Introduction
the titration is aimed at a fixed pH value which corresponds to a color
Titration is one of the oldest methods to determine content in chemicals.
Contrary to gravimetry, no poorly soluble compounds are dried or
weighed, but a reagent with a known concentration is added to the
dissolved sample until the chemical conversion is complete.
Even today, titration is widely used in chemical analytics. First, a
titration is very easy and quick to perform, and also, titration yields a
very precise measuring result after only a few minutes - with optimal
conditions. A relative standard deviation of less than one percent is
normal. There is a reason why numerous standards still require titration
as the method of choice.
Titration basics
Titration in today's computer age, just like 200 years ago, is performed
under the same conditions:
• Stoichiometric and quick response
• Stable, precisely dosable reagent
• Detection of the end of the reaction by color reaction or
electro-chemical detection
After the reaction is known, the user is merely responsible for the
adherence to the correct conditions. Accordingly, special attention
should be paid to the dosing of the reagent and the detection of the end
of the reaction.
Titration can be performed with simple glass burettes or automated with
chip-controlled titrators. Today, the latter are mostly used, as the accuracy
and comparability are improved, but manual titration also has its place. Tab.
1 compares the advantages and disadvantages of the types of use.
Manual titration Automatic titration
+ Very fast + Fast
+ Precise + Very accurate
+ Simple + Easy after implementation
+ Versatile + Versatile
Many standards and Many standards and regulations
+ +
regulations
- Traceability + Traceability, documentation
- Comparability + Correctness and comparability
- Automation capacity + Automation capacity
- Use of many reagents - Use of many reagents
Tab. 1: Comparison of manual and automatic titration.
During the titration process, the content of the measuring solution is
precisely defined and a correction factor (titer) is determined in order to
increase the measuring accuracy. After that, a reagent of known
concentration is dripped into a sample solution by means of a burette
until the equivalence point or end point is reached.
With the automated method, an exact dosing of the titration agent is the
core function of the modern titrator. The standard ISO 8655 describes
the requirements and testing of the exact dosing and must be used in
certain time intervals. The reaction is usually monitored by
potentiometric sensors; usually, a pH electrode is used for this. In order
to create a comparability with formerly manually derived results,
change.
This end point titration (EP) requires a calibration of the electrode. Other
titrations are performed as equivalence point titrations (equivalence point,
EQ). Here, only the change of the potential or pH value is of importance. A
calibration of a pH electrode only serves the quality monitoring process. The
end point detection can take place in multiple ways using different chemical
and physical methods.
Contrary to wide belief, the measuring value of the titration is neither "pH"
nor "mV" but "ml" for the volume. The accuracy of the volume must be
proven for each consumption. The consumption at the equivalence point,
end point or color change therefore shews the equivalence of the sample
substance and the added reagent.
Fig. 1 Modern titrator with sample changer in use.
Titrations can be differentiated by means of their chemical reaction; these
are called different reaction types.
Acid-basic titrations: Here, the pH value changes during the
titration. This can also be detected via a color change or by means
of a pH electrode.
ORP titrations: Here, the oxidation level in the sample changes. The
titration is performed with an oxidation or reduction agent and the endpoint is
detected via a color change or an ORP electrode (such as a platinum
electrode). Precipitation titrations: The added reagent leads to
precipitation. This can be traced with silver nitrate by means of a color
change like with a chloride titration or with a silver electrode.
Complexometric titrations: Metals are titrated with a complexing
agent. Their reaction can be traced by means of ion-sensitive
electrodes or via an indicator.
Phase transfer titrations: The detection takes place during a different
phase than the reaction.
Load titrations: The number of loads to the loading neutral point.
Often, titrations are differentiated by the type of detection of the titration end:
• Chemical detection via color change or precipitation.
• Potentiometrically by ORP electrodes / pH glass electrodes.
• Biamperometrically by double platinum electrodes.
• Conductometrically by conductivity electrodes.
• Thermometrically by temperature changes.
Titration is usually performed as a direct titration, where the reagent is
added directly. However, there are cases where an auxiliary reagent is
added and where its surplus is determined via reverse titration.
 Measuring
solutions
Sample solution
Fig. 2: Manual titration. Source:
Wikipedia, Liquid 2003
Titration application scope
Titrations are performed in the most differentiated areas of chemical
analysis. For example in the following areas:
• Food industry
• Water and environment
• Chemical industry
• Pharmaceutical industry
• Coating and metal processing, galvanic
• Oil industry
One of the application fields is the titration in food analysis. As per
§ 64 LFBG (Foods, articles for daily use and feeding stuff), a number of
products or contents in these products is quantified by means of
titration. Among other things, the acid content, the sodium content, the
protein content and nitrogen functions are determined on bases or
oxidation fragments.
An important area is the determination of moisture or water content
in foods. The water content influences various characteristics such
as the shelf life, the processability and the taste of foods. Here, the
Karl-Fischer titration is the method of choice as it is comparably
selective in addition to yielding a high accuracy.
Also, in environmental applications, the water analysis is very important.
In addition to the drinking water analysis methods, titrations are used for
wastewater, surface water and sea water [1], [2].
Many different methods are used in the chemical industry. Mostly codes
for production raw materials or finished products are determined, but
wastewater must be examined as well. Numerous methods are
documented in standards. The ISO standards as well as the ASTM
regulations are used worldwide.
The pharma industry uses strictly regulated and uniform methods that
are defined in pharmacopoeia. These are content measurements of the
pharmaceutically effective substances. The moisture content is
determined by means of the Karl-Fischer titration as well.
The galvanic sample pose a really uncomfortable issue. They often
contain strong acids and different metals. The titration is the most
important method and is often used directly in the production area.
It is a wonder that you can titrate in oil as well. This works in suitable
solvents. Acids are determined in order to obtain a measure for the
aging of oil by oxidation and exposure to air. Also, base numbers and
water contents are typically titrated.
Method overview
In the past 200 years, many different procedures have been developed.
Today, more than 100 titration methