3;mol/L

Measured
Sample
value
size NaOH
(mL)
mL HCl
EP1
mL HCl
EP2
c(NaOH)
in mol/L
c(CO32) in
mol/L
15.000
14.841
14.880
0.0991
0.0003
EP2 = added volume up to second

15.000
14.832
14.873
0.0990
0.0003
C00 = volume of NaOH solution

[mL]
15.000
14.832
14.874
0.0991
0.0003
15.000
14.824
14.869
0.0990
0.0003
C01 = concentration of HCl solution (0.1) [mol/L]
15.000
14.851
14.890
0.0992
0.0003
15.000
14.827
14.865
0.0991
0.0003
C02 = titer (1.0021) []
15.000
14.853
14.893
0.0992
0.0003
This results in c(NaOH)

and c(carb.) having the unit
[mol/L]. The concentrations
should be given to three
decimal places.
15.000
14.831
14.873
0.0991
0.0003
15.000
14.821
14.865
0.0990
0.0003
10
15.000
14.831
14.872
0.0991
0.0003
0.0991
0.0003
0.0001
0.1
Srel %

Possible sources of error in the titration could be, for example, pipetting errors, or an HCl solution with an inaccurate
63
II.1.6 Titration of sulfuric acid H2SO4

Learning topics
Titration of a strong acid with a
strong base.
endpoint.
Leveling (of acids, i.e. the two dissociation steps of sulfuric acid) in
aqueous solution.
With purchased and fresh ready-to-use standard solution the titer determination can be
avoided. However, the titer has to be determined in regular time intervals with self-made
or used standard solutions.
Reaction equations
1. H2SO4 + 2 H2O 2 H3O+ + SO42
dissociation of acid
2. H3O+ + OH 2 H2O neutralization
Exchange Unit 20 mL
Ecotrode
6.0232.100
Nitrogen from the cylinder
Buret tip as gas inlet
NaOHaq c = 0.1 mol/L accurate titer
Riedel-de Han 35263
c(H2SO4) = ca. 0.1 mol/L
Remark
1
Ready-to-use standard solutions are commercially

available standard solutions whose titer has been
adjusted to 1.000 at 20 C. We recommend the purchase of such ready-to-use solutions in preference to
preparing them yourself. Alkaline titrants in particular
do not have a stable titer (see titration of NaOH).
Procedure
8 mL of the H2SO4 is pipetted into 10 beakers
(100 mL) and made up to approx. 60 mL with
distilled water.
During the titration, nitrogen is continuously passed through the analyte solution to remove any dissolved CO2 that could interfere
with the titration. By setting a waiting period
of 35 seconds before the titration, the CO2
contained in the water is also displaced.
The titration is carried out using the following
parameters:
DET pH
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
35 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
ON
mean
n=
10
res.tab:
original
>evaluation
EPC
10
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
64

Calculation
In order to obtain the concentration of the H2SO4 solution the following formula
must be entered in the instrument:
c(H2SO4) = EP1 x CO1 x
C02 / C03 / C00;3;mol/L
EP1 = added volume up to the first
C00 = volume of H2SO4 solution
[mL]
C01 = concentration of NaOH solution (0.1) [mol/L]
C02 = titer (1.0000 for volumetric
standard solution) []
C03 = valency of the acid (2) []
This results in c(H2SO4) having the unit [mol/L]; the concentration of the acid should
be given to three decimal
places.

Measured value
Sample size
H2SO4 (mL)
Consumption of
NaOH (mL)
c(H2SO4) in
mol/L
8.000
15.169
0.0948
8.000
15.211
0.0951
8.000
15.187
0.0949
8.000
15.195
0.0950
8.000
15.214
0.0951
8.000
15.183
0.0949
8.000
15.194
0.0949
8.000
15.182
0.0949
8.000
15.213
0.0951
10
8.000
15.240
0.0953
0.0950
0.0001
Srel %
0.16

Possible sources of error in the titration could be, for example, pipetting errors, or an NaOH solution with an inaccurate
If two equivalence points are found in the titration the possible cause could be dissolved CO2. In this case a higher nitrogen throughput and/or a freshly made NaOH solution should
provide help. Small amounts of carbonate in NaOH solution
can change the value of the EP to a pH value of >7.0.
65
II.1.7 Titration of acetic acid, DET and endpoint titration (SET)

Learning topics
Titration of a weak acid with a strong
base.
endpoint.
Determining the titration endpoint
and SET titration; buffering range.
The equivalence point of the titration curve

lies on the alkaline side as a weak acid is titrated with a strong base. In order to reduce
the titration time for routine measurements a
SET titration can be carried out to the true
endpoint. This endpoint/equivalence point is
first determined in a DET titration. A precondition is that the electrode is first calibrated
using buffer solutions. In our example the EP
is at pH = 8.16.
Reaction equations
1. CH3COOH + H2O CH3COO + H3O+
2. H3O+ + OH 2 H2O
3. CH3COOH + NaOH CH3COONa + H2O
Exchange Unit 20 mL
6.0232.100

Titrant
In order to obtain the concentration of the

acetic acid solution the following formula
must be entered in the Titrino:
mol/L acetic acid = EP1 x C01 x C30 / C00
EP1
C00
C01
C30
=
=
=
=
mL NaOH up to endpoint [mL]

sample volume in mL
0.1 (concentration of NaOH in mol/L)
titer of NaOH
The following parameters are entered in the

Titrino:
Principles
Ecotrode
Calculation
c(NaOH) = 0.1 mol/L
Sample c(CH3COOH) = approx. 0.1 mol/L.

5.75 mL glacial acetic acid is made
up to 1 liter with dist. H2O
Procedure
5.00 mL c(CH3COOH) = 0.1 mol/L is diluted
to approx. 50 mL with dist. H2O in a beaker
and then titrated with c(NaOH) = 0.1 mol/L.
DET titration
794 Titrino
OE2/239
794.0010
date 2002-04-19
time 10:42
2
pH(init)
3.47
DET pH
HAC
smpl size
5 ml
id#1
1
id#2
1
id#3
1
EP1
5.156 ml
8.16
c(VINEGAR)
0.103 mol/l
manual stop
no new com.var.
-----------pa
794 Titrino
OE2/239
794.0010
Date 2002-04-19
time 10:42
2
DET pH
HAC
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
abs.
start V
0.0 ml
dos.rate
max. ml/min
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
E
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
Example of a titration curve (DET titration)
66

Sample size
CH3COOH (mL)
Consumption of
NaOH (mL)
c in mol/L
5.00
5.156
0.1031
5.00
5.145
0.1029
5.00
5.145
0.1029
5.00
5.189
0.1038
5.00
5.186
0.1037
5.00
5.194
0.1039
5.00
5.193
0.1039
5.00
5.222
0.1044
5.00
5.189
0.1038
10
5.00
5.208
0.1042
0.1037
0.0005
Srel %
0.50
SET titration
794 Titrino
OE2/239
794.0010
date 2002-04-19
time 13:19
34
pH(init)
3.48
SET pH
HAC2
smpl size
5 ml
id#1
1
id#2
1
id#3
1
EP1
5.239 ml
8.45
ACETIC AC
0.105 mol/l
-----------pa
794 Titrino
OE2/239
794.0010
Date 2002-04-19
time 13:19
34
SET pH
HAC2
parameters
>SET1
EP at pH
8.16
dynamics
OFF
max.rate
20.0 ml/min
min.rate
25.0 l/min
stop crit:
drift
stop drift
20 l/min
>SET2
EP at pH
OFF
titr.direction:
auto
start V:
abs.
start V
4.50 ml
dos.rate
max. ml/min
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
filling rate
max. ml/min
>statistics
status:
OFF
>preselections
conditioning:
OFF
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
67

Measured
value
Sample size
CH3COOH
(mL)
Consumption of
NaOH (mL)
c in mol/L
5.00
5.239
0.1048
5.00
5.233
0.1047
5.00
5.243
0.1049
5.00
5.242
0.1048
5.00
5.241
0.1048
5.00
5.226
0.1045
5.00
5.230
0.1046
5.00
5.248
0.1050
5.00
5.249
0.1050
10
5.00
5.241
0.1048
0.1048
S
Srel %
0.0002
0.15
68
II.1.8 Titration of phosphoric acid (H3PO4), DET and MET

Learning topics
Titration of a mixture of acids with a
strong base.
endpoints.
Titration sequence according to acid
strength.
Difference between dynamic / monotonic titration and its influence on the
results.
Reaction equations
1. H3PO4 + NaOH NaH2PO4 + H2O
(EP1 at pH = approx. 4.7)
2. NaH2PO4 + NaOH Na2HPO4 + H2O
(EP2 at pH = approx. 9.3)
3. Na2HPO4 + NaOH Na3PO4 + H2O
(no EP)
H3PO4 + 3 NaOH Na3PO4 + 3 H2O
Exchange Unit 20 mL
Ecotrode
6.0232.100
Principles
Phosphoric acid is said to be a tribasic

acid, it corresponds theoretically to a mixture of three acids with the pKa values 1.96,
7.12 and 12.32. The first proton corresponds
to a strong acid, the second to a weak one
and the third to a very weak acid. The strongest acid in a mixture is always titrated first.
In aqueous solution only the first two acid
groups have an endpoint, while the third
acid group (as it is too weak) is not detected
(leveling).
Titrant
If it is assumed that the titration is carried out

with a carbonate-free base then the NaOH
consumption up to the second endpoint will
be exactly twice the NaOH consumption up
to the first endpoint. However, if the NaOH
contains carbonate then more than double
the amount will be required for EP2 than that
for EP1 (the more, the greater the amount
of carbonate in the base), as the amount of
carbonate is also determined at EP2. As the
carbonate/CO2 equilibrium is not achieved
very quickly, the titration up to EP2 must be
carried out slowly. The difference is demonstrated by using a DET (quick) and a MET
(slow) titration. For routine measurements
we recommend titrating only up to EP1 (so
that the carbonate error is eliminated).
Calculation
c(NaOH) = 0.1 mol/L
Sample c(H3PO4) = approx. 0.1 mol/L.

Approx. 7 mL w(H3PO4) = 85% is
made up to 1 liter with dist H2O
Procedure
5.00 mL c(H3PO4) = 0.1 mol/L is diluted with
dist. H2O to approx. 50 mL in a beaker and titrated with c(NaOH) = 0.1 mol/L to after the
second endpoint.
The following formulas must be entered into

the Titrino in order to obtain the concentration of the phosphoric acid:
mol/L H3PO4 = EP1 x C01 x C30 / C00
or
(EP2 EP1) x C01 x C30 / C00
or
EP2 x C01 x C30 / C02 / C00
EP1 =
EP2 =
C00 =
C01 =
C02 =
C30 =
mL NaOH up to first endpoint

mL NaOH up to second endpoint
sample volume in mL (5)
0.1 (concentration of NaOH in mol/L)
2 (double consumption up to EP2)
titer of NaOH
DET titration
Parameters
pa
794 Titrino
OE2/239
794.0010
date 2002-05-03
time 09:47
14
DET pH
PHOSPH 1
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
69

Measured
value
Sample
size
H3PO4
(mL)
Consumption of
NaOH
EP1
(mL)
c in
mol/L
Consumption of
NaOH
EP2
(mL)
c in
mol/L
5.00
7.205
0.1441 14.613 0.1461
5.00
7.203
0.1441 14.648 0.1465
5.00
7.216
0.1443 14.658 0.1466
5.00
7.205
0.1441 14.643 0.1464
5.00
7.224
0.1445 14.651 0.1465
5.00
7.207
0.1441 14.644 0.1464
5.00
7.230
0.1446 14.669 0.1467
5.00
7.252
0.1450 14.737 0.1474
5.00
7.219
0.1444 14.678 0.1468
10
5.00
7.216
0.1443 14.697 0.1470
0.1444
0.1466
0.0003
0.0004
0.20
0.25
Srel %
Calculation of carbonate portion with DET titration:

0.1466 mol/L 0.1444 mol/L = 0.0022 mol/L
70
MET titration
Parameters
pa
794 Titrino
OE2/239
794.0010
date 2002-05-03
time 12:49
28
MET pH
PHOSPH 2
parameters
V step
0.10 ml
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
0.50
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------

Measured
value
Sample
size
H3PO4
(mL)
Consumption of
NaOH
EP1
(mL)
c in
mol/L
Consumption of
NaOH
EP2
(mL)
c in
mol/L
5.00
7.217
0.1443 14.642 0.1464
5.00
7.227
0.1445 14.642 0.1464
5.00
7.227
0.1445 14.635 0.1464
5.00
7.232
0.1446 14.678 0.1468
5.00
7.225
0.1445 14.666 0.1467
5.00
7.241
0.1448 14.690 0.1469
5.00
7.258
0.1452 14.699 0.1470
5.00
7.226
0.1445 14.670 0.1467
5.00
7.260
0.1452 14.724 0.1472
10
5.00
7.230
0.1446 14.660 0.1466
0.1447
0.1467
0.0003
0.0003
0.21
0.19
Srel %
Calculation of carbonate concentration with

MET titration:
0.1467 mol/L 0.1447 mol/L = 0.0020 mol/L.
With this small carbonate content, the difference between the DET and MET mode is irrelevant.
71
II.1.9 Titration of boric acid (H3BO3) with and without addition of mannitol
Titration of boric acid
Learning topics

base.
Exchange Unit 20 mL

endpoint.
Ecotrode
6.0232.100
Buffering range.
Titrant
Increasing the acid strength by complex formation with the release of a

proton.
Sample c(H3BO3) = approx. 0.1 mol/L.

6.2 g H3BO3 is dissolved in
dist. H2O and made up to 1 liter.
Principles
The equivalence point of the titration curve
lies on the alkaline side as a weak acid is titrated with a strong base.
Boric acid is a weak acid (pK 9.24) and, in
aqueous solution, only shows a weakly pronounced, flat titration curve. However, its titration is no problem for modern titrators.
Formerly this was not the case. This is why a
chemical reaction between boric acid and a
polyalcohol was used to obtain a steeper titration curve that was easier to evaluate.
With polyvalent alcohols, which must have at
least three neighboring alcohol groups, boric acid forms an ester. As boron always attempts to achieve a coordination number of
4, this means that a further bond is formed
to the oxygen atom of a neighboring alcohol
group. This weakens its bond to hydrogen;
the OH hydrogen splits off as H+. This converts the boric acid-mannitol ester into a medium-strength acid. The polyalcohol should
be present in excess so that a 1:2 compound
can be formed. The polyalcohol used in our
experiment is D()mannitol. The structure of
the boric acid complex can be depicted as
follows:
c(NaOH) = 0.1 mol/L
D()mannitol solution approx. 200 g mannitol is dissolved in 800 mL dist. H2O. The solution is saturated.
Procedure
5.00 mL c(H3BO3) = 0.1 mol/L is diluted with
dist. H2O to approx. 50 mL in a first glass beaker and titrated with c(NaOH) = 0.1 mol/L.
5.00 mL c(H3BO3) = 0.1 mol/L is treated with
10 mL mannitol solution and diluted to approx. 50 mL with dist. H2O in a second glass
beaker. It is then titrated with c(NaOH) = 0.1
mol/L.
Calculation
The following formula is entered in the Titrino in order to obtain the concentration of the
boric acid:
mol/L H3BO3 = EPn x C01 x C30 / C00
EPn = mL NaOH up to endpoint at pH
= approx. 10 (EPn = EP1 or EP2)
C00 = sample volume in mL (5)
C01 = 0.1 (concentration of NaOH in mol/L)
C30 = titer of NaOH
72
Boric acid determination without the addition of mannitol

Parameters
pa
794 Titrino
OE2/239
794.0010
date 2002-05-10
time 10:37
3
DET pH
BOR AC1
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------

Measured
value
Sample
size H3BO3
(mL)
Consumption of
NaOH (mL)
c(H3BO3) in
mol/L
5.00
5.095
0.1019
5.00
5.089
0.1018
0.1019

Frequently, in the titration
of weak acids, the initial
curve section has nothing
to do with the species to
be determined (blank value,
EP1). Since the pKa value is
>9, the titration curve rises
steeply on the way from the
initial pH to the buffer plateau, which is interpreted by
the Titrator as a first EP.
73
Boric acid determination with the addition of mannitol

Parameters
pa
794 Titrino
OE2/239
794.0010
date 2002-05-10
time 10:44
4
DET pH
BOR AC1
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------

Measured
value
Sample
size H3BO3
(mL)
Consumption of
NaOH (mL)
c(H3BO3) in
mol/L
5.00
5.078
0.1016
5.00
5.082
0.1016
5.00
5.114
0.1023
5.00
5.083
0.1017
5.00
5.105
0.1021
5.00
5.079
0.1016
5.00
5.087
0.1017
5.00
5.120
0.1024
5.00
5.089
0.1018
10
5.00
5.083
0.1017
0.1019
0.0003
Srel %
0.30
The titration curve with added mannitol is noticeably steeper in the endpoint region.
74
II.1.10 Titration of the acid and base capacity (p and m values) with fixed EPs and calculation of
the carbonate hardness
mines hydroxide, carbonate and hydrogen
carbonate anions.
Learning topics
Titration of weak bases (salts) with a
strong acid.
endpoints.
CO2/CaHCO3/CaCO3
water.
equilibria
in
Water hardness.
Principles
Carbon dioxide gas (CO2) dissolves in water.
Depending upon the pH value three species
can be present: carbonate, hydrogen carbonate and free CO2. If, for example, Ca2+ or
Mg2+ ions are present in the water, their solubility depends upon the counter-ion (anion)
and the pH value.
If sufficient free carbonic acid is present then
calcium will remain dissolved as the hydrogen carbonate. If additionally excess free
carbonic acid is dissolved then it will attack,
for example, limestone (corrosion of concrete) the water is said to be aggressive.
If calcareous water is heated then carbon dioxide is driven off and the lime-carbonic acid
equilibrium is displaced to the carbonate
side: boiler scale is deposited. The sum of
the dissolved calcium and magnesium ions
in mmol/L that are then precipitated as sparingly soluble salts corresponds to the carbonate hardness or temporary hardness
of the water. Together with the non-carbonate hardness or permanent or sulfate hardness (obtainable as the sum of the concentrations of the two alkaline earth ions minus
the hydrogen carbonate concentration) it
forms a part of the total harness of the particular water (see below).
The alkalinity or acid capacity of a water is
equal to the number of mmol hydrochloric
acid that is consumed for the titration of 1 mL
water to the color change of methyl orange
or to pH = 4.3. This titration mainly deter-
The acidity or base capacity of a water is

equal to the number of mmol sodium hydroxide consumed for the titration of 1 mL water
to the color change of phenolphthalein or to
pH = 8.2. This titration mainly determines
weak acids, particularly carbonic acid, and
hydrogen carbonate. In each of these titrations up to two equivalence points could be
found; these correspond to the carbonate/
hydrogen carbonate equilibrium and hydrogen carbonate/carbonic acid equilibrium.
The p and m values are given for the analytical characterization of water. If a basic water
is titrated with HCl solution to determine the
acid capacity then the p value corresponds
to the consumption of c(HCl) = 1 mol/L in mL
for the titration of 1 mL water up to the phenolphthalein endpoint or pH = 8.2. In particular, this determines the amount of CO32. The
m value (pH = 4.3) corresponds to the consumption of hydrochloric acid c = 1 mol/L in
mL up to the color change of methyl orange
or pH = 4.3 (0.05 mval/L is subtracted for the
m value of neutral water without any buffering constituents); this mainly determines the
amount of hydrogen carbonate.
If acidic water samples are titrated with sodium hydroxide to determine the base capacity then the terms used are negative m and
p values.
The carbonate hardness of a water is that
part of the total hardness (see also II.5.4. and
II.5.5.) caused by the alkaline earth ion fraction that is equivalent to the carbonate and
hydrogen carbonate ions as well as the hydroxyl ions formed by their hydrolysis.
a) The carbonate hardness is calculated
from the p and m values; if 2 p is smaller than or equal to m then the carbonate
hardness x = m
b) If 2 p is larger than m the carbonate hardness x = 2 (m p)
75
c) If p = m the carbonate hardness x = 0

If a higher value is obtained for the carbonate hardness than for the total hardness, then this indicates that in the water
there are more carbonate and hydrogen
carbonate ion equivalents than alkaline
earth ions (determination see II.5.2.). The
carbonate hardness is then given as being
the total hardness.
Reaction equations
CO2 + H2O H2CO3
(formation of carbonic acid by hydration of
CO2)
H2CO3 + H2O HCO3 + H3O+
(dissociation of first proton)
HCO3 + H2O CO32 + H3O+
(dissociation of second proton)
HCO3 + H3O+
CO2 + H2O
(displacement of CO2 from HCO3)
H2CO3 + 2 H3O+
CO2 + 3 H2O
(displacement of CO2 from H2CO3)
2 HCO3
CO2 + CO32 + H2O
(formation of boiler scale on heating)
Exchange Unit 10 mL
Aquatrode II
6.0253.100

Distilled or deionized water
Ready-to-use standard solution c(HCl) = 0.1
mol/L, Riedel-de Han, order no. 35335
Tap water
Procedure
100 mL of a sample of drinking water is pipetted from a volumetric pipet into a 150 mL
beaker and a magnetic stirrer bar is added.
Always fill off one water sample only and
process it immediately as atmospheric CO2
could dissolve in the sample or CO2 could be
released from the solution.
The stirrer speed is set so that no air bubbles
are entrained as additional dissolved carbon
dioxide would lead to incorrect results. The

electrode and the buret tip are immersed in
the sample solution so that the flow of freshly
added titrant is not directed toward the electrode.
When the water sample has been prepared it
is titrated according to the following dynamic
pH program:
Dynamic titration program for carbonate
hardness in drinking water
794 Titrino
01102
794.0010
date 2002-08-23
time 10:24
37
DET pH
CO2Hard
parameters
meas.pt.density
4
min.incr.
5 l
titr.rate
5 ml/min
signal drift
15 mV/min
equilibr.time
43 s
start V:
OFF
pause
90 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
OFF
fix EP1 at pH
8.2
fix EP2 at pH
4.3
fix EP3 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
76

Measured
value no.
Sample size water (mL)
Consumption
(mL c(HCl) =
0.1 mol/L)
Carbonate hardness in mmol/L
100
5.253
5.25
100
5.257
5.25
100
5.252
5.25
100
5.251
5.25
100
5.253
5.25
100
5.250
5.25
100
5.253
5.25
100
5.251
5.25
100
5.251
5.25
10
100
5.249
5.25
5.25
0.003
Srel %
0.06

Particular care must be taken that the water samples
are only filled off directly before the titration as otherwise
they would continuously absorb atmospheric carbon
dioxide. In order to achieve
good results we recommend
that you adapt the titration
parameters in the parameter program.
The titration speed and the
measured value drift should
be lowered step by step until
a correct result is obtained.
During this procedure the
waiting time for the equilibrium to become established
will be automatically increased by the Titrino.
If, apart from carbonic acid
and its anions, other substances are present in the
water that have a buffering
effect at about pH 4.3 or pH
8.2, this titration cannot be
used.
77
II.1.11 Formol number in vegetable juices

Learning topics
Titration of mixtures of amino acids
after reaction with the release of a
proton.
Endpoint titrations and determining
the optimal titration endpoint.
Principles
The formol number is purely a characteristic
number. It is a cumulative parameter for the
amount of all amino acids in certain natural
products, chiefly fruit and vegetable juices.
The formol number stands for the amount of
amino nitrogen that can be titrated by formalin in mg/g dry substance.
The determination has no relationship to the
size and amount of amino acid molecules
and has been adapted to meet practical requirements. In order to avoid interference by
weak acids the titration is carried out at a correspondingly high pH value: All the carboxyl
groups present are first neutralized with sodium hydroxide (pH 8.50). The addition of
formaldehyde then releases a proton from
each amino group. Only primary amines
release a proton readily. With secondary
amines not all compounds release a proton, while tertiary amines have no proton and
therefore cannot react.
A formaldehyde excess must be present in
order to ensure complete reaction. The released protons are titrated with NaOH. Monoamino-monocarboxylic acids and monoamino-dicarboxylic acids correspond to 1 H+,
diamino-carboxylic acids to 2 H+.
Reaction using a monoamino-monocarboxylic acid as an example:
Reaction equation
OOC R NH3+ + CH2 =O
R NHCH2OH + H+
OOC
Exchange Unit 10 mL
Profitrode
6.0255.100

Deionized water self-prepared
Formaldehyde solution w(HCHO) = 35%
adjusted to pH 8.50 with NaOH
NaOH standard solution
c(NaOH) = 0.1 mol/L Riedel-de Han 35263
Procedure
25 mL homogenized sample solution is pipetted into a beaker from a volumetric pipet
and diluted with water to approx. 40 mL. A
magnetic stirrer bar is added and the solution is titrated according to a SET program
(FormolN1) in order to adjust the sample to
pH 8.50. A Profitrode with double junction is
used for detecting the pH value; this must be
immersed in the solution until the groundjoint diaphragm is covered.
When the titration has been completed, 15
mL of the formaldehyde solution adjusted to
pH 8.50 is added to the beaker from a Dosimat or volumetric pipet and the sample is
immediately titrated according to the SET
program (FormolN2). The formaldehyde attaches itself to the amino acids in the sample
with the release of a proton. When the set
waiting time has elapsed the freshly formed
protons (oxonium ions) are again titrated to
pH = 8.5 with c(NaOH) = 0.1 mol/L.
78
Parameter settings
Calculation
pa
The formol number is given in mL c(NaOH)

= 0.1 mol/L per 100 mL sample.
794 Titrino
01102
794.0010
date 2002-09-03
time 10:50
5
SET pH
FormolN1
parameters
>SET1
EP at pH
8.50
dynamics
0.5
max.rate
10.0 ml/min
min.rate
10 l/min
stop crit:
drift
stop drift
20 l/min
>SET2
EP at pH
OFF
titr.direction:
auto
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
filling rate
max. ml/min
>statistics
status:
OFF
>preselections
conditioning:
OFF
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
-----------pa
794 Titrino
01102
794.0010
date 2002-09-03
time 10:51
5
SET pH
FormolN2
parameters
>SET1
EP at pH
8.50
Dynamics
0.5
max.rate
10.0 ml/min
min.rate
10 l/min
stop crit:
drift
stop drift
20 l/min
>SET2
EP at pH
OFF
titr.direction:
+
start V:
OFF
pause
60 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
filling rate
max. ml/min
>statistics
status:
OFF
>preselections
conditioning:
OFF
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
Formol number = EP1 x C01 x C30

EP1 = consumption of c(NaOH) = 0.1 mol/L in mL
C01 = 4
C30 = titer of NaOH

Measured
value
Sample
size fruit
juice (mL)
Consumption of
NaOH (mL)
Formol
number
25.0
6.009
24.04
25.0
6.026
24.10
25.0
5.973
23.89
25.0
5.992
23.97
25.0
6.007
24.03
25.0
6.026
24.10
25.0
5.995
23.98
25.0
5.989
23.96
25.0
5.998
23.99
10
25.0
6.023
24.09
24.02
0.06
Srel %
0.23

Formaldehyde solution not preneutralized.
Electrode not calibrated or incorrect endpoint selected for the SET titration.
79
II.2 Acid-base titrations and methods, non-aqueous

II.2.1 General and additional remarks about non-aqueous titrations
Under Sections I.2.1 Acid-base reactions
(autoprotolysis) and I.5 Titrants: (I.5.9 and
I.5.10), some information on this subject has
already been provided. Some additions to it
are given here:
Non-aqueous titrations are primarily carried
out when:
the substance is not soluble in water
the samples are fats or oils, or
components of mixtures of acids or bases
have to be determined separately by titration.
Instead of water (suitable) organic solvents
are used. These should:
dissolve the sample and not react with it,
permit the determination of components in
a mixture, and, if possible, should not be
toxic or water-endangering
In most cases only a few solvents are required. These are: acetone, ethanol, isopropanol, methanol, toluene and glacial acetic
acid (concentrated acetic acid) or, occasionally, binary mixtures of them.
The titrants are also not prepared with water.
Examples are: NaOH in ethanol, KOH in isopropanol, HCl in ethanol or HClO4 in glacial
acetic acid.
If acids or bases are dissolved in protic solvents (e.g. H2O), protolysis occurs. But salts
produced during the titration can also be
broken down protolytically. In such solvents
the differentiation of strong acids with a similar strength is not possible by titration.
mixture is not possible in protic solvents is

leveling. Instead of the strong acid or base
itself lyonium or lyate ions of the solvent are
produced. In the particular system these represent the strongest acids or bases that can
possibly occur in the corresponding solvents. The differences in strength that were
present in the original mixture of acids or
bases are compensated or, as one says, leveled. A classical example of this is the aqueous solution of strong mineral acids.
With these acids water practically quantitatively forms the oxonium ion H3O+. This is
why only their total can be determined in
aqueous solution
Other frequently used terms:
Amphiprotic solvent
Also known as protic. Noticeable self-dissociation, e.g.:
2 CH3OH
CH3OH2+ + CH3O
Aprotic solvent
No self-dissociation.
Dielectric constant (DC)
Proportional factor between the electric flux
density D and the electric field strength E in
vacuum. It is strongly temperature-dependent. Solutions with a higher DC promote
the dissociation of electrolytes. In nonpolar
solvents with a small DC even strong electrolytes (e.g. KCl, HClO4) are only weakly dissociated. Examples of DCs:
Water
80.4 (20 C)
Methanol
33.6 (20 C)
The situation is different if the titration is carried out in non-aqueous solvents. Examples
are phenol and boric acid in water or ethanol
or aromatic amines in water or DMF, which
can easily be titrated in a non-aqueous medium.
Ethanol
25.1 (20 C)
Acetone
21.2 (20 C)
MIBK
18.5 (25 C)
Pyridine
13.5 (20 C)
Acetic acid
6.2 (20 C)
A further reason why the titrimetric determination of acidic or basic components of a
Toluene
2.4 (20 C)
80
Dissociation
Formation of ions, e.g. CH3OOK CH3COO
+ K+
Solvents for non-aqueous titrations can be
split up into different classes:
a) Amphiprotic acidic
e.g. glacial acetic acid, trifluoroacetic acid,
phenol, cresol. Solvents for bases.
b) Amphiprotic basic
e.g. ethylenediamine, benzylamine, butylamine. Solvents for weak acids.
c) Amphiprotic neutral
e.g. ethanol, isopropanol, ethylene glycol.
Solvents for strong and weak acids and
salts.
d) Aprotic acidic
e.g. nitromethane, nitroethane. Solvents
for strong and weak acids and salts (seldom used, explosion hazard)
e) Aprotic basic
e.g. pyridine, dimethylformamide (DMF),
dimethylsulfoxide (DMSO). Solvents for
weak acids.
f) Aprotic neutral
e.g. acetone, acetonitrile, nitrobenzene,
diethyl ether, dioxan, hydrocarbons (hexane, heptane, toluene), chlorinated hydrocarbons (chloroform, methylene chloride).
Carbohydrates, ether, dioxan and chlorinated hydrocarbons are only used as solubility promoters (for nonpolar substances such as fats and oils). Potentiometric
indication cannot be carried out in these
solvents (high electrical resistance). Used
as solvents for amines or (if appropriate)
for weak acids.
II.2.2. Titer determination of perchloric acid, c(HClO4) = 0.1 mol/L in glacial acetic acid
Learning topics
Coefficient of expansion of organic
solvents/titrants.
Titration curve.
Use of suitable electrodes.
Principles
As a dilute HClO4 standard solution is frequently not adjusted exactly to a defined
concentration, but only has an approximate
concentration of e.g. 0.1 mol/L, its accurate
concentration must be determined by using
a standard titrimetric substance. This also
applies when dealing with an acid in a nonaqueous solvent. The titer of HClO4 is determined by using tris(hydroxymethyl)-aminomethane (Tris) as the standard titrimetric
substance. The titration of HClO4 is a nonaqueous acid-base titration. As the pH value
is only defined for water, the presentation of

the pH value for a non-aqueous titration is
only a formal transfer of this expression.
Reaction equation
(CH2OH)3CNH2 + HClO4 (CH2OH)3C
NH3+ + ClO4
Exchange Unit
20 mL
Solvotrode
6.0229.100
Analytical balance 5-digit Sartorius 1702

c(HClO4) = 0.1 mol/L in glacial acetic acid
(Merck no. 9065)
Tris
(Fluka no. 93350)
CH3COOHconc
(Fluka no. 45730)
81
Procedure
Calculation
Tris is dried in a weighing bottle in a drying

oven for 2 h at 105 C and then cooled down
and stored in a desiccator. 10 samples between 50 and 100 mg are then weighed out
accurately to 0.1 mg and each is placed in a
100 mL beaker. 70 mL water-free acetic acid
is added and the titration carried out using
the following parameters:
In order to obtain the titer of perchloric acid

the following formula is entered in the instrument:
DET pH
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
abs.
start V
0 ml
dos.rate
max. ml/min
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
ON
mean
n=
5
res.tab:
original
>evaluation
EPC
5
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
Titer = C00 x C01 / C02 / EP1;4;

EP1 = added volume up to first equivalence point [mL]
C00 = weight of standard titrimetric substance [g]
C01 = correction factor
(c = 0.1 mol/L = 10000 mL/mol)
C02 = molar weight of Tris (121.17 g/mol)
The titer has no unit and should be given to 4 decimal
places.

Measured
value
Sample
size Tris
(g)
Consumption of
HClO4 (mL)
Titer
0.1007
8.240
1.0086
0.0799
6.535
1.0090
0.0613
5.023
1.0072
0.0661
5.423
1.0059
0.0837
6.863
1.0065
0.0608
4.976
1.0084
0.1013
8.279
1.0076
0.0612
5.020
1.0061
0.0859
7.031
1.0083
10
0.0652
5.351
1.0056
1.0073
0.0012
Srel %
0.12

Possible sources of error in

the titration could be incorrectly weighed-out standard
titrimetric substance or incorrect handling of the Solvotrode. We recommend
that the weighing is carried
out with great care. Before
each use the Solvotrode
should be first rinsed with
the solvent, then with distilled water and finally with
the solvent again.
82
II.2.3 Titer determination of alcoholic c(KOH) = 0.1 mol/L

Procedure
Learning topics
Coefficient of expansion of organic
solvents/titrants.
Influence of CO2 absorption from the
atmosphere on the titrant.
Titration curve.
Use of suitable electrodes.
Principles
Strong bases such as NaOH or KOH absorb
carbon dioxide to form Na2CO3 or K2CO3.
This changes their titer and a second equivalence point is found, which means that the titrations would be incorrect.
To determine the titer of the KOH solution an
alcoholic solution of benzoic acid is used to
react volumetrically with the KOH to be determined. The solvent used is ethanol, in which
the KOH is also dissolved.
Reaction equation
C6H5COOH + KOH C6H5COOK +
H2O
Exchange Unit 20 mL
Solvotrode
6.0229.100

Ethanol analytical grade >99.5%
Fluka
Ready-to-use c(KOH) = 0.1 mol/L in isopropanol
Merck 1.05544.1000
Benzoic acid
Fluka 12349
Benzoic acid is dried in a drying oven for

2 hours at 105 C and then allowed to cool
down to room temperature in a desiccator. 10 portions between 60 and 100 mg
are weighed out into separate beakers using weighing boats. A magnetic stirrer bar
is added and the benzoic acid is dissolved
in approx. 50 mL ethanol. When it has completely dissolved the 10 beakers are titrated
using the following dynamic pH titration program:
794 Titrino
date 2002-08-26
DET pH
Parameters
01102
794.0010
time 17:38
37
KOHniWae
meas.pt.density
min.incr.
titr.rate
signal drift
equilibr.time
start V:
pause
meas.input:
temperature
>stop conditions
stop V:
stop V
stop pH
stop EP
filling rate
>statistics
status:
>evaluation
EPC
EP recognition:
fix EP1 at pH
pK/HNP:
>preselections
req.ident:
req.smpl size:
activate pulse:
------------
4
10.0
max.
50
26
OFF
0
1
25.0
l
ml/min
mV/min
s
s
C
abs.
10 ml
OFF
9
max. ml/min
OFF
5
all
OFF
OFF
OFF
OFF
OFF
83

Calculation
The titer is the quotient of the actual and theoretical values for
the concentration of a standard solution.
Titer = C00/C01/EP 1 (input parameters Titrino)

EP1 = standard solution KOH in mL consumed up to endpoint
C00 = weight of benzoic acid in mg
C01 = 12.212 (molecular weight of benzoic acid in g/mol x 0.1 = 122.12 x
0.1 in mg/L)

Measured value
Sample size
benzoic acid
(mg)
Consumption of
KOH (mL)
Titer
103.77
9.434
0.9007
105.44
9.594
0.9000
101.24
9.232
0.8980
101.28
9.217
0.8998
92.81
8.454
0.8990
104.81
9.533
0.9003
89.60
8.144
0.9009
82.26
7.483
0.9002
87.57
7.990
0.8975
10
84.75
7.746
0.8959
0.8992
0.0016
Srel %
0.18
Before the titer is determined, the KOH standard

solution should be checked
for a fine white precipitate of
potassium carbonate. The
largest error encountered in
the calculation is the relative
inaccuracy when weighing
out the standard titrimetric
substance. During the titration care must be taken that
no air bubbles are entrained
by the stirrer bar, as any carbon dioxide absorbed from
the air could produce a second endpoint caused by
freshly formed potassium
carbonate (or high-bias results are obtained for the titration of weak acids as a result of leveling).
84
II.2.4 Titration of nitrating acid (HNO3 / H2SO4 mixture)

Learning topics
Meaning of relative acid strength
(pKa values).
Separation of different acids in a single titration.
Titration sequence according to acid
strength:
EP1 = 12 H2SO4 + HNO3:
EP2 EP1 = 12 H2SO4
(reaction equations are given below)
Potentiometric determination of nitrating acid

Principles
In industry nitrating acid is used in the production of nitro compounds such as explosives, pharmaceuticals and plastics. Nitrating acid is a mixture of concentrated
sulfuric acid and concentrated nitric acid.
In order to obtain the content of nitric acid
and sulfuric acid analytically, the nitrating
acid is dissolved in methanol and titrated
with a standard solution of cyclohexylamine
(C6H11NH2). The first endpoint corresponds
to the sum of the first step of the sulfuric acid
with the nitric acid. The considerably weaker
endpoint of the second step of the sulfuric
acid is only reached at a considerably higher
pH value.
Compared with other alkaline titrants, cyclohexylamine has the great advantage that it
is not affected by carbon dioxide; the formation of tertiary amines by deamination is also
eliminated.
Reaction equations
H2SO4 + C6H11NH2 C6H11NH3+ + HSO4
HNO3 + C6H11NH2 C6H11NH3+ NO3
HSO4 + C6H11NH2 C6H11NH3+ + SO42
Exchange Unit 5 mL
Solvotrode
6.0229.100

Methanol, reagent grade >99.8%
Fluka
65543
Cyclohexylamine, reagent grade >99.5%
Fluka
29300
Nitric acid, reagent grade >65%
Fluka
84380
Sulfuric acid, reagent grade 9597%
Fluka
84720
Deionized water
self-prepared
Procedure
2 mL each of nitric acid and sulfuric acid
are pipetted into a 200 mL volumetric flask
and mixed with 40 mL deionized water. After the cooling fill with methanol to the mark
and mix.
If no ready-to-use cyclohexylamine standard
solution is available then 49.08 g cyclohexylamine is dissolved in 1 liter of methanol. After thorough mixing the standard solution is
ready and can be used for the titration.
A volumetric pipet or a piston pipet is used to
pipet 3 mL nitrating acid into a 50 mL beaker where it is treated with 25 mL methanol. A
magnetic stirrer bar is added and the titration
is carried out until 2 endpoints have been
detected or the maximum volume has been
reached. A DET method is drawn up according to the following parameters and used for
titrating the nitrating acid:
794 Titrino
01102
794.0010
date 2002-08-28
time 15:37
55
DET pH
Nitr.Ac
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
35 mV/min
equilibr.time
30 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
4 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
85

mL
Meas- Sample
size ni- titrant
ured
value tric acid EP1
(mL)
mL
titrant
EP2
g/L
H2SO4
g/L
HNO3
2.50
1.6143 2.4964 17.302
9.227
2.50
1.6113 2.4927 17.288
9.198
2.50
1.6214 2.5114 17.457
9.217
2.50
1.6118 2.4949 17.321
9.183
2.50
1.6166 2.5046 17.418
9.182
2.50
1.6098 2.4917 17.298
9.173
2.50
1.6053 2.4809 17.174
9.196
2.50
1.6025 2.4780 17.172
9.162
2.50
1.6073 2.4878 17.270
9.159
10
2.50
1.6014 2.4725 17.086
9.203
17.279
9.190
0.112
0.022
Srel %
0.65
0.24
(A dilute mixture of HNO3 and H2SO4 has been used)

Calculation
g/L H2SO4
= (EP2
EP1) x C01/C00
C00 = sample size in mL
C01 = 49.039
C02 = 31.506
g/L HNO3 = [EP1 (EP2

EP1)] x C02 / C00
86
II.2.5 Acid number in petrochemical products with alcoholic KOH

Learning topics
Determination of weak acids, produced by the breakdown of lubricants, by non-aqueous titration with
a strong base.
Principles
The so-called acid number TAN (Total Acid
Number) is a cumulative parameter for all
free acids in petrochemical products that
can react with KOH. Lubricants (fats/oils) are
subjected to high mechanical and/or thermal
stresses when used in motors, gearboxes,
etc. The thermal breakdown of lubricants
produces acids which could cause corrosion. This is why additives are added to the
lubricants to bind the acids produced. These
additives could be, for example, amines or
metallic soaps.
The determination of the TAN value is used
to check the extent to which the additives
have already been used up, or how much
free acid can already be determined in the
oil. The acid number provides information
about how long and how intensively the oil
has been used. The acids found in the oil
have a negative effect on the working life of
the motor, which is why the acid number is
particularly important.
It is not possible to differentiate between
the different acids titrimetrically. Their total
content (TAN Total Acid Number) is determined. In this case the solvent used is a mixture of isopropanol, toluene and water; a Solvotrode is used to detect the endpoint. The
titrant is tetra-n-butylammonium hydroxide.
Acids with a pKa >9 are normally not determined.

Exchange Unit 20 mL
Solvotrode
6.0229.100
Tetra-n-butylammonium hydroxide
standard solution, c = 0.1 mol/L
Merck
1.09162.1000
Toluene analytical grade >99%
Fluka
89682
Isopropanol analytical grade >99.5%
Fluka
59302
Deionized water
self-prepared
Procedure
If no solvent mixture is already available then
it must first be prepared by mixing 500 mL
toluene, 495 mL isopropanol and 5 mL water.
The sample size depends on the expected
acid number. If the acid number is unknown
then one or more preliminary titrations must
be carried out with the sample size being increased step by step until one or more endpoints can be found. However, the sample
size should not exceed 10 g. The oil sample
is weighed out into a beaker, a stirrer bar is
added and the oil is dissolved in 50 mL of the
solvent mixture.
Before the start of the titration care must be
taken that the sample has been completely
dissolved in the solvent mixture and that no
precipitate can be recognized. We recommend that samples that are difficult to dissolve are mixed thoroughly for some time on
a magnetic stirrer.
The electrode is immersed in the beaker until the ground-joint diaphragm is completely
wetted by the solvent. The titration is then
carried out according to the dynamic pH
program given below.
At the end of the titration the solvent mixture
should be used to rinse thoroughly in order
to prevent the carryover of adhering residues
to the next titration.
After several measurements the Solvotrode

should be immersed in distilled water for
some time without moistening the groundjoint diaphragm, as otherwise electrolyte solution would be washed out.
794 Titrino
01102
794.0010
date 2002-08-29
time 08:55
0
DET pH
TAN
parameters
meas.pt.density
4
min.incr.
10.0 l
min.incr.alternative 100.0 l
titr.rate
max. ml/min
signal drift
10 mV/min
equilibr.time
38 s
start V:
OFF
pause
50 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
4 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
last
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
value
activate pulse:
OFF
------------
87
Calculation
As the acid number parameter is a cumulative parameter and stands for a number of
acidic compounds, it does not refer to a particular acid. The unit of the acid number is:
mg/g (mg KOH per g sample).
The Titrino calculates the acid number according to the following entered formula:
RS1 = (EP1 C31) x C01 x C02 x C03 / C00;1;mg/g
EP1 = consumption of titrant in mL up to first endpoint
C00 = sample weight in g
C01 = concentration of standard solution in mol/L (0.1)
C02 = titer of standard solution
C03 = molecular weight KOH in g/mol (56.106)
C31 = blank value for KOH for solvent in mL
Remarks
It is particularly important that the oil sample
is completely dissolved in the solvent mixture before the start of the titration. To obtain
a better comparison of the results, an internal standard is used, which is dissolved in
the solvent before addition. This standard
contained an amount of benzoic acid corresponding to a titrant consumption of approx. 3 mL.
88
II.2.6 Determining the ephedrine hydrochloride content according to Pharm. Europe

Learning topics
Direct non-aqueous titration of
amine hydrochlorides with a strong
base. Titration sequence according
to acid strength.
Principles
Pharm. Europe describes an elegant, modern method. As the products usually still contain traces of free HCl [pKa (HCl) <pKa (hydrochloride)], this means that two endpoints
are found in non-aqueous solvents (this cannot be observed in aqueous solutions because of leveling). It is difficult to determine
the HCl traces quantitatively. For this reason
some HCl is deliberately added to the sample solution. This makes the first endpoint
more noticeable. It is important that carbonate-free NaOH is used. If this is not the case
then high-bias results will be obtained as the
carbonate will be titrated together with the
amine hydrochloride.
EP1
= HCl (not used for the calculation)
(EP2 EP1) = amine hydrochloride

Reaction equation
R NH2 x HCl + NaOH R NH2 + NaCl
+ H2O
Exchange Unit 20 mL
Solvotrode
6.0229.100
Titrant:
sodium hydroxide c(NaOH) = 0.1 mol/L
ready-to-use standard solution
Auxiliary solution:
hydrochloric acid c(HCl) = 0.01 mol/L
self-prepared
Solvent:
ethanol analytical grade 96%
Procedure
The sample containing ephedrine is weighed
out into a beaker with an accuracy of 0.1 mg
and dissolved in approx. 50 mL ethanol. 5
mL hydrochloric acid is added to the beaker
from a volumetric pipet together with a stirrer
bar and the sample is thoroughly mixed on a
magnetic stirrer.
The endpoint is detected by immersing a Solvotrode in the beaker: The titration is carried
out with c(NaOH) = 0.1 mol/L up to the second endpoint using the following program:
794 Titrino
01102
794.0010
date 2002-09-12
time 08:26
0
DET pH
EphedrEU
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop pH
OFF
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
value
activate pulse:
OFF
------------
89
Calculation
1 mL c(NaOH) = 0.1 mol/L corresponds to 20.17 mg ephedrine
Ephedrine = (EP1EP2) x C01
EP1 = consumption of mL NaOH up to first endpoint
EP2 = consumption of mL NaOH up to second endpoint
C01 = 20.17 (equivalent weight of ephedrine)

Measured value Sample size (mL)
(EP2 EP1)
mL
%
Ephedrine x HCl
10.0
4.965
100.14
10.0
4.968
100.20
10.0
4.969
100.22
10.0
4.973
100.31
10.0
4.970
100.24
10.0
4.975
100.35
100.24
0.08
Srel %
0.08

If bases containing carbonate are used then high-bias results
will be obtained (carbonate/weak acid leveling).
90
II.2.7 Determining the ephedrine hydrochloride content according to USP 24/25

Learning topics
Indirect, non-aqueous titration of
amine hydrochlorides with HClO4 in
glacial acetic acid.
Conversion of the hydrochlorides
to acetates conjugated acid-base
pairs.
Principles
This method is also used for the analytical
determination of amine hydrochlorides in a
non-aqueous titration.
This conventional method, which is not environmentally compatible, is still frequently
stipulated in the USP instructions. The substance is dissolved in glacial acetic acid, an
excess of Hg(II) acetate is added and the
amine acetate formed is titrated (as a weak
base) with the strong acid HClO4. Acetic acid
and mercury(II) acetate convert the amine
hydrochlorides (RNH2 x HCl) to amine acetates (RNH2 x CH3COOH) and mercury(II)
chloride. Perchloric acid can be used to convert the amine acetate to amine perchlorate
(RNH2 x HClO4) in a displacement reaction.
Reaction equations
2 R NH2 x HCl + Hg(CH3COO)2 2 R
NH2 x CH3COOH + HgCl2
R NH2 x CH3COOH + HClO4 R NH2 x
HClO4 + CH3COOH
Exchange Unit 20 mL
Solvotrode
6.0229.100
Perchloric acid in glacial acetic acid
c(HClO4) = 0.1 mol/L
Hg(CH3COO)2 in glacial acetic acid
(3.19 g / 100 mL)
Anhydrous acetic acid (glacial acetic acid)
Deionized water
Procedure
Depending on the expected ephedrine content, 0.250 g to 0.500 g sample is weighed
out into a titration beaker. The sample is dissolved in glacial acetic acid and treated with
10 mL Hg(CH3COO)2. A stirrer bar is added
and the solution is titrated with c(HClO4) =
0.1 mol/L up to the first endpoint. The endpoint is detected with the Solvotrode and the
following dynamic program is used for the titration:
pa
794 Titrino
01102
794.0010
date 2002-09-12
time 08:15
0
DET pH
EphedrUS
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop pH
OFF
stop EP
1
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
91
Calculation
1 mL c(HClO4) = 0.1 mol/L corresponds to 20.17 mg ephedrine
Mass fraction of ephedrine = EP1 x C01 x C02 x C31 / C00
EP1
C00
C01
C02
C31
=
=
=
=
=
perchloric acid consumption up to endpoint in mL

sample weight in mg
equivalent weight of ephedrine (20.17)
100 (for %)
titer of HClO4

Measured value
Sample size
(mg)
mL c(HClO4) =
0.1 mol/L
%
Ephedrine x HCl
100.22
4.951
99.64
111.25
4.500
99.72
106.73
5.285
99.87
112.14
5.543
99.70
99.72
0.08
Srel %
0.08

In this type of titration the glacial acetic acid continuously removes water from the electrode; this could result in an uncontrolled electrode drift. After each titration the glass ring of
the ground-joint diaphragm must be checked to ensure that
it is seated loosely. A small amount of electrolyte solution
should escape. It is necessary to immerse the electrode in a
beaker containing deionized water after each sample.
92
II.2.8 Benzoic acid in H2O, ethanol, acetone, methyl isobutyl ketone (MIBK) and acetonitrile
Learning topics
base in various solvents.
Influence of the solvent on the shape
of the titration curve and the position
of the endpoint.
Autoprotolysis and dielectric constant of the solvent used.
Choice of a suitable solvent for weak
acids.
Principles
Benzoic acid can be titrated directly both in
water and in non-aqueous solvents with sodium hydroxide or other strong bases. In this
case sodium hydroxide c(NaOH) = 0.1 mol/L
dissolved in ethanol is used as the standard
solution. A Solvotrode is used to detect the
endpoint instead of a colored indicator.
Reaction equation
C6H5COOH + NaOH C6H5COONa +
H2O
Exchange Unit 20 mL
Solvotrode
6.0229.100
Benzoic acid
analytical grade >99.5%
Sodium hydroxide
c(NaOH) = 0.1 mol/L in ethanol
Acetone
analytical grade
Acetonitrile
analytical grade
Methyl isobutyl ketone (MIBK)
analytical grade
Deionized water
Procedure
Benzoic acid is dried overnight in a drying
oven at 105 C and then allowed to cool
down to room temperature in a desiccator
for one hour. It is then weighed out into a titration beaker and dissolved in approx. 50
mL of the particular solvent. A stirrer bar is
added and the benzoic acid is stirred continuously until it has fully dissolved. The buret
and the Solvotrode are positioned in the solution such that the added standard solution
is not led directly to the electrode. The titration is carried out according to the following
dynamic pH program:
pa
794 Titrino
01102
794.0010
date 2002-09-12
time 08:48
0
DET pH
BENZOICA
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop pH
OFF
stop EP
1
filling rate
max. ml/min
>statistics
status:
ON
mean
n=
2
res.tab:
original
>evaluation
EPC
5
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
value
activate pulse:
OFF
------------
93

Example of a titration in acetone. Please carry out titrations in the other solvents
and compare the titration
curves.
Calculation
1 mL c(NaOH) = 0.1 mol/L corresponds to 12.212 mg
C7H6O2
mg benzoic acid / sample weight = EP1 x C01
EP1 = consumption; mL c(NaOH) = 0.1 mol/L
C01 = 12.212 (mg/mL)
II.2.9 Aniline in H2O, ethanol, acetone, dioxan/IPA 1:1 and acetonitrile

Learning topics
Titration of a weak base with a strong
acid in various solvents.
Influence of the solvent on the shape
of the titration curve and the position
of the endpoint.
Autoprotolysis and dielectric constant of the solvent used.
Choice of a suitable solvent for weak
bases.
Principles
Aniline (aminobenzene) is a weakly alkaline
compound that reacts with hydrochloric acid
to form the so-called aniline salt (aniline hydrochloride). In contrast to aniline itself, this
salt is easily soluble in water. Aniline is sparingly soluble in water, but is soluble in alcohols.
Reaction equation
C6H5 NH2 + HCl C6H5 NH2 x HCl
Exchange Unit 20 mL
Solvotrode
6.0229.100
94

Hydrochloric acid
c(HCl) = 0.1 mol/L in ethanol,
Deionized water
self-prepared
Ethanol
analytical grade 96%
Acetone
analytical grade
Dioxan
analytical grade
2-Propanol
analytical grade
Acetonitrile
analytical grade
Aniline
analytical grade
Procedure
Approx. 7080 mg aniline is carefully
weighed out into a titration beaker using an
analytical balance and dissolved in approx.
50 mL of the particular solvent. A stirrer bar is
added and the buret tip and the Solvotrode
are immersed in the solution so that the added hydrochloric acid solution is not led directly to the electrode. The sample is then titrated according to the following program up
to the first endpoint:

pa
794 Titrino
01102
794.0010
date 2002-09-12
time 09:10
0
DET pH
ANILINE
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop pH
OFF
stop EP
1
filling rate
max. ml/min
>statistics
status:
ON
mean
n=
2
res.tab:
original
>evaluation
EPC
5
EP recognition:
all
fix EP1 at pH
OFF
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
value
activate pulse:
OFF
------------

Calculation
1 mL c(HCl) = 0.1 mol/L corresponds to 9.312 mg C6H8N
mg aniline / sample weight =
EP1 x C01 x C30
EP1 = consumption; mL
c(HCl) = 0.1 mol/L
C01 = 9.312 (M aniline in g/mol
x 0.1 = 93.12 x 0.1 in
mg/mL)
C30 = titer of HCl solution
95
II.3 Precipitation titrations and methods

II.3.1 Titer determination of c(AgNO3) = 0.1 mol/L
Learning topics
Potentiometric indication.
Shape of titration curve.
Choice of suitable electrode.
Principles
As a dilute AgNO3 standard solution is frequently not adjusted exactly to a particular
concentration, but only an approximate concentration of, for example, 0.1 mol/L, its accurate concentration must be determined by
using a standard titrimetric substance. The titer of the AgNO3 solution is determined by
using NaCl as the standard titrimetric substance.
Reaction equation
Ag+ + Cl AgCl (s)
Precipitation of Cl by Ag+
Exchange Unit
20 mL
Ag Titrode
6.0430.100
Titrant:
c(AgNO3) = 0.1 mol/L
Merck 1.09081.1000
Acid:
c(HNO3) = 2 mol/L
Standard titrimetric substance:
NaCl analytical grade
Fluka 71380
Procedure
The sodium chloride is dried in a drying oven
for 2 h at 120 C and then cooled down and
stored in a desiccator. 10 samples of between 80 and 105 mg are weighed out with
an accuracy of 0.1 mg into individual 100 mL
beakers. Each sample is acidified with 5 mL
c(HNO3) = 2 mol/L and made up to approx.
60 mL with dist. H2O. The following parameters are used for the titration:
DET U
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
OFF
filling rate
max. ml/min
>statistics
status:
ON
mean
n=
10
res.tab:
original
>evaluation
EPC
5
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
value
activate pulse:
OFF
------------
96
Calculation
In order to obtain the titer of AgNO3, the following formula
Titer = C00 x C01 / C02 / EP1;4;
EP1
C00
C01
C02
added volume up to first endpoint [mL]

weight of standard titrimetric substance [g]
10000 (correction factor)
molecular weight of NaCl = 58.44 [g/mol]
The titer has no unit and should be given to 4 decimal places.

Measured value
Sample size
NaCl (g)
Consumption of
AgNO3 (mL)
Titer
0.0918
15.766
0.9963
0.0881
15.064
1.0007
0.1048
17.888
1.0025
0.0652
11.172
0.9986
0.0762
12.424
0.9999
0.0882
15.059
1.0022
0.0790
13.510
1.0006
0.0821
14.038
1.0007
0.0866
14.823
0.9997
10
0.0922
15.766
1.0006
1.0002
0.0018
Srel %
0.18

Too fast titration leads to inclusions in the precipitate and
therefore incorrect results.
97
II.3.2 Chloride (NaCl) in meat bouillon

Procedure
Learning topics
Analysis of foodstuffs.
Sample preparation.
Salt content.
Principles
This titration represents applications in the
food sector in which the salt content of a
product is to be determined. Examples of
possible matrices are, for example, crispbread, ready-to-serve meals, spice mixtures.
With the usual salt contents encountered the
precipitation titration is a simple and favorably priced method that can be automated.
Reaction equation
Ag++ Cl AgCl (s)
precipitation of Cl by Ag+
Exchange Unit
20 mL
Ag Titrode
6.0430.100

Titrant:
Merck 1.09081.1000
Acid:
c(HNO3) = 2 mol/L
Bouillon:
0.2 L (one cube dissolved in 200 mL warm
H2O)
5 mL bouillon is pipetted into each of 10 beakers (100 mL); care must be taken that the
bouillon is always well shaken to prevent
its constituents from being deposited. 5 mL
c(HNO3) = 2 mol/L is added to each beaker
followed by dist. H2O to make up to approx.
60 mL. The following parameters are used
for the titration:
DET U
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
OFF
filling rate
max. ml/min
>statistics
status:
ON
mean
n=
10
res.tab:
original
>evaluation
EPC
5
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
98

Calculation
In order to obtain the concentration of NaCl in the
bouillon, the following formula is entered in the instrument:
(NaCl) = EP1 x CO4 x C05
x C06 / C00;2;g/L
EP1
added volume up to first

C00
bouillon sample size [mL]
C04
molecular weight of NaCl =

58.44 [g/mol]
C05
concentration of standard
solution = 0.1 [mol/L]
C06
titer (1.0000) []
This results in (NaCl) having the

unit [g/L]; the concentration of
NaCl should be given to two decimal places.

Measured value
Sample size
bouillon (mL)
Consumption of
AgNO3 (mL)
g/L NaCl
5.00
16.535
19.33
5.00
16.524
19.31
5.00
16.489
19.27
5.00
16.472
19.25
5.00
16.573
19.37
5.00
16.478
19.26
5.00
16.457
19.23
5.00
16.529
19.32
5.00
16.494
19.28
10
5.00
16.532
19.32
19.29
0.043
Srel %
0.22

The bouillon should always be thoroughly shaken before pipetting as otherwise its constituents will be deposited. Care
must also be taken that any suspended matter in the bouillon, e.g. parsley or vegetable pieces, does not block the pipet.
99
II.3.3 Chloride in drinking water

Learning topics
Solubility product.
Exchange Unit 20 mL
Ag Titrode with Ag2S coating 6.0430.100
Analysis of drinking water.
Solubility.
Titrant:
c(AgNO3) = 0.01 mol/L Merck
Principles
In this case we are concerned with determining very small amounts of chloride, such as
are found in drinking water, by a precipitation
titration. The determination limit is approx. 3
mg/L chloride.
Standard titrimetric substance:

NaCl Fluka 71380
Acid:
c(HNO3) = 2 mol/L
Tap water from Herisau
Reaction equation
Procedure
Ag + Cl AgCl (s)
precipitation of Cl by Ag+
100 mL tap water is measured out into the titration beaker, treated with 2 mL c(HNO3) = 2
mol/L and then titrated with c(AgNO3) = 0.01
mol/L to after the first endpoint:
Calculation
1 mL c(AgNO3) = 0.01 mol/L corresponds to 0.3545 mg Cl
mg/L Cl = EP1 x C01 x C02 / C00
C01
C02
C00
= 0.3545
= 1000 (for 1 liter)
= sample size in mL (100)
100
II.3.4 Sulfide in wastewater

Learning topics
Environmental analysis.
Sample preparation.
Influence of pH and oxygen or air on
sulfides.
100 mL water sample is pipetted into a beaker from a volumetric pipet and made alkaline by the addition of 1 mL w(NaOH) = 30%.
A magnetic stirrer bar is added and the water
sample is titrated with silver nitrate solution
c(AgNO3) = 0.001 mol/L up to the first endpoint. An Ag Titrode is used for detecting the
endpoint. The following parameter settings
are used:
Principles
pa
Sulfides occur in wastewater and mineral water, among other things (e.g. spas, therapeutic water sources).
794 Titrino
01102
794.0010
date 2002-09-12
time 12:15
12
DET U
H2S-ABW.
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
Sulfide dissolved in water is precipitated as

silver sulfide; the endpoint is determined by
potentiometric detection with an Ag Titrode.
The water sample must be made alkaline
with NaOH in order to prevent the highly volatile H2S from escaping.
In this case a small amount of sodium sulfide is added to an alkaline water sample (O2free) and the free sulfide determined analytically with silver nitrate solution.
Reaction equation
H2S + 2 AgNO3 Ag2S + 2 HNO3
Exchange Unit
10 mL
AgNO3 standard solution
Procedure
101
Calculation
1 mL c(AgNO3) = 0.001 mol/L corresponds to 0.017 mg H2S
H2S = EP1 x C01 x C02 / C00;2;mg/L
EP1
C00
C01
C02
=
=
=
=
mL silver nitrate solution up to endpoint

sample size in mL (100)
0.017
1000 (for 1 liter)
Measured values and statistics:

Measured value
Sample size
water (mL)
Consumption of
AgNO3 (mL)
mg/L H2S
100
17.820
3.029
100
17.721
3.013
100
17.514
2.977
100
18.403
3.129
100
17.952
3.052
3.038
0.057
Srel %
1.89

Sample not made alkaline escape of H2S.
102
II.3.5 Cyanide in wastewater

Learning topics
Complex formation constant.
Solubility product.
Relative acid strengths.
Environmental/wastewater analysis.
Principles
Free cyanide ions in aqueous solution can
be determined analytically by a potentiometric titration with silver nitrate. The titration endpoint is determined by using an Ag
Titrode with a sulfide coating. When working
with cyanides particular care should be taken that an alkaline medium is always used,
as otherwise volatile hydrocyanic acid would
be formed. Apart from the danger to life this
would, of course, produce completely incorrect results.
The first endpoint corresponds to the free cyanide, the second to the silver-dicyano complex [Ag(CN)2].
Reaction equations
Ag+ + CN AgCN
AgCN + CN [Ag(CN)2]
Exchange Unit
10 mL
KCN
analytical grade
AgNO3
standard solution
NaOH solution
w(NaOH) = 30%
Cyanide standard
c(KCN) = 0.1 mol/L in

c(NaOH) = 0.1 mol/L
Procedure
Approx. 50 mL deionized water is placed
in a beaker and made alkaline with 1 mL
w(NaOH) = 30%. A volumetric pipet is used
to add 10 mL cyanide standard, a stirrer bar

is added and the sample is titrated with silver nitrate standard solution c(AgNO3) =
0.1 mol/L to the second endpoint according
to the following program (in practical work
one generally titrates only to the first, more
pronounced endpoint).
pa
794 Titrino
01102
794.0010
date 2002-09-12
time 13:36
12
DET U
Cyanide
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
103
Calculation
1 mL c(AgNO3) = 0.1 mol/L corresponds to 2.6018 mg CN (at
EP2) or 5.2036 mg CN (at EP1)
Cyanide (g/L) = EP1 x C01 / C00
EP1 = consumption of silver nitrate standard solution (mL)
C00 = size of standard in mL (10)
C01 = 5.2036
Measured values and statistics:

Measured value
Sample size
standard (mL)
Consumption of
AgNO3 (mL at
EP1)
Cyanide in g/L
10.0
4.998
1.3004
10.0
5.002
1.3014
10.0
4.999
1.3006
10.0
5.003
1.3017
10.0
5.001
1.3012
1.3011
0.0005
Srel %
0.04
104
II.3.6 Mixture of chloride, bromide and iodide with and without added acetone
Procedure
Learning topics
Solubility and solubility product.
Precipitation.
Differentiation.
Titration according to solubility product.
Reducing the solubility.
Principles
Because of their different solubility products,
chloride, bromide and iodide present in a
mixture can be determined individually by
titration. In the example given below, a solution is prepared that contains comparable
amounts of all the ions. The standard solution contains 0.1 mol/L each of NaCl, KBr
and KI. The mixture is acidified with nitric
acid and titrated up to the third endpoint with
silver nitrate. The difficulty with this particular titration is caused by the low difference
in solubility between silver chloride and silver bromide. An investigation is made into
whether acetone improves the separation.
Reaction equations
KI + AgNO3 AgI + KNO3
KBr + AgNO3 AgBr + KNO3
KCl + AgNO3 AgCl + KNO3
Exchange Unit
20 mL
Sodium chloride
analytical grade
Potassium bromide analytical grade

Potassium iodide
analytical grade
Silver nitrate ready-to-use standard solution

Nitric acid
c(HNO3) = 2 mol/L
6 mL of the thoroughly mixed halides mixture is pipetted into a beaker from a volumetric pipet and acidified with 1 mL c(HNO3)
= 2 mol/L. After the addition of approx. 50
mL deionized water and a magnetic stirrer
bar the titration is carried out according to
the following DET program:
pa
794 Titrino
01102
794.0010
date 2002-09-12
time 14:26
16
DET U
Cl,Br,I
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
6 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
105
Examples of titration curves

Titration without acetone
Titration with acetone
Calculation
1 mL c(AgNO3) = 0.1 mol/L corresponds to 3.5453 mg Cl or
7.9909 mg Br or 12.69 mg I
mg/L chloride
= (EP3EP2) x C01 / C00
mg/L bromide = (EP2EP1) x C02 / C00

mg/L iodide
C00
C01
C02
C03
=
=
=
=
= EP1 x C03 / C00
sample size in mL
3.5453
7.9909
12.69
106
II.3.7 Cationic surfactant in mouth rinses

Learning topics
Substantivity*.
Disinfectants.
Analysis of drugs.
* In this case substantivity is understood to be
the characteristic property of surfactants (particularly cationic surfactants) of adhering to
surfaces. With respect to washing agents this
is also known as the so-called Lenor effect
(fabric conditioners).
Principles
In order to determine cetylpyridinium chloride (CPCl), a cationic surfactant, the mouth
rinse sample is titrated with sodium dodecylsulfate (SDS), an anionic surfactant. Cetylpyridinium chloride is used in these formulations as a mouth and throat disinfectant.
For many years surfactants were determined
by the classical two-phase titration with colored indicators and visual indication. As this
involved the use of chloroform, the potentiometrically indicated surfactant titration
today offers an environmentally more favorable alternative. An ion-sensitive surfactant electrode is used, namely a PVC liquid-membrane electrode whose membrane
composition has been optimized for the determination of surfactants. The measurement
is made against a reference electrode.
Reaction equation
CPCl + SDS CPCl SDS (ion associate)
Exchange Unit
20 mL
Ionic Surfactant Electrode
6.0507.120
Ag/AgCl reference electrode 6.0726.100
Buffer solution pH = 3.0 citrate/HCL
Merck Titrisol no. 109883
Titrant:
c(SDS) = 0.004 mol/L.
Procedure
10 mL portions of mouth rinse are pipetted
into 10 beakers (100 mL), 5 mL buffer is added and the solution is made up to approx. 50
mL with dist. H2O.
The following parameters are used for the titration:
MET U
parameters
V step
0.10 ml
titr.rate
max. ml/min
signal drift
OFF mV/min
equilibr.time
10 s
start V:
OFF
pause
30 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
5 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
1 mV
EP recognition:
greatest
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
107

Calculation
In order to determine the
CPCl content in a mouth
rinse, the following formula
CPCl = EP1 x C01 x C02 x
C03 / C00;1;ppm
EP1 = mL titrant up to first equivalence point
C01 = conversion factor:
1 mL SDS 0.004 mol/L
corresponds to 1.432 mg
CPCl
C02 = correction factor for mg/L
(1000)
C03 = titer (1)

Measured value
Sample size
(mL)
Consumption of
SDS (mL)
ppm CPCl
100
1.550
222.0
100
1.532
219.4
100
1.500
214.8
100
1.500
214.8
100
1.550
224.4
100
1.567
222.0
100
1.550
224.4
100
1.481
212.1
100
1.477
211.5
10
100
1.500
214.8
218.0
5.0
Srel %
2.29

In surfactant titrations it must be noted that
the otherwise usual degree of accuracy cannot be achieved. This is primarily because of
the reaction mechanism, but inhomogeneities are also involved.
Methanol can be added if foam is produced. If
the electrode is allowed to remain too long in
the titrated solution, it will either not respond
at all in the following titration or respond incorrectly. In such cases the electrode must
be rinsed with methanol and placed in sodium dodecylsulfate solution, c(DSS) = 0.004
mol/L, for several minutes.
Three to four conditioning titrations should

be carried out before the titration proper. Before each titration the electrode should be
immersed in the sample solution for approx.
2030 s in order to ensure that it is adapted to the sample matrix. The working life of
the electrode can be lengthened by storing
it dry.
108
II.3.8 Anionic surfactants and soaps in washing powder, potentiometric two-phase titration
Learning topics
Surfactant analysis.
Characteristics of anionic surfactants and soaps.
pH dependency of surfactant group
structure.
Titration curve.
Two-phase titration.
Choice of a suitable electrode.
Principles
The separation of anionic surfactants and
soaps is based on the fact that soaps lose
their wash-active properties under acidic
conditions. In an acidic medium soaps are
present as undissociated fatty acids; these
cannot be determined analytically with Hyamine. In contrast, anionic surfactants can
be titrated with Hyamine a cationic surfactant in both acidic and alkaline solution
as in each case they are present as an ionic
compounds.
This means that the analytical determination
of both types of surfactant in a single sample
is only possible by carrying out two separate
titrations.
In the first titration at pH 2.0 only the anionic surfactants are determined.
In a second titration at pH 11.5 both anionic surfactants and soaps are determined.
The surfactants are determined in a twophase titration in which a solvent mixture
consisting of a 1 : 1 mixture of methyl isobutyl ketone and ethanol is used.
The ion-sensitive electrode Surfactrode Refill is used for detection (together with an Ag/
AgCl reference electrode).
Before the start of the titration the pH must
be adjusted with NaOH or HCl. This is done
using a combined pH glass electrode that
can be used in addition to the Surfactrode
Refill.

Exchange Unit
Viscotrode
Surfactrode Refill
Ag/AgCl reference electrode
Propeller stirrer
20 mL
6.0239.100
6.0507.140
6.0726.107
727

Hyamine standard solution
c(Hyamine) = 0.005 mol/L
Solvent mixture
methyl isobutyl ketone / ethanol 1 : 1 (V/V)
Solubility promoter
Metrohm TEGOadd
Deionized water
self-prepared
Procedure
Step 1: Anionic surfactants
Approx. 0.2 g of the homogenized sample is
weighed out into a 150 mL beaker and fully
dissolved in approx. 70 mL deionized water.
After the addition of 0.2 mL TEGOadd, the
combined glass electrode is immersed in the
solution and the pH is adjusted to 2.0 by the
addition of hydrochloric acid.
The Surfactrode Refill is then immersed in
the beaker in place of the combined glass
electrode and 20 mL of the solvent mixture
is added. The propeller stirrer is immersed
deeply in the sample so that the sample and
solvent can be thoroughly mixed. A homogeneous suspension of the solvent mixture and
dissolved sample should be formed. The titration is then carried out up to the endpoint
using the Hyamine standard solution and a
DET program.
Step 2: Sum of the anionic surfactants and
soaps
Approx. 0.2 g of the homogenized sample is
weighed out into a 150 mL beaker and fully
dissolved in approx. 70 mL deionized water.
After the addition of 0.2 mL TEGOadd, the
combined glass electrode is immersed in
the solution and the pH value is adjusted to
11.50 by the addition of sodium hydroxide.
The Surfactrode Refill is then immersed in
the beaker in place of the combined glass
electrode and 20 mL of the solvent mixture
is added. The propeller stirrer is immersed
deeply in the sample so that the sample and
solvent can be thoroughly mixed. Care must
be taken that no air bubbles are entrained
and that no deep vortex is formed. Nevertheless, a homogeneous suspension of the solvent mixture and dissolved sample should
still be formed.
A magnetic stirrer bar cannot mix the solvent
mixture and the dissolved sample satisfactorily and cannot be used for such a determination.
109
The following parameters are used for the titration:

pa
794 Titrino
01102
794.0010
date 2002-09-06
time 16:07
47
DET U
TensM3
parameters
meas.pt.density
2
min.incr.
50.0 l
titr.rate
max. ml/min
signal drift
OFF mV/min
equilibr.time
15 s
start V:
OFF
pause
30 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
ON
mean
n=
3
res.tab:
original
>evaluation
EPC
2
EP recognition:
greatest
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
110

(Titration curve at
pH = 11.5)
Calculation
mmol/100 g surfactants
EP1
C01
C02
C00
=
=
=
=
= EP1 x C01 x C02 / C00
consumption of Hyamine standard solution

concentration of Hyamine = 0.005 mol/L
100 (for 100 g)
sample size in g

Measured value
Sample size
(g)
Hyamine consumption (mL)
Total A.T. mmol/

100 g
0.2022
17.414
43.061
0.2315
19.477
44.065
0.2210
19.461
44.029
0.2255
18.944
42.004
0.2004
17.275
43.101
43.252
0.849
Srel %
1.96
111
3.9 Calibration factor for nonionic surfactants

Learning topics
Use of a calibration factor instead of
determining the titer.
300 mL water under heating. Add 10 mL

buffer solution pH = 10. Combine and
make up to 1000 mL with H2O.
Non-stoichiometric behavior.
Polyethylene glycol
Make up 1 g/L with deionized water.
Pseudo-complexes*.
Procedure
Choice of suitable electrodes.
10 mL standard surfactant solution is pipetted from a volumetric pipet into a beaker and
diluted to approx. 60 mL with water. 10 mL
barium chloride solution is added followed
by a magnetic stirrer bar and the solution is
thoroughly mixed. The solution is then titrated with the STPB standard solution up to the
first endpoint using the DET program given
below.
* See Application Bulletin no. 230 for additional

information.
Principles
In many formulations, nonionic surfactants
are used as co-surfactants to increase effectiveness (washing power, emulsifiability, etc.
see also literature reference 17).
The calibration factor states how much standard surfactant (e.g. polyethylene glycol) reacts with one milliliter of the standard solution.
Reaction equations
NIO + x Ba2+ [NIOBax]2x+
[NIOBax]2x+ + 2xTPB [NIOBax]TPB2x
TPB = tetraphenylborate ion

Exchange Unit
10 mL
NIO surfactant electrode
6.0507.010

6.0726.100
(outer electrolyte NaCl, c = 1 mol/L)
Buffer solution pH 10
1.24 g H3BO3 is treated with 10 mL
c(NaOH) = 1 mol/L and made up to 100
mL with H2O.
BaCl2 solution 21 g
BaCl2 x 2 H2O + 1 mL conc. HCl is made
up to 100 mL with H2O.
STPB standard solution
3.4223 g sodium tetraphenylborate is dissolved in 300 mL H2O. In a second beaker 10 g polyvinyl alcohol is dissolved in
The electrode must be rinsed with methanol

after every 3 to 4 titrations or wiped with a
methanol-moistened tissue.
pa
794 Titrino
01102
794.0010
date 2002-09-12
time 10:57
0
DET U
TensMe11
parameters
meas.pt.density
4
min.incr.
50.0 l
titr.rate
max. ml/min
signal drift
OFF mV/min
equilibr.time
20 s
start V:
OFF
pause
30 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
greatest
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
112
Calculation
mg NIO surfactant / mL STPB standard solution = C00 x
EP1
EP1 = consumption of STPB standard solution
C00 = volume of standard surfactant solution used

Measured value
Sample size
standard (mg)
Consumption of
STPB (mL)
Calibration
factor (mg/mL)
10.0
4.354
2.2967
10.0
4.427
2.2589
10.0
4.414
2.2655
10.0
4.412
2.2665
10.0
4.265
2.3477
10.0
4.207
2.3770
2.2966
0.0488
Srel %
2.12
113
II.3.10 Nonionic surfactants in household cleaners

Acetic acid c = 2 mol/L
Learning topics
Special surfactant analysis.
Influence of ionic surfactants.
Principles
Household cleaners can contain up to 5%
nonionic surfactants in addition to cationic
surfactants. In the titration with STPB standard solution the pH only plays a minor role,
but it should not be below pH = 3 or above
pH = 9.
If the cleaning agent contains sulfates, incorrect results may be obtained because of the
precipitation of barium sulfate. In such cases
more BaCl2 must be added.
As barium also forms a precipitate with carbonates, the titration should be carried out
under slightly acidic conditions to prevent
any precipitation.
Exchange Unit 20 mL
NIO surfactant electrode
6.0507.010

6.0726.100
(outer electrolyte c(NaCl) = 1 mol/L)
Buffer solution pH 10
1.24 g H3BO3 is treated with 10 mL
c(NaOH) = 1 mol/L and made up to
100 mL with H2O.
BaCl2 solution 21 g BaCl2 x 2H2O + 1 mL
conc. HCl is made up to 100 mL with
H2O.
STPB standard solution
3.4223 g sodium tetraphenylborate is dissolved in 300 mL H2O. In a second beaker
10 g polyvinyl alcohol is dissolved in 300
mL water under heating. Add 10 mL buffer
solution pH = 10. Combine and make up
to 1000 mL with H2O.
Deionized water
Procedure
Approx. 1 g household cleaner is weighed
out exactly on an analytical balance and dissolved in approx. 80 mL deionized water. The
pH is adjusted to approx. 4 with dilute acetic acid and a magnetic stirrer bar is added
followed by 10 mL barium chloride solution.
The solution is stirred vigorously and titrated
with STPB standard solution using the following parameter settings:
pa
794 Titrino
01102
794.0010
date 2002-09-12
time 11:31
0
DET U
TENSME12
parameters
meas.pt.density
4
min.incr.
50.0 l
titr.rate
max. ml/min
signal drift
OFF mV/min
equilibr.time
20 s
start V:
OFF
pause
30 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
greatest
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
114
Calculation
% NIO surfactants = EP1 x C01 x C02 / C00
EP1
C00
C01
C02
=
=
=
=
consumption of STPB standard solution in mL

sample weight in g
0.1 (for %)
2.2966 (calibration factor)

Measured value
Sample size (g)
Consumption of
STPB (mL)
% NIOs
0.2975
0.440
0.3397
0.4648
0.746
0.3658
2.0518
3.072
0.3439
2.5060
3.624
0.3321
2.5836
3.743
0.3327
2.8033
4.020
0.3293
0.3400
0.0135
Srel %
3.98
115
II.4 Redox titrations and methods

II.4.1 Iodometry (iodine/thiosulfate)
Learning topics
Redox reactions.
Redox potential; titration curve.
In order to analytically determine the concentration of an unknown iodine solution, it

is titrated against a thiosulfate solution. The
thiosulfate (S2O32) reduces the iodine to be
determined to iodide (I) and oxidizes the
thiosulfate to tetrathionate (S4O62).
Mechanism*
Principles and reaction equations

Iodometry is probably the most versatile
method used in redox titrations. The wide
range of applications is based on the oxidizing effect of iodine and the reducing effect of
the iodide ions. The basic process is completely reversible:
I2 + 2 e
2 I
The mechanism of this redox reaction is similar to that observed in organic nucleophilic
substitution reactions. In the first step iodine
undergoes nucleophilic attack by the thiosulfate with the formation of iodide and an
intermediate product (OSO2SI). In the second step the iodine undergoes nucleophilic
displacement from the intermediate product
(OSO2SI) as iodide with the formation of tetrathionate.
This means that there are two possible ways

of using iodometry:
* According to A.D. Awtrey and R.E. Connick, J. Am.

Chem. Soc. 73 (1951) 1341
A) Reducing agents can be titrated directly

with iodine, for example:
Sn2+ + I2 Sn4+ + 2 I
B) Oxidizing agents are treated with an excess of KI solution (usually in an acidic
solution) and the released iodine is titrated, for example with thiosulfate solution:
2 Fe3+ + 2 I 2 Fe2+ + I2
2 S2O32 + I2 S4O62 + 2 I
As iodine solutions are unstable and their iodine content changes rapidly (iodine sublimates off), this means that titer determinations
have to be carried out frequently. As an alternative to KI3 solutions, a mixture of KI / KIO3 in
a 5:1 molar ratio can be used; this solution
releases iodine when acidified:
IO3 + 5 I + 6 H3O+ 3 I2 + 9 H2O
In this case the reaction rate depends strongly on the pH (Landolt reaction) this is why
work is usually carried out under strongly
acidic solutions (H2SO4).
Exchange Unit
20 mL
Pt Titrode
6.0431.100

Na thiosulfate solution
c(Na2S2O3) = 0.1 mol/L
Triiodide solution
c(KI3) = 0.05 mol/L
Acid
c(H2SO4) = 0.5 mol/L
Fluka 57665
116
Procedure
7 mL of the triiodide solution is pipetted into
a beaker (100 mL), 10 mL c(H2SO4) = 0.5
mol/L is then added and made up to approx.
60 mL with dist. H2O.
As iodine sublimates very easily, only that
particular beaker which is to be titrated immediately is prepared. A total of 10 samples
is titrated.
parameters:
DET U
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
20 mV/min
equilibr.time
38 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
ON
mean
n=
10
res.tab:
original
>evaluation
EPC
5
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
Calculation
To obtain the concentration of the iodine solution, the following formula must be entered in the instrument:
c(iodine) = EP1 x C01 / C02 / C00
Variables used
EP1
=
C00
=
C01
=
C02
=
added volume up to equivalence point [mL]

volume of triiodide solution [mL]
concentration of thiosulfate solution (0,1) [mol/L]
stchiometric factor (2) []
This results in c(iodine) having the unit [mol/L]. The concentration should be given to four decimal places.
117

Measured value
Sample size of
triiodide solution (mL)
Consumption of
thiosulfate (mL)
c(I2) in mol/L
7.000
7.095
0.0507
7.000
7.061
0.0504
7.000
7.074
0.0505
7.000
7.072
0.0505
7.000
7.090
0.0506
7.000
7.070
0.0505
7.000
7.080
0.0506
7.000
7.062
0.0504
7.000
7.079
0.0506
10
7.000
7.078
0.0506
0.0505
0.0001
Srel %
0.19
Possible sources of error:

Possible sources of error in the titration could be, for example, pipetting errors or the premature sublimation of iodine
from the triiodide solution. We recommend that pipetting
should be carried out as carefully as possible and that each
individual sample is prepared immediately before it is titrated
so that as little iodine as possible sublimates off.
118
II.4.2 Chromatometry
Procedure
Learning topics
Redox potential.
pH dependency of redox potential.
Altering the oxidation state.
c(1/6 K2Cr2O7) = 0.1 mol/L (or c(K2Cr2O7) =

1/60 mol/L)
Principles
Chromium(VI) is a relatively strong oxidizing
agent and is able to oxidize a large number
of reducing agents under acidic conditions.
In this process (which also involves hydrogen ions) dichromate, which is stable in acidic solution, accepts 6 electrons supplied by
the particular reducing agent and is reduced
to chromium(III):
Cr2O72 + 14 H3O+ + 6 e 2 Cr3+ + 21 H2O
Dichromates have the advantage that they
are very stable and can also be prepared
from a standard titrimetric substance
K2Cr2O7.
In our example the Fe(II) content of a solution
is titrated. The Fe(II) in an inorganic acid solution is oxidized to Fe(III) even at room temperature.
Reaction equation
Cr2O72 + 6 Fe2+ + 14 H3O+ 2 Cr3+ +
6 Fe3+ + 21 H2O
Exchange Unit
10 mL
Pt Titrode
6.0431.100

Potassium dichromate standard solution
c(1/6 K2Cr2O7) = 0.1 mol/L
(NH4)2Fe(SO4)2
analytical grade
Sulfuric acid
w(H2SO4) = 96%
K2Cr2O7 is dried overnight at 130 C in a drying oven and left to cool down in a desiccator
for at least 2 h. 4.9032 g K2Cr2O7 is dissolved
in dist. H2O in a 1000 mL volumetric flask,
made up to the mark and mixed.
Approx. 2 g ammonium iron(II) sulfate is dissolved in 100 mL water and 10 mL portions

are pipetted into beakers. Approx. 50 mL water is added and the solution is carefully acidified with 1 mL concentrated sulfuric acid. A
magnetic stirrer bar is added and the solution is titrated with K2Cr2O7 standard solution
c = 0.1 mol/L up to the first endpoint. A Pt
Titrode is used for recognizing the endpoint;
the titration is carried out according to the following program:
pa
794 Titrino
01102
794.0010
date 2002-09-12
time 17:50
12
DET U
Chromate
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
119
Calculation
1 mL c(1/6 K2Cr2O7) = 0.1 mol/L corresponds to 28.404 mg
(NH4)2Fe(SO4)2
g/L (NH4)2Fe(SO4)2 = EP1 x C01 / C00
EP1 = mL dichromate solution up to endpoint
C01 = 28.404
120
II.4.3 Cerimetry
Learning topics
Strength of the oxidizing agent,
oxidation performance.
pH dependency.
Principles
Ce(IV) is a very strong oxidizing agent. Solutions in sulfuric acid are also stable when
warm. Ce(IV) can only be used under acidic
conditions. The reaction takes place in one
step, no interfering intermediate products
are formed:
Ce4+ + e Ce3+
Ce(IV) can be used for the determination
of reducing agents in the presence of large
amounts of chloride.
Our example shows the titration with
hexacyanoferrate(II).
Reaction equation
[Fe(CN)6]4 + Ce4+ [Fe(CN)6]3 + Ce3+
Exchange Unit
10 or 20 mL
Pt Titrode
6.0431.100

Deionized water
Cerium(IV) sulfate solution
Merck 1.09092.100
Potassium hexacyanoferrate(II) trihydrate
ultrapure analytical grade
Fluka 60280
Concentrated sulfuric acid
95...97%
Fluka 84720
Procedure
Approx.
250
mg
potassium
hexacyanoferrate(II) is dissolved in 100 mL
water. 10 mL portions of the solution are pi-
petted into 100 mL beakers from a volumetric pipet. The portions are diluted to approx.
50 mL with deionized water and a magnetic
stirrer bar is added.
A graduated pipet is used to carefully add 5
mL concentrated sulfuric acid under vigorous stirring; care must be taken that the solution does not become too hot. If necessary
it should be cooled in an ice bath so that delayed boiling cannot occur.
Although the solution can also be titrated
when warm, it is advisable to allow it to cool
down to room temperature.
The sample is then titrated according to the
following DET U program (Pt Titrode):
pa
794 Titrino
01102
794.0010
date 2002-09-12
time 17:10
12
DET U
Cerimetr
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
121
Calculation
1 mL Ce(IV), c = 0.1 mol/L corresponds to 36.8346 mg
K4[Fe(CN)6]
%
= EP1 x C01 x C02 / C00
EP1
C00
C01
C02
=
=
=
=
mL Ce(IV) solution up to endpoint

sample weight in mg (250)
36.8346
100 (for %)

Measured value
Sample size
(mg)
Consumption of
Ce(IV) (mL)
% K4[Fe(CN)6]
246.2
5.890
88.12
253.8
6.068
88.07
250.3
5.980
88.00
261.7
6.256
88.05
88.06
0.05
Srel %
0.06
122
II.4.4 Permanganatometry
Procedure
Learning topics
Alteration of the oxidation state.
Redox processes.
pH dependency of redox potential.

KMnO4 is always used for standard solutions. This utilizes the high oxidation performance of this compound. The majority of titrations are carried out under strongly acidic
solutions (but not in HCl, which is oxidized
to chlorine and chlorine dioxide and would
therefore interfere).
In strongly acidic solutions, Mn(VII) is reduced to Mn(II):
MnO4 + 8 H3O+ + 5 e Mn2+ + 12 H2O
In weakly acidic or neutral solutions, Mn(VII)
is reduced to Mn(IV) and manganese dioxide
is formed:
MnO4 + 4 H3O+ + 3 e {MnO2}+ 6 H2O
and in alkaline solutions manganate:
MnO4 + e MnO42
Our example is the determination of oxalic
acid:
2 MnO4 + 5 C2O42 + 16 H+ 2 Mn2+
+ 10 CO2 + 8 H2O
Exchange Unit
20 mL
Pt Titrode
6.0431.100

Oxalic acid dihydrate
standard titrimetric substance
Sulfuric acid
c(H2SO4) = 2 mol/L
Potassium permanganate
standard solution c(KMnO4) = 0.02 mol/L
Manganese sulfate
analytical grade >99.5%
Fluka 84720
Approx. 20 mg oxalic acid dihydrate is

weighed out into a beaker on an analytical
balance and diluted with 50 mL deionized
water. 5 mL sulfuric acid and 0.5 g manganese sulfate* are then added, followed by a
magnetic stirrer bar, and the fine deposit of
manganese sulfate is completely dissolved
by vigorous stirring. A Pt Titrode is used for
endpoint recognition.
* Used as a catalyst so that the titration can be carried
out at room temperature.

parameter settings:
pa
794 Titrino
01102
794.0010
date 2002-09-13
time 09:18
0
DET U
Perm.
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
123
Calculation
1 mL c(KMnO4) = 0.02 mol/L corresponds to 6.303 mg
H2C2O4 x 2 H2O
%
= EP1 x C01 x C02 / C00
EP1
C00
C01
C02
=
=
=
=
mL permanganate solution up to endpoint

sample weight in mg
6.303
100 (for %)
124
II.4.5 Thiosulfate with iodine; potentiometric, biamperometric and bivoltametric titration

Procedure
Learning topics
Indication methods.
Dilute solutions.
Determination of thiosulfate with iodine solution

Principles
The irreversible reaction between iodine and
thiosulfate leads to the formation of iodide
and tetrathionate.
The endpoint of the titration can be indicated biamperometrically, potentiometrically as
well as bivoltametrically.
For potentiometric titration a platinum ring
electrode is used, whereas for bivoltametric
and biamperometric titration a separate double Pt-sheet electrode is used.
Reaction equation
2 S2O32 + I2 S4O62 + 2 I
Exchange Unit
20 mL
Combined Pt-ring electrode
6.0451.100
Separate double Pt-sheet

electrode
6.0309.100

Iodine solution
c(I2) = 0.05 mol/L
Sulfuric acid
c(H2SO4) = 2 mol/L
Potassium iodide
analytical grade
Sodium thiosulfate
standard solution c(Na2S2O3) = 0.1 mol/L
10 mL sodium thiosulfate standard solution

c = 0.1 mol/L is pipetted into a beaker from
a volumetric pipet and treated with 2 mL
c(H2SO4) = 2 mol/L. The solution is made up
to approx. 50 mL with deionized water and
thoroughly stirred. The sodium thiosulfate is
titrated with the standard iodine solution using the following MET program:
MET program for potentiometric titration
794 Titrino
01102
794.0010
date 2002-09-13
time 08:46
0
MET U
Thiosul1
parameters
V step
0.10 ml
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
30 mV
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
125
MET program for biamperometric titration
MET program for bivoltametric titration
pa
794 Titrino
01102
794.0010
date 2002-09-13
time 09:07
0
MET Upol
Thiosul2
parameters
V step
0.10 ml
titr.rate
max. ml/min
signal drift
50 A/min
equilibr.time
26 s
start V:
OFF
pause
0 s
U(pol)
200 mV
electrode test:
OFF
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop I
OFF A
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
2 A
EP recognition:
all
fix EP1 at I
OFF A
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
pa
794 Titrino
01102
794.0010
date 2002-09-13
time 09:09
0
MET Ipol
Thiosul3
parameters
V step
0.10 ml
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
I(pol)
1 A
electrode test:
OFF
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
30 mV
EP recognition:
all
fix EP1 at U
OFF mV
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------

Potentiometric titration
126
Bivoltametric titration
Biamperometric titration
With the biamperometric titration the true enpoint coincides

with the first breaking point (EP1). However, if the titrator
evaluates a potentiometric titration curve independently, additional, wrong endpoints can appear (EP2 and EP3 in the
example shown).
Calculation
1 mL c(I2) = 0.05 mol/L corresponds to 15.810 mg Na2S2O3
g/L Na2S2O3 = EP1 x C01 x C30 / C00
EP1
C00
C01
C30
=
=
=
=
mL iodine solution up to endpoint

sample size in mL
15.81
titer of iodine solution
127
II.4.6 Bromine index in petrochemical products

Learning topics
Non-aqueous redox titration.
Polarized electrodes.
Analysis of petrochemical products.
Electrophilic addition of bromine at
double bonds:
R CH = CH R + Br2
R CHBr CHBr R
Titrant:
bromide bromate solution
c = 0.00333 mol/L (0.02 N)
Solvent mixture consisting of:
714 mL glacial acetic acid
134 mL tetrachloromethane
or 1,1,1-trichloroethene
or 1-methyl-2-pyrrolidone
134 mL methanol
18 mL H2SO4 w(H2SO4) = 20%
Principles
Procedure
Bromium is added electrophilically at C=C

double bonds and becomes decolorized.
This reaction is regarded as being a specific
identification for olefines and is also know as
the Bayer Test.
When connecting the electrode please make

sure that the connector for the platinum electrode is plugged into the POL socket.
The bromine index or bromine number is

the amount of bromine consumed by 100 g
sample. Under cold conditions bromine reacts with numerous unsaturated compounds
in the petrochemical product. Instead of the
exact identification and quantification of the
individual olefines, the bromine consumption
is given as a cumulative parameter. This is
purely a characteristic number, with the bromine index being used for substances with a
low bromine consumption and given in mg
Br2/100g sample. In contrast, the bromine
number is determined for substances whose
bromine consumption lies in the range from
one to several g Br2 / 100 g sample.
Reaction equation
R CH = CH R + Br2 R CHBr
CHBr R
Exchange Unit
10 mL

electrode
6.0309.100
Temperature sensor Pt 1000
6.1110.100
Ice bath or thermostat
The sample size depends on the expected

bromine index. For a bromine index of approx. 100 the sample size is one gram. When
making up the solvent mixture the toxic and
not readily degradable chlorinated hydrocarbons should, if possible, be replaced by nonchlorinated products.
The sample is dissolved in 100 mL of the solvent mixture and cooled to 05 C in an ice
bath or with a thermostat. The mixture should
be thoroughly stirred with a magnetic stirrer
bar.
128
The following program is used for the titration:

pa
794 Titrino
01102
794.0010
date 2002-09-09
time 13:59
15
MET Ipol
Br index
parameters
V step
0.05 ml
titr.rate
max. ml/min
signal drift
OFF mV/min
equilibr.time
30 s
start V:
OFF
pause
60 s
I(pol)
1 A
electrode test:
OFF
temperature
14.1 C
>stop conditions
stop V:
abs.
stop V
50 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
>evaluation
EPC
EP recognition:
fix EP1 at U
>preselections
req.ident:
req.smpl size:
activate pulse:
------------
OFF
200 mV
all
OFF mV
Id1
all
OFF

Calculation
Bromine index (mg Br2 / 100
g) = EP1 x C01 x C02 / C00
EP1 = consumption of bromide/
bromate solution
c = 0.00333 mol/L
(0.02 N)
C00 = sample weight of petrol
C01 = 0.02 (normality of
bromide/bromate solution)
C02 = 7990

Measured value
Sample size (g)
Consumption of
titrant (mL)
BI engine oil
(mg Br2 / 100 g)
22.253
1.502
10.79
20.047
1.249
9.96
25.532
1.779
11.13
10.63
0.60
Srel %
5.66
129
II.4.7 Free sulfurous acid (SO2) in wine

Procedure
Learning topics
50 mL wine is pipetted into a beaker from

a volumetric pipet and approx. 1 g potassium iodide is added followed by 5 mL sulfuric acid w = 25% and a magnetic stirrer bar.
A separate double Pt-sheet electrode is used
for endpoint recognition; this continuously
measures the potential in the solution.
Analysis of foodstuffs.
Dilute solutions.
Polarized electrodes.
Principles
Sulfite (sulfurous acid) is added to wine for
two reasons:
to stop enzymatic sugar degradation (alcoholic fermentation)
as an antioxidant (protection against atmospheric oxygen)
Different countries permit different maximum
levels in wine. The majority of the SO2 is present in the wine in bound form. In order to determine the total SO2 the wine must first be saponified with NaOH. Sulfite is oxidized to sulfate by
iodine. The titration of sulfites with iodine solution is indicated by bivoltametric endpoint recognition with a double Pt-sheet electrode. The
potential is measured between two polarized
platinum sheets. As long as there is an excess
of free sulfite in the solution, the potential remains at approx. 300 mV. As soon as the sulfite
has been consumed and only iodine and sulfate or sulfuric acid are present in the solution,
the potential drops to approx. 0 mV.
Reaction equations
SO2 + H2O
H2SO3
H2SO3 + 2 H2O
SO32 + 2 H3O+
SO32 + I2 + H2O SO42 + 2 HI
pa
794 Titrino
01102
794.0010
date 2002-09-09
time 15:22
19
SET Ipol
SO2 wine
parameters
>SET1
EP at U
20 mV
dynamics
300 mV
max.rate
5 ml/min
min.rate
10 l/min
stop crit:
time
t(delay)
10 s
>SET2
EP at U
OFF mV
titr.direction:
auto
start V:
OFF
pause
20 s
I(pol)
1 A
electrode test:
OFF
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
filling rate
max. ml/min
>statistics
status:
OFF
>preselections
conditioning:
OFF
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
Calculation

Exchange Unit
electrode
The sample is titrated with the standard solution c(I2) = 1/128 mol/L using the following
program:
20 mL
6.0309.100

Iodide/iodate standard solution
c(I2) = 1/128 mol/L
Sulfuric acid
w = 25%
Potassium iodide analytical grade >99%
1 mL c(I2) = 1/128 mol/L corresponds to 0.50

mg SO2
mg/L SO2 = EP1 x C01 x C02 / C00
EP1
C00
C01
C02
=
=
=
=
mL iodine solution up to endpoint

0.5
1000 (for 1 liter)
130

Measured value
Sample size
wine (mL)
Consumption of
titrant (mL)
Free SO2 in
mg/L
50
2.115
21.15
50
2.134
21.34
50
2.199
21.99
50
2.177
21.77
50
2.130
21.30
50
2.252
22.52
21.68
0.52
Srel %
2.40
II.4.8 Oxygen content in water Winkler method

Learning topics

Exchange Unit
10 mL
Iodometry.

electrode
6.0309.100
Water analysis.
6.0451.100
Redox processes.
Principles
The Winkler method is an elegant method for
determining the oxygen content in water.
Manganese(II) chloride and NaOH solution
are added to the water sample. The oxygen
leads to the formation of Mn(III) hydroxide.
After being dissolved in acid, the Mn(III) is
reduced to Mn(II) in the presence of iodide
ions. At the same time an amount of iodine
that is equivalent to the oxygen is released
and can be titrated with thiosulfate.
Reaction equations
MnCl2 + 2 NaOH Mn(OH)2 + 2 NaCl
2 Mn(OH)2 + O2 + H2O 2 Mn(OH)3 +
2 H3O+
2 Mn(OH)3 + 6 HCl 2 MnCl3 + 6 H2O
2 MnCl3 + 2 KI 2 MnCl2 + 2 KCl + I2

Titrant
c(Na2S2O3) = 0.05 mol/L
Winkler I
400 g MnCl2 x 4 H2O is dissolved in dist.
H2O and made up to 1 liter
Winkler II
500 g NaOH, 1 g NaN3 et 150 potassium
iodide are dissolved in dist. H2O and made
up to 1 liter
Acid mixture
350
mL each of w(H3PO4) = 85% and w(HCl)
= 36% are mixed and made up to 1 liter
with dist. H2O
131
Procedure
The water sample is filled bubble-free into
the sample bottle, e.g. with a tube that fills
the bottle from below, with inclined stopper until it overflows and then sealed. After
removing the stopper, 2 mL each of Winkler
solution I (40% MnCl2 x 4 H2O) and Winkler
solution II (50% NaOH and 15% KI) are added just below the surface of the water, the
bottle is immediately sealed again and the
contents mixed. After deposition of the precipitate (several hours) approx. 1/3 of the supernatant water is carefully aspirated off, 10
mL acid mixture is added (conc. HCl / conc.
H3PO4 1:1), the bottle is then sealed and the
contents mixed. A magnetic stirrer bar is
added and the released iodine is titrated with
c(Na2S2O3) = 0.05 mol/L to SET Ipol (1 A,
separate double Pt-sheet electrode).
The iodine formed is titrated with c(Na2S2O3) = 0.05 mol/L according to the following SET or
MET programs:
MET titration
pa
794 Titrino
SET titration:
01102
794.0010
date 2002-09-12
time 16:26
MET Ipol
O2WiMET
parameters
V step
0.10 ml
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
I(pol)
1 A
electrode test:
OFF
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
12
794 Titrino
01102
794.0010
date 2002-09-12
time 16:27
12
SET Ipol
O2Winkl
parameters
>SET1
EP at U
240 mV
dynamics
220 mV
max.rate
5 ml/min
min.rate
10 l/min
stop crit:
time
t(delay)
10 s
>SET2
EP at U
OFF mV
titr.direction:
auto
start V:
OFF
pause
0 s
I(pol)
1 A
electrode test:
OFF
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
filling rate
max. ml/min
>statistics
status:
OFF
>preselections
conditioning:
OFF
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
EPC
30 mV
EP recognition:
all
fix EP1 at U
20 mV
fix EP2 at U
OFF mV
------------
132

Oxygen by Winkler method
with combined Pt-ring electrode MET method
Oxygen by Winkler method with separate double Ptsheet electrode SET method
Calculation
1 mL c(Na2S2O3) = 0.05 mol/L corresponds to 0.40 mg O2
mg/L O2 = EP1 x C01 x C02 x C30 / (C00 4)
EP1
C00
C01
C02
C30
4
= mL thiosulfate solution up to endpoint

= sample size/bottle contents in mL
= 0.4
= 1000 (for 1 liter)
= titer of thiosulfate solution
= mL Winkler solution I and II
133
Additional remarks
The oxygen absorption ability of water depends on three different factors:
Temperature: As the temperature increases, the oxygen absorption decreases.
Pressure: As the pressure increases, the oxygen absorption increases.
Salt content: As the salt content increases, the oxygen absorption decreases by approx.
0.554% per g/L salt (rule of thumb).
The following tables give an overview:
Air pressure as a function of the height above

sea level
101.325 kPa = 1 atm = 760 mm Hg
SL/m = height above sea level in meters,
kPa = mean air pressure in kilopascal
Oxygen solubility (oxygen saturation in mg/L

O2) as a function of the temperature and air
pressure
Te m p .
in C
111.5
kPa
101.3 91.2 kPa 81.1 kPa 70.9 kPa

kPa
(1.1 atm) (1.0 atm) (0.9 atm) (0.8 atm) (0.7 atm)
SL/m
kPa
SL/m
kPa
0.0
16.09
14.62
13.14
11.69
10.21
101.3
900
90.5
5.0
14.06
12.77
11.48
10.20
8.91
100
100.1
1000
89.4
10.0
12.43
11.29
10.15
9.00
7.86
200
98.8
1100
88.3
15.0
11.10
10.08
9.05
8.03
7.01
300
97.6
1200
87.2
20.0
10.02
9.09
8.14
7.23
6.30
400
96.4
1300
86.1
25.0
9.12
8.62
7.40
6.56
5.70
500
95.2
1400
85.0
30.0
8.35
7.56
6.76
5.99
5.19
600
94.0
1500
84.0
35.0
7.69
6.95
6.22
5.47
4.75
700
92.8
1600
82.9
800
91.7
1700
81.9
To be able to calculate the oxygen saturation

of a sample, the air pressure, the temperature (at the time the sample was taken) and
the salt content of the sample have to be taken into account.
134
II.4.9 Hydrogen peroxide (H2O2) in disinfectants with KMnO4

Procedure
Learning topics
Redox potential.
Redox pairs.
Relativity of oxidation / reducing
agents (redox amphotery).
Principles
Hydrogen peroxide is redox-amphoteric. It
oxidizes reducing agents such as the thiol
groups of hair proteins when applied for a
permanent wave and is itself reduced to water. However, strong oxidizing agents such as
permanganate oxidize it to oxygen.
In this case an aqueous solution of hydrogen
peroxide is titrated up to the first endpoint
with potassium permanganate standard solution in the presence of sulfuric acid. A combined Pt-ring electrode is used to detect the
endpoint.
Reaction equation
2 MnO4 + 5 H2O2 + 6 H3O+ 2 Mn2+ +
5 O2 + 14 H2O
Exchange Unit
10 mL
6.0451.100

Hydrogen peroxide solution
Sulfuric acid
concentrated, approx. 96%
Potassium permanganate
Ready-to-use titrant c = 0.02 mol/L (0.1 N)
Deionized water
75 mL of the sample solution is pipetted into

a beaker from a volumetric pipet. A magnetic stirrer bar is added and 5 mL concentrated sulfuric acid is carefully added under vigorous stirring. Care must be taken that the
solution does not become too hot. It is then
titrated with potassium permanganate solution up to the first endpoint according to the
following program:
pa
794 Titrino
01102
794.0010
date 2002-09-12
time 14:26
12
DET U
H2O2Des
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
135
Calculation
1 mL c(KMnO4) = 0.02 mol/L corresponds to 1.701 mg H2O2
% H2O2 = EP1 x C01 x C02 / C00
EP1
C00
C01
C02
=
=
=
=
mL permanganate up to endpoint
1.701
0.1 (for %)

Measured value
Sample size
H2O2 (mL)
Consumption of
KMnO4 (mL)
% H2O2
75.0
13.150
0.0298
75.0
13.159
0.0298
75.0
13.162
0.0299
75.0
13.055
0.0296
75.0
13.088
0.0297
0.0298
0.0001
Srel %
0.67
136
II.4.10 Diazotization titration with NaNO2

Procedure
Learning topic
Diazotization of primary amines,
analysis of drugs, nitrite titrations.
Principles
Primary amino groups can be diazotized by
nitrous acid in a solution of hydrochloric acid
whereby the diazonium salt is formed.
As nitrous acid is not stable, sodium nitrite is
used as the titrant. The acid used is normally HCl in order to accelerate the diazotization reaction, bromide ions can also be added (usually HBr as a catalyst). As NaNO2 and
hydrochloric acid immediately form (volatile)
HNO2, this means that vigorous stirring must
be applied during the titration and the solution cooled down to approx. 15 C.
Instructions according to this method can be
found, for example, in the USP for the determination of sulfonamides and other drugs.
Reaction equation
RNH2 + HNO2 + HCl [RN+N]Cl
+ 2 H2O
Exchange Unit
20 mL
6.0451.100

Titrant
c(NaNO2) = 0.1 mol/L
Hydrochloric acid
w(HCl) = 10%
Using sulfanilamide as an example

Approx. 0.140 g sample is weighed out
into the titration vessel and dissolved in 50
mL w(HCl) = 10%. The mixture is cooled
down to approx. 10 C and then titrated with
c(NaNO2) = 0.1 mol/L to after the first endpoint (combined Pt-ring electrode).
Parameters
pa
794 Titrino
01102
794.0010
date
2003-01-30
time 08:18
0
DET U
M 23
parameters
meas.pt.density
3
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
17.3 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
all
activate pulse:
OFF
------------
137
Calculation
1 mL c(NaNO2) = 0.1 mol/L corresponds to 17.22 mg
C6H8N2O2S
w = EP1 x C01 x C02 x C36 / C00;2;%
C00
C01
C02
C36
=
=
=
=
sample weight in mg
equivalent weight of titrated substance (17.22)
conversion factor to % (100)
titer of the NaNO2
Measured values
Measured value
Sample size
(mg)
Consumption of
NaNO2 (mL)
% Sulfanilamide
142.5
8.215
99.30
155.8
8.984
99.30
138
II.4.11 Bromatometry
Analytical use in the pharmaceutical sector
Learning topics
Bromate/bromium
agent.
as
oxidizing
Direct and indirect determination

methods.
Determination of drugs and metal
ions.

Bromates are strong oxidizing agents and
can be used under acidic conditions for the
direct determination of e.g. As(III), Sb(III),
Sn(II), Cu(I) and hydrazine. In an acidic solution the bromate is reduced to bromide:
BrO3 + 6 H3O + + 6 e Br + 9 H2O
The titration makes use of the fact that bromate comproportionates with bromide to
form elemental bromine.
BrO + 5 Br + 6 H3O
9 H2O + 3 Br2
Under acidic conditions an excess of bromate is added to the dissolved substance,

which is oxidized. The excess bromate is allowed to react with potassium iodide and the
iodine formed is titrated with thiosulfate.
A large number of indirect determinations is
possible. Examples from the pharmaceutical
sector and determinations of metal ions are
mentioned below.
Preparation of the titrant c(1/6 KBrO3) =
0.1 mol/L
KBrO3 is available in very pure form as a
standard titrimetric substance. It is dried in a
drying oven for two to three hours at 180 C
and allowed to cool down in a desiccator for
at least 2 h.
2.7833 g KBrO3 is weighed out into a 1000
mL volumetric flask, dissolved in dist. H2O,
made up to the mark and mixed. The solution is very stable and also has a stable titer,
but must not contain any bromide ions!
A suitable amount of substance is weighed

out into an Erlenmeyer flask and dissolved in
dist. H2O. It is treated with an excess of c(1/6
KBrO3) = 0.1 mol/L, KBr and acid are added
and the flask is then sealed and the contents
mixed. After a reaction time of 15 min the potassium iodide is added and the released iodine is titrated with c(Na2S2O3) = 0.1 mol/L
(Pt Titrode).
Titrant c(Na2S2O3) = 0.1 mol/L
According to the Pharm. Europe and the
USP the content of the following substances can be determined by this method: chlorocresol, cysteine, hexylresorcinol, hydroxyethylsalicylate, parachlorophenol, phenol,
phenylephrine hydrochloride and resorcinol.
Determination of metal ions
The method is based on the fact that numerous metal ions under suitable pH conditions
can be precipitated as oxinate complexes by
8-hydroxyquinoline (bivalent metal ions bind
two, trivalent metal ions bind three oxine ligands).
The precipitate formed is filtered through
a glass filter crucible and rinsed with warm
water. A dilute solution of hydrochloric acid
is then added. This releases oxine, which is
converted to 5,7-dibromo-8-hydroxyquinoline with Br2.
This is done by adding an excess of c(KBrO3)
= 0.1 mol/L and some KBr solution and allowing the reaction to take place for 5 min in
a sealed Erlenmeyer flask. After the addition
of potassium iodide solution the released iodine is titrated with c(Na2S2O3) = 0.1 mol/L
(Pt Titrode).
Literature reference
Jander/Jahr
Massanalyse (titrimetric analisis)
Walter de Gruiter, Berlin 1989
ISBN 3-11-011975-7
139
Calculation
Procedure
1 mol oxine corresponds to 2 mol Br2 (or 4

mol Br). KBrO3 and KBr together produce 3
mol Br2 from 1 mol KBrO3. 1 equivalent of a
bivalent metal ion corresponds to 8 equivalents of bromine; a trivalent metal ion to 12
equivalents of bromine. Or:
Approx. 0.7 g sample is weighed out into a

500 mL volumetric flask, dissolved in dist. H2O,
made up to the mark and mixed.
1 mL c(1/6 KBrO3) = 0.1 mol/L corresponds

to, e.g.:
0.22485 mg Al
1.4050 mg Cd
0.73667 mg Co
0.7943 mg Cu
0.46539 mg Fe
0.30381 mg Mg
0.68673 mg Mn
0.733 mg Ni
1.9836 mg U and
081713 mg Zn
25.0 mL (1/20 of the sample weight) is pipetted

into an Erlenmeyer flask, 25.00 mL c(KBrO3) =
1/60 mol/L and 5 mL w(HCl) = 35% are added
and the flask is immediately sealed. It is swirled
around for 1 min and then allowed to stand for
2 min. 10 mL w(KI) = 10% is added, the flask is
sealed again and thoroughly mixed. The flask
walls and stopper are rinsed with dist. H2O and
the contents are titrated with c(Na2S2O3) = 0.1
mol/L to after the first endpoint. A blank containing 25.00 mL c(KBrO3) = 1/60 mol/L is
treated in the same manner as the sample.
Parameters
Example: determination of resorcinol

Exchange Unit
20 mL
Pt Titrode
6.0431.100

Reaction solution
c(KBrO3) = 1/60 mol/L
Hydrochloric acid solution
w(HCl) = 35%
Potassium iodide solution
w(KI) = 10%
Titrant
c(Na2S2O3) = 0.1 mol/L
pa
794 Titrino
01102
794.0010
date 2003-01-30
time 09:06
0
DET U
M 25
parameters
meas.pt.density
2
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
30 mV/min
equilibr.time
32 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
40.8 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
all
activate pulse:
OFF
------------
Calculation
w = (C33 EP1) x C01 x C02 / C00;2;%

C00
C01
C02
C33
= sample weight in mg
= equivalent weight of the titrated substance (1.835)
= conversion factor to % (100)
= blank value
140
Measured values
Measured value
Sample size
resorcinol (mg)
Consumption
(C33 EP1) mL)
% Resorcinol
36.2
19.234
97.50
36.2
19.307
97.87
141
II.5 Complexometry / Chelometry methods

II.5.1 Titer determination of c(Na2EDTA) = 0.1 mol/L with CaCO3
Procedure
Learning topics
Complex formation.
Indication methods.
Principle
CaCO3 is suitable for use as the standard titrimetric substance for determining the titer
of Na EDTA solutions.
CaCO3 is dried overnight in a drying oven at

140 C and allowed to cool down in a desiccator for at least 2 h.
Approx. 100 mg CaCO3 is weighed out accurately to 0.1 mg into a titration beaker and
suspended in approx. 20 mL dist. H2O. Under stirring c(HCl) = 5 mol/L is added drop
by drop until everything has dissolved. After
the addition of approx. 30 mL dist. H2O, 5 mL
buffer solution pH = 10 and 1 mL auxiliary solution, the mixture is titrated with c(Na2EDTA)
= 0.1 mol/L to after the first endpoint.
Ca2+ + Na2EDTA CaEDTA + 2 Na+
Care must be taken that the temperature remains constant during the titration. The titer
determination is normally carried out three
times and the mean value is used.
Parameters
Reaction equation
Exchange Unit
20 mL
Cu ISE
6.0502.140
6.0726.107

Titrant
c(Na2EDTA) = 0.1 mol/L
Auxiliary solution
c(Cu(NH4)2EDTA) = 0.1 mol/L
Buffer solution
NH3/NH4Cl, pH = 10
c(HCl) = 5 mol/L
Standard titrimetric substance
CaCO3
pa
794 Titrino
01102
794.0010
date 2003-01-29
time 08:47
12
DET U
Me5
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
30 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
OFF
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
greatest
up lim.1 U
2000 mV
low lim.2 U
OFF mV
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
all
activate pulse:
OFF
------------
142
Calculation
Titer = C00 / C01 / EP1;4
EP1 = mL Na2EDTA up to endpoint
C00 = weight of CaCO3 in mg
C01 = equivalent weight of the titrated substance (10.009)

Measured value
Sample size
CaCO3 (mg)
Consumption of
Na2EDTA (mL)
Titer
100.7
9.877
1.0186
104.8
10.302
1.0164
102.5
10.067
1.0173
103.7
10.195
1.0163
99.8
9.815
1.0159
105.6
10.352
1.0191
104.2
10.225
1.0182
103.8
10.206
1.0163
100.9
9.913
1.0169
10
100.7
9.898
1.0184
1.0173
0.0011
Srel %
0.11
143
II.5.2 Ca and sulfate content in tap water with the Ca ISE

Procedure
Learning topics
Solubility product.
Selectivity.
Titration curve.
Principles
The following instructions describe an elegant method that allows the sulfate and
calcium content of water to be determined
in one run. In the acidified sample (so that
carbonate does not interfere) the sulfate is
treated with an excess of barium chloride
and precipitated as barium sulfate. After alkaline buffering the (unprecipitated) excess
barium is back-titrated with EGTA. Two endpoints are found. EP1 corresponds to the Ca
and the difference EP2 EP1 to the Ba (Mg
does not interfere as EGTA only forms weak
complexes with it).
Reaction equations
Ba2+ + SO42+ {BaSO4}
Excess BaCl2:
Ba2+ + Na2H2EGTA + 2 H2O Na2BaEGTA
+ 2 H3O+
Exchange Unit
20 mL
Ca ISE
6.0508.110
6.0726.107

Titrant
c(EGTA) = 0.05 mol/L
Barium chloride solution
c(BaCl2) = 0.05 mol/L in c(HCl) = 0.001
mol/L
Buffer solution
NH3/NH4Cl, pH = 10
c(HCl) = 2 mol/L
If necessary, the sample solution is adjusted to pH <4 with HCl and treated with 5 mL
c(BaCl2) = 0.05 mol/L. The reaction is allowed to take place for 3 min under stirring.
Then 5 mL buffer solution pH = 10 is added,
allowed to react for a further 30 s and then titrated with EGTA, c(EGTA) = 0.05 mol/L.
Two equivalence points are obtained, the first
one corresponding to the Ca2+ content and
the difference between the second and the
first equivalence point to the excess Ba2+.
By using a blank sample (without sulfate),
which is prepared and titrated in the same
way, the titrant consumption for the added
amount of c(BaCl2) = 0.05 mol/L is first determined. This blank value is stored in the titrator as common variable C30.
Parameters
pa
794 Titrino
01102
794.0010
date 2003-01-29
time 10:40
0
MET U
Sulfate
parameters
V step
0.10 ml
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
25 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5 mV
EP recognition:
window
low lim.1 U
-50 mV
up lim.1 U
0 mV
low lim.2 U
-100 mV
up lim.2 U
-75 mV
low lim.3 U
OFF mV
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
144
Calculation
1 mL c(EGTA) = 0.05 mol/L corresponds to 2.004 mg Ca or
4.803 mg SO4
Ca
= EP1 x C01 x C02 / C00;2;mg/L
RS2
= EP2EP1;2;mL
SO4
C00
C01
C02
C03
C30
= (C30 RS2) x C03 xC02 / C00;2;mg/L

=
=
=
=
=
sample size in mL
2.004 for Ca
1000 (conversion factor mL/L)
4.803 for sulfate
blank consumption in mL
Measured values
Measured
value
Sample
size water
(mL)
EP1 (mL)
EP2 (mL)
(Ca)
(mg/L)
(SO4)
(mg/L)
50.0
1.999
6.684
80.12
30.26
50.0
1.990
6.675
79.76
30.26
145
II.5.3 Ca and Mg content (total hardness) in water with the Ca ISE

Learning topics
Ca ISE. Response behavior and selectivity.
Recomplexing/auxiliary complexing
agents.
Titrant
c(Na2EDTA) = 0.05 mol/L in
c(KOH) = 0.1 mol/L
Titration curve.
Auxiliary complexing agent

c(acetylacetone) = 0.1 mol/L in
c(Tris) = 0.2 mol/L
Water analysis.
Procedure
Principles
The chief hardness formers in water are Ca
and Mg salts. The more calcium and/or magnesium dissolved in the water, the harder it
is. Objects that remain in contact with hard
water for a long time frequently acquire a
scale deposit made up of the precipitated
salts of these metals. Higher fatty acids form
precipitates that are insoluble in water with
these metals; these can also be found on the
walls of baths.
The sum of the two alkaline earth ions in
mmol/L corresponds to the total hardness
(see also II.5.4. and II.5.5.). In this experiment calcium and magnesium are determined separately in a complexometric titration. In order to obtain a better differentiation
between the Ca and Mg jumps in the titration curve, an auxiliary complexing agent is
added, this also masks interfering Fe3+ and
Al3+.
Reaction equation
Mg2+ + Ca2+ + 2 Na2H2EDTA + 4 H2O
Na2MgEDTA + Na2CaEDTA + 4 H3O+
Exchange Unit
20 mL
Ca ISE
6.0508.110
6.0726.107
100 mL sample is placed in the titration beaker. 15 mL auxiliary complexing agent solution is then added and, after a short waiting
period, the solution is titrated with Na2EDTA
using the Ca ISE. The first equivalence point
corresponds to the Ca2+ content, the difference between the second and first equivalence point to the Mg2+ content.
pa
794 Titrino
01102
794.0010
date 2003-01-28
time 10:50
0
DET U
Ca/Mg
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
30
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------
146
Calculation
1 mL c(Na2EDTA) = 0.05 mol/L corresponds to 2.004 mg Ca
or 1.216 mg Mg
Ca = EP1 x C01 x C02 / C00;2;mg/L
Mg = (EP2 EP1) x C03 x C02 / C00;2;mg/L
C00
C01
C02
C03
=
=
=
=

2.004 for Ca
1000 (conversion factor in mL/L)
1.216 for Mg

Measured
value
EP1
(mL)
EP2
(mL)
c(Ca)
mmol/L
(Ca)
mg/L
c(Mg)
mmol/L
(Mg)
mg/L
2.151
2.903
2.151
86.21
0.752
18.28
2.150
2.882
2.150
86.17
0.732
17.80
2.148
2.871
2.148
86.09
0.723
17.58
2.155
2.901
2.155
86.37
0.746
18.14
2.150
2.890
2.150
86.17
0.740
17.99
2.199
2.925
2.199
88.14
0.726
17.65
2.153
2.883
2.153
86.29
0.730
17.75
2.153
2.923
2.153
86.29
0.770
18.72
2.149
2.874
2.149
86.13
0.725
17.63
10
2.152
2.884
2.152
86.25
0.732
17.80
2.156
86.41
0.738
17.93
0.015
0.61
0.015
0.36
Srel %
0.70
0.71
2.00
2.07
147
II.5.4 Total hardness in drinking water with the Ca ISE

Learning topics
Recomplexing.
ISE.
Selectivity.
Calculation of water hardness.
Principles (see also II.1.10 and II.5.3)
The total hardness of a water is given in
mmol alkaline earth ions/L and replaces the
different and confusing units such as German, French, USA hardness degrees, etc.
The knowledge of the water hardness plays
a great role in the daily use of water; for example in adding the right amount of washing
powder to washing machines, water softening (hot water production), etc. Coarse divisions into different types of water are made:
soft, medium-hard, hard and very hard water:
Alkaline earth ion content Water type
in mmol/L
Below 1.3
soft
1,32,5
medium-hard
2,53,8
hard
Above 3.8
very hard
Soft waters can be expected in sources in

granite areas, medium-hard water in lakes
and hard waters in areas with a predominantly limestone-containing subsurface.
The titration curve shows two equivalence
points; the first equivalence point corresponds to the Ca2+ content, the difference
between the second and first equivalence
point to the Mg2+ content.
Reaction equations
Frequently, the anion ETDA is shortened with
Y; the equations then present themselves as
follows:
1. Ca2+ + H2Y2 + 2 H2O CaY2 + 2 H3O+
2. Mg2+ + H2Y2 + 2 H2O MgY2 + 2 H3O+
Exchange Unit
20 mL
Ca ISE
6.0508.110
6.0726.107

Titrant
Auxiliary complexing agent
c(acetylacetone) = 0.1 mol/L in
c(Tris) = 0.2 mol/L
Procedure
100 mL water is pipetted into each of 10 beakers (150 mL). 15 mL auxiliary complexing
solution is added and, after a waiting period
of approx. 5 min, the solution is titrated with
c(Na2EDTA) = 0.1 mol/L.
parameters:
DET U
parameters
meas.pt.density
min.incr.
titr.rate
signal drift
equilibr.time
start V:
pause
meas.input:
temperature
>stop conditions
stop V:
stop V
stop U
stop EP
filling rate
>statistics
status:
>evaluation
EPC
EP recognition:
fix EP1 at U
pK/HNP:
>preselections
req.ident:
req.smpl size:
activate pulse:
------------
1
10.0
max.
20
38
OFF
0
1
25.0
l
ml/min
mV/min
s
s
C
abs.
5 ml
OFF mV
9
max. ml/min
OFF
5
all
OFF mV
OFF
OFF
OFF
OFF
148

Calculations of hardness
To obtain the total hardness
and the concentrations of
the calcium and magnesium
ions, the following formulas
Calcium =
EP1 x C01 x C02 /
C00;2;mmol/L
Magnesium =
(EP2 EP1) x C01 x C02 /
C00;2;mmol/L
TH =
EP2 xC01 x
C00;2;mmol/L
C02

endpoint [mL]
EP2 = added volume up to second
endpoint [ [mL]
C00 = sample size (100) [mL]
C01 = correction factor (1000) []
C02 = concentration of EDTA solution (0.1) [mol/L]
The total hardness is given in mmol/
L, with 0.1 mmol Ca/Mg corresponding to 4.008 mg Ca or 2.431
mg Mg. The total hardness should
be given to two decimal places.

Measured
value
EP1 (mL)
EP2 (mL)
c(Ca)
mmol/L
c(Mg)
mmol/L
c(TH)
mmol/L
2.1806
2.9472
2.181
0.766
2.947
2.1748
2.9414
2.175
0.766
2.941
2.1715
2.9386
2.172
0.767
2.939
2.1757
2.9386
2.176
0.763
2.939
2.1758
2.9358
2.176
0.760
2.936
2.1761
2.9439
2.176
0.768
2.944
2.1642
2.9383
2.164
0.774
2.938
2.1693
2.9431
2.169
0.774
2.943
2.1760
2.9343
2.176
0.758
2.934
10
2.1759
2.9394
2.176
0.763
2.939
2.174
0.766
2.940
0.005
0.005
0.004
Srel %
0.22
0.65
0.13

In order to obtain reliable results we recommend that you
always prepare only the beaker that is to be titrated immediately. Care should also be taken that no air bubbles are
entrained. Ca electrodes that have been stored dry are conditioned for 10 min in c(CaCl2) = 0.01 mol/L before the titration.
149
II.5.5 Total hardness in drinking water with the Spectrosense 610 nm

Procedure
Learning topics
Colored indicators; photometric titration.
Complex formation, recomplexing.
Color change.
pH dependency.
Titration curve.
Determining the total hardness of
drinking water
Principles
As the complex formation constants of EDTA
are very small in acidic or neutral solution,
the solution must be buffered to pH = 10
during the whole titration. The indicator used
for the titration is eriochrome black T, the
color change of the indicator is determined
photometrically using the Metrohm Spectrosense 610 nm.
Reaction equations
1. Ca2+ + H2Y2 (EDTA) + 2 H2O CaY2 +
2 H3O+
2. Mg2+ + H2Y2 (EDTA) + 2 H2O MgY2 +
2 H3O+
Exchange Unit
20 mL
Spectrosense 610 nm
6.1109.110

Titrant
Buffer solution
NH3/NH4Cl, pH = 10
Indicator solution
w(eriochrome black T) = 0.1%
Auxiliary reagent
magnesium complexonate (MgEDTA)
100 mL water is pipetted into each of 10

glass beakers (150 mL). Approx. 0.1 g
MgEDTA and 10 mL buffer solution are added. The solution is then treated with 0.5 mL
eriochrome black indicator and titrated with
c(Na2EDTA) = 0.1 mol/L. Correct results will
only be obtained if the Spectrosense 610 nm
is allowed to warm up for approx. 15 min before the titration.
parameters:
MET U
parameters
V step
titr.rate
signal drift
equilibr.time
start V:
pause
meas.input:
temperature
>stop conditions
stop V:
stop V
stop U
stop EP
filling rate
>statistics
status:
>evaluation
EPC
EP recognition:
fix EP1 at U
pK/HNP:
>preselections
req.ident:
req.smpl size:
activate pulse:
------------
0.10
max.
50
26
OFF
0
1
25.0
ml
ml/min
mV/min
s
s
C
abs.
5 ml
OFF mV
9
max. ml/min
OFF
30 mV
all
OFF mV
OFF
OFF
OFF
OFF
150

Calculation
In order to obtain the total
hardness, the following formula must be entered in the
instrument:
TH = EP1 x C01 x C02 /
C00;2;mmol/L
EP1 = added volume up to equivalence point [mL]
C00 = water sample size (100)
[mL]
C01 = correction factor (1000) []
C02 = concentration of EDTA solution (0.1) [mol/L]
The total hardness is given in
mmol/L, with 0.1 mmol Ca/Mg
corresponding to 4.008 mg Ca
or 2.4305 mg Mg. The total hardness should be given to two decimal places.

Measured value
Sample size
water (mL)
Consumption of
Na2EDTA (mL)
c(TH) mmol/L
100.0
3.000
3.000
100.0
2.998
2.998
100.0
2.998
2.998
100.0
2.997
2.997
100.0
2.999
2.999
100.0
2.999
2.999
100.0
2.999
2.999
100.0
2.997
2.997
100.0
2.999
2.999
10
100.0
2.997
2.997
2.998
0.001
Srel %
0.04

In order to obtain good results we recommend that you always prepare only that beaker which is to be titrated immediately. Care should also be taken that no air bubbles are
entrained and that no air bubbles adhere to the mirror of the
Spectrosense, as these could affect the measurement.
151
II.5.6 Nickel in a nickel electroplating bath with the Cu ISE

Procedure
Learning topics
Approx. 50 mL dist. H2O and 1.00 mL bath

sample are placed in a glass beaker. After
the addition of 1 mL auxiliary solution and 10
mL buffer solution the titration is carried out
with c(Na2EDTA) = 0.1 mol/L to after the first
endpoint.
Recomplexing.
Selectivity.
Analysis of metals.
Parameters
Principles
In certain cases, ion-selective electrodes are
suitable for the indication of the titration process. In this example, a Cu-selective electrode is used (see also under II.5.2).
The main constituent of nickel-plating baths
is, of course, nickel. This metal has to be monitored; its content is normally in the region of
70 g/L Ni. The starting substances used are
normally sulfates or sulfamates (salts of amidosulfonic acid). Depending on whether the
baths are matt or bright nickel baths, various
additives are used to ensure optimal nickel
deposition. In matt nickel baths these could
include boric acid, ammonium and Mg(II), in
bright nickel baths cobalt, formate, formaldehyde, sulfonic acid, saccharin, etc.
Reaction equation
CuEDTA + Ni(II) NiEDTA + Cu(II)
Exchange Unit
20 mL
Cu ISE
6.0502.140
6.0726.107

Titrant
Auxiliary solution
c(Cu(NH4)2EDTA) = 0.1 mol/L
Buffer solution
NH3/NH4Cl, pH = 10
pa
794 Titrino
01102
794.0010
date 2003-01-28
time 11:25
0
DET U
Me13
parameters
meas.pt.density
4
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
OFF
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5 mV
EP recognition:
greatest
up lim.1 U
2000 mV
low lim.2 U
OFF mV
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
all
activate pulse:
OFF
------------
152
Calculation
1 mL c(Na2EDTA) = 0.1 mol/L corresponds to 5.869 mg Ni
Ni = EP1 x C01 x C34 / C00;2;g/L
C00 = sample size in mL (100)
C01 = equivalent weight of Ni (5.869)
C34 = titer of the Na2EDTA solution
Measured values
Measured value
Sample size
Ni bath (mL)
Consumption of
Na2EDTA (mL)
g/L Ni
1.00
13.038
76.52
1.00
12.995
76.27
153
II.5.7 Calcium in milk with the Cu ISE

Procedure
Learning topics
Ca bonding forms.
Food analysis.
Principles
In addition to water, dairy products are one
of the main sources of calcium in human nutrition. Their calcium is easily taken up by
the human body. Calcium supply plays a
key role in preventing symptoms of malnutrition (keyword: osteoporosis particularly
in women, but recently also more frequent
in men). Calcium in milk is only partly in an
ionogenic state. The majority is present in
bound form, but can be complexed by EGTA
in alkaline solution. With EGTA, calcium(II)
can be selectively determined in the presence of Mg(II) (Mg only forms weak complexes with EGTA).
Reaction equation
CuEGTA + Ca2+ CaEGTA + Cu2+
Exchange Unit
20 mL
Cu ISE
6.0502.140
6.0726.107

Titrant
c(EGTA) = 0.1 mol/L
Auxiliary solution
c(Cu(NH4)2EGTA) = 0.1 mol/L
Buffer solution
NH3/NH4Cl, pH = 10
Approx. 10 g sample is weighed out exactly

into a glass beaker and diluted with approx.
90 mL dist. water. The prepared sample is
treated with 1 mL CuEGTA solution and 10
mL buffer solution pH = 10. It is allowed to
react under stirring for 10 to 30 s and then titrated with c(EGTA) = 0.1 mol/L to after the
first endpoint.
Parameters
pa
794 Titrino
01102
794.0010
date 2003-01-29
time 09:58
0
DET U
Milk
parameters
meas.pt.density
1
min.incr.
10.0 l
titr.rate
max. ml/min
signal drift
OFF mV/min
equilibr.time
5 s
start V:
OFF
pause
20 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
5 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
5
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
all
activate pulse:
OFF
------------
154
Calculation
1 mL c(EGTA) = 0.1 mol/L corresponds to 4.008 mg Ca
Calcium = EP1 x C01 x C02 / C00;3;%
EP1
C00
C01
C02
=
=
=
=
mL EGTA up to endpoint
sample size in g
4.008 for Ca
0.1 (conversion factor to %)
Measured values
Measured value
Sample size
milk (g)
Consumption of
EGTA (mL)
% Ca
11.565
9.218
0.319
10.020
7.997
0.320
155
II.5.8 Aluminum in stomach tablets (antacids) with the Spectrosense 610 nm

Procedure
Learning topics
Complex formation.
pH dependency of complex formation.
Principles
Hyperacidity (HCl) can cause gastric disorders (heartburn) that may also affect the
esophagus. So-called antacids are taken
to alleviate these disorders. They neutralize
the acid, but are not a cure and only provide short-term relief. Previously NaHCO3
was mainly used. It only helps very briefly,
as it stimulates acid production. Modern antacids contain, among other things, MgCO3,
CaCO3, Al(OH)3 and/or silicates of these cations. Here we are titrating Al(III) with EDTA.
At room temperature aluminum only forms
the complex very slowly. This is why an excess of EDTA is added, the solution heated and, after the reaction, the excess EDTA
back-titrated with ZnSO4.
Reaction equation
Al3+ + Na2H2EDTA NaAlEDTA + 2 H3O+
Exchange Unit
20 mL
Spectrosense 610 nm
6.1109.110

Titrant I
Titrant II
c(ZnSO4) = 0.1 mol/L
Buffer solution
acetate buffer, pH = 4.7
Hydrochloric acid
w(HCl) = 25%
Indicator solution
dithizone, 25.6 mg / 100 mL ethanol
Alcohol
ethanol, analytical grade
20 tablets are weighed out and pulverized.

A portion of sample containing approx. 2 g
Al(OH)3 is weighed out into a beaker. 20 mL
dist. H2O and, under stirring, 15 mL w(HCl)
= 25% are added. The mixture is carefully
heated until all the Al(OH)3 has dissolved. After cooling down the solution is filtered into
a 200 mL volumetric flask, the filter is rinsed
with dist. H2O and the solution is then made
up to the mark and mixed. A 10.00 mL aliquot
is pipetted into the titration beaker, 20.00 mL
c(Na2EDTA) = 0.1 mol/L and 20 mL acetate
buffer are added, heated and boiled for 5
min. After cooling down, 50 mL ethanol and
2 mL dithizone indicator are added and titrated with c(ZnSO4) = 0.1 mol/L to after the
first endpoint. A blank containing 20.00 mL
c(Na2EDTA) = 0.1 mol/L is also titrated.
Parameters
pa
794 Titrino
01102
794.0010
Date 2003-01-30
time 11:51
0
MET U
M 33.2
parameters
V step
0.1 ml
titr.rate
max. ml/min
signal drift
50 mV/min
equilibr.time
26 s
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
20 ml
stop U
OFF mV
stop EP
9
filling rate
max. ml/min
>statistics
status:
OFF
>evaluation
EPC
10 mV
EP recognition:
all
fix EP1 at U
OFF mV
pK/HNP:
OFF
>preselections
req.ident:
OFF
req.smpl size:
all
activate pulse:
OFF
------------
156
Calculation
1 mL c(Na2EDTA) = 0.1 mol/L corresponds to 7.80 mg
Al(OH)3
Al(OH)3 = (C33 EP1) x C01 / (C00 x C02);2;%
EP1
C00
C01
C02
C33
=
=
=
=
=
mL ZnSO4 up to endpoint
sample size
7.8 for Al
10 (conversion factor)
blank value (mL ZnSO4 used in the back-titration)
Measured values
Measured value
Sample size
tablets (mg)
Consumption of
Na2EDTA (mL)
% Al(OH)3
906.6
16.667
14.34
906.6
16.668
14.34
157
II.5.9 Iron in cement with the Spectrosense 610 nm

Nitric acid
w(HNO3) = 32.5%
Learning topics
Complex formation.
pH dependency of complex formation.
Colored indicators.
Principles
Cements are finely ground hydraulic binders
which, on absorbing water, harden like stone
and are water-resistant when they have hardened. They consist mainly of Ca silicates, Ca
aluminates and Ca ferrites. They are made
of mixtures of raw materials (limestone, clay,
marl) by heating them (at approx. 1500 C),
usually in revolving cylindrical furnaces, to
form the so-called clinkers. Depending on
the application, other constituents may be
added (aggregates), these then determine
the most important properties of the cement (time taken for setting and hardening,
strength, chemical resistance, etc.). Example
of composition:
Tricalcium silicate
4080%
Dicalcium silicate
030%
Tricalcium aluminate
715%
Calcium-aluminate ferrite
415%
Reaction equation
Fe3+ + Na2H2EDTA + 2 H2O NaFeEDTA
+ 2 H3O+ + Na+
Exchange Unit 20 mL
6.1109.110

Titrant
Hydrochloric acid
w(HCl) = 36%
Indicator solution
w(sulfosalicylic acid) = 4% in dist. H2O
Procedure
Specificity.
Spectrosense 610 nm
Ammonia solution
w(NH3) = 25%
Approx. 1 g cement is mixed with 1.5 g NH4Cl

and treated with 8 mL HCl and 0.5 mL HNO3.
The mixture is boiled and stirred occasionally with a glass rod. After the addition of 50
mL hot water the mixture is filtered through
a black ribbon filter into a 500 mL volumetric flask and the filter thoroughly rinsed with
hot water. The combined filtrate is allowed to
cool down and then made up to the mark
with dist. water.
25 mL sample solution is diluted to 50 mL
with 25 mL dist. water. 1 g ammonium chloride and 20 drops of the indicator solution
are added and the mixture is heated to boiling. Ammonia is used to adjust the pH to
1.5...2.0 and the solution is then diluted to
150 mL with dist. water. This solution is then
titrated with c(Na2EDTA) = 0.1 mol/L until the
color changes from red-violet to colorless/
slightly yellow.
158
Parameters
pa
794 Titrino
01102
794.0010
Date 2003-01-29
time 11:44
0
SET U
Cement
parameters
>SET1
EP at U
400 mV
dynamics
150 mV
max.rate
10.0 ml/min
min.rate
25.0 l/min
stop crit:
drift
stop drift
20 l/min
>SET2
EP at U
OFF mV
titr.direction
auto
start V:
OFF
pause
0 s
meas.input:
1
temperature
25.0 C
>stop conditions
stop V:
abs.
stop V
10 ml
filling rate
max. ml/min >statistics
status:
OFF
>preselections
conditioning:
OFF
req.ident:
OFF
req.smpl size:
OFF
activate pulse:
OFF
------------

Calculation
1 mL c(Na2EDTA) = 0.1 mol/
L corresponds to 7.985 mg
Fe2O3
Fe2O3 = EP1 x C01 x C02 /
(C03 x C00 x C04);2;%
EP1 = mL Na2EDTA up to endpoint
C00 = weight of cement in g
(1.1026)
C01 = 7.8985 for Fe2O3
C02 = volume of whole sample solution (500)
C03 = sample volume (25)
C04 = 10 (conversion factor to %)
Measured values
Measured value
Sample size
cement (mg)
Consumption of
Na2EDTA (mL)
% Fe2O3
55.0
0.304
4.41
55.0
0.302
4.38
159
III. Appendix
Further and/or cited literature
Metrohm Application Bulletins, Application Notes and Monographs can be obtained free
of charge from your local Metrohm agency). Much information can also be found on the
Metrohm Internet page
www.metrohm.com
1.
Bruttel, P.
Non-aqueous titration of acids

and bases with potentiometric
endpoint indication
Metrohm monograph
50243 04.1999
2.
Derek Cooper,
Chris Doran,
Analytical Chemistry by Open

Learning.
Classical Methods Vol. 1.
John Wiley & Sons. Chichester 1987
3.
Metrohm
FOOD PAC
The know-how package for the
titrimetric/potentiometric determination of foodstuffs
Metrohm no. 6.6055.003
4.
Fritz, J.S.,
Schenk G.H.
Quantitative Analytische Chemie.

Translation from the American by
Ingo Lderwald and Leo Gros
Vieweg Verlag, Wiesbaden,

1989
pH Measurement. Fundamentals,
Methods, Applications, Instrumentation
VCH Weinheim, 1991
5.
Galster, H.
ISBN 3-528-08484-7
ISBN 3-527-28237-8
6.
Thomas Gassner
Systematische Untersuchungen
zur Genauigkeit von Titrationen
Metrohm monograph in
German 50021 - 1979
7.
Harris, D.C.
Lehrbuch der Quantitativen Analyse
Vieweg-Verlag, Wiesbaden
1997,
8.
Huber, W.
Titrationen in nichtwssrigen Lsungen
Akademische Verlagsgesellschaft, Frankfurt a.M.

(1964)
9.
Kunze, U.R. /
Schwedt, G.
Grundlagen der qualitativen und

quantitativen Analyse
Wiley-VCH, Weinheim 2002

ISBN 3-527-30858-X
ISBN 3-528-06756-X
10. MERCK
Die Untersuchung von Wasser
11. Metrohm
Application Bulletins
Please ask the table of contents
12. Metrohm
Ti Application Notes
Please ask the table of contents
13. Metrohm
OIL PAC
The know-how package for the determination of petrochemical products
160
14. Metrohm
PHARM PAC
The know-how package for the
titrimetric/potentiometric determination of pharmaceutical ingredients
15. Metrohm
PLATE PAC
The know-how package for the titrimetric/ potentiometric analysis of
electroplating baths
16. Richter, W.,

Tinner, U.
La technique des titrages
Metrohm monograph in
French 8.016 5002
17. Schulz, R.
Titrimetric determination of surfactants and pharmaceuticals.

Modern methods for analytical
practice
Metrohm monograph 1999

52243
18. Georg Schwedt
Analytische Chemie. Grundlagen,

Methoden und Praxis
Thieme Verlag Stuttgart

1995
19. Metrohm
SURF PAC
The know-how package for the titrimetric/ potentiometric determination of surfactants
20. Tinner, U.
Electrodes in Potentiometry
Metrohm monograph
8.015.5003
21. Julian Tyson
Analysis
What Analytical Chemists Do.
Royal Society of Chemistry

Paperbacks. London 1988
22. Valcrcel, M.
Principles of Analytical Chemistry Springer, Berlin, Heidelberg

2000 ISBN 3-540-64007-X
23. Metrohm
WINE PAC
The know-how package for the titrimetric/ potentiometric analysis of
wine and must
Standardized methods
Metrohm always attempts to meet the requirements of company-specific, national and international standards with its instruments and large range of accessories. To a considerable extent we have been successful in this and our customers can be sure that they have purchased
the correct instrument/correct accessories for working in accordance with such standards.
From the great number of such standards a few are mentioned below that concern titrimetric
methods and which indicate how universal the use of such methods is. Abbreviations:
AOAC
ASTM
DIN
EN
EPA
ISO
Official Methods of Analysis of the Official Analytical Chemists (USA)

American Society for Testing and Materials
Deutscher Normenausschuss
European Norm
US Environmental Protection Agency
International Organization for Standardization
161
AOAC 950.07 Acidity (total) of beer. Potentiometric titration method

AOAC 960.14 Quarternary ammonium compounds. Potentiometric titration method
AOAC 970.37 Monosodium gluconate in food. Potentiometric titration method
AOAC 971.27 Sodium chloride in canned vegetables. Method III. Potentiometric method
AOAC 979.02 Fentin in pesticide formulations. Potentiometric titration method
ASTM D 664-04
Standard Test Method for Acid Number of Petroleum Products by Potentiometric Titration
ASTM D 6174-97
Standard Test Method for Hydroxyl Groups Using Reaction with p-Toluene Sulfonyl Isocyanate (TSI) and Potentiometric Titration with Tetrabutylammonium Hydroxide
ASTM D 3341-91
Standard Test Method for Lead in Gasoline Iodine Monochloride Method
ASTM D 6174-97
Standard Test Method for Inorganic Sulfate in Surfactants by Potentiometric Lead Titration
DIN EN 25663 Water quality; determination of Kjeldahl nitrogen
DIN EN 25813 Water quality; determination of dissolved oxygen; iodometric method
DIN 38406-3
Determination of calcium and magnesium, complexometric tritation (E 3)
DIN 38409-7
Determination of acid and base capacity (waters)
DIN EN ISO 8467
Water quality Determination of permanganate index
EPA method 325.3 Chloride (drinking water)
EPA method 330.1 Chlorine (waters)
EPA method 360.2 Dissolved oxygen (waters)
European Pharmacopoeia 4th Edition & Supplements
ISO 13756
Determination of silver in silver jewellery alloys Volumetric (potentiometric) method using
sodium chloride or potassium chloride
ISO 3839
Petroleum products Determination of bromine number of distillates and aliphatic olefins
Electrometric method
ISO 4220
Ambient air Determination of a gaseous acid air pollution index Titrimetric method with
indicator or potentiometric endpoint detection
ISO 6326-3
Natural gas Determination of sulfur compounds Part 3: Determination of hydrogen sulfide, mercaptan sulfur and carbonyl sulfide sulfur by potentiometry
ISO 8298
Nuclear fuel technology Determination of milligram amounts of plutonium in nitric acid
solutions Potentiometric titration with potassium dichromate after oxidation by Ce(IV) and
reduction by Fe(II)
U.S. Pharmacopeia USP 26 NF-23, 2003
162
275 years the history of titrimetric analysis
Year
Who ?
What ?
1729
G.J. Geoffroy
Acidity of vinegar with potash
1747
L.G. Le Monnier
Carbonate content of mineral water with H2SO4
1750
G.F. Venel
Mineral water analysis with violet excerpt as indicator
1756
F. Home
First titrations with volumetric measurements (K2CO3 with HNO3; water hardness with Na2CO3)
1767
W. Lewis
Titration of K2CO3 with HCl and litmus as colored indicator
1779
V.A. Gioanette
Titrates carbonate in drinking water with acetic acid
1782
L.B. Guyton de Morveau
Content of HCl and HNO3 in mother liquors with K2CO3 and Curcuma indicator
1784
L.B. Guyton de Morveau
Prototype of a buret (gaso-mtre), glass tube with scale
1809
F.A.H. Descroizilles
Describes for the first time a measuring flask
1824
J.L. Gay-Lussac
Use of the names pipette (mesure petite) and burette
1828
J.L. Gay-Lussac
Term titre for content and/or quality designation
1840
A. Du Pascier
Uses iodine in ethanol as measuring solution
1843
M.J. Fordos, A. Glis
Titrate sulfite and thiosulfate with iodine solution
1851
J. von Liebig
Oldest complex formation titration (cyanide with AgNO3)
1855
F. Mohr
Publishes textbook on titration methods
1877
E. Luck
Uses phenolphthalein as the first synthetic color indicator
1893
R. Behrend
First potentiometric titration (argentometry)
1894
H. Tromssdorff
Describes 14 synthetic acid-base indicators
1897
W. Bttger
Acid-base titrations using the hydrogen electrode (potentiometric)
1900
F. Crotogino
Pt electrode for the indication of redox titrations
1909
F. Haber, Z. Klemensiewicz
pH electrode for the indication of potentiometric acid-base titrations
1915
J. Knop
Diphenylamine as the first redox indicator
1923
E. Mller
First monograph about potentiometric titrations
1926
C.W. Foulk, A.T. Bawden
Dead-stop titrations (Upol biamperometry) with two polarized Pt electrodes
1935
K. Fischer
Determinations with Karl Fischer reagent (KFR)
1936
Schellbach, C.R. Fresenius
Strip as a reading-off assistance of rod burettes
1945
G. Schwarzenbach
Complexometric titrations with EDTA
1947
M.D. Cannon
First combined pH glass electrode
1956
Metrohm
First piston burette
1958
Metrohm
First automatic titrator (E 336 Potentiograph)
1964
Metrohm
First Exchange Unit
1968
Metrohm
First digital titrator (Titroprint)
1973
Metrohm
Automatic analyzer (E 553 Sample Changer)
1979
Metrohm
First Titroprocessor (636)
1989
Metrohm
First Titrino (701 KF)
2002
Metrohm
First Titrando
163
164

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Practical Titration

Training Manual for Titrimetric Volumetric Analysis

Prof. Dr. Leo Gros

Peter A. Bruttel and Marcus von Kloeden

All rights reserved, including those of translation.

Titrimetric analysis with Titrino or Titrando

Titrimetric analysis with Titrino or Titrando

Acid-base titrations and methods, aqueous ............................................................

II. 1.1 Electrode calibration and electrode handling ............................................................ 55

Acid-base titrations and methods, non-aqueous

General and additional remarks about non-aqueous titrations................................. 79

Titer determination of c(AgNO3) = 0.1 mol/L............................................................. 95

Redox titrations and methods

Iodometry (iodine/thiosulfate) .................................................................................. 115

Complexometric and chelometric methods

Titer determination of c(Na2EDTA) = 0.1 mol/L with CaCO3 ................................... 141

Titrimetric analysis with Titrino or Titrando

I. 1 Introduction: titration means counting!

Titrimetric analysis with Titrino or Titrando

Important symbols used in the methods:

Molar concentration of substance X in mol/L, often written as [X]

Molar mass of substance or atomic mass (relative mass) of substance X in g/mol

Mass fraction of substance X, e.g. w (NaOH) = 40%

Mass concentration of substance X, e.g. (NaCl) = 20 g/L

Autoprotolysis constant of a solvent

a(H3O+) a(OH) / a2(H2O) = KW = 1014

Titrimetric analysis with Titrino or Titrando

H2O, neutral pH = - log

Acid-base reactions with water

HB (s) + H2O (b)

In order to be able to achieve the separate determination of the components in an aqueous

Titrimetric analysis with Titrino or Titrando

pKa values of some selected acids

pKb values of some selected bases

Hydrogen sulfide acid 1 stage

Hydrogen sulfide acid 2nd stage

Oxalic acid 1st stage

Oxalic acid 2nd stage

Phosphoric acid 1 stage

Phosphoric acid 2 stage

Phosphoric acid 3 stage

Sulfuric acid 1 stage

Sulfuric acid 2 stage

Source: see literature reference 8.

Titrimetric analysis with Titrino or Titrando

c) Titration of a weak base with a strong acid

c(A+) c(B) = KL (for the stoichiometric solubility product)

Titrimetric analysis with Titrino or Titrando

8.1 x 109 mol2/L2

1.08 x 1019 mol2/L2

3.95 x 1011 mol3/L3

2.57 x 109 mol2/L2

1.77 x 1014 mol2/L2

1.06 x 108 mol2/L2

3.4 x 1028 mol2/L2

7.7 x 1013 mol2/L2

6.15 x 1012 mol3/L3

1.56 x 1010 mol2/L2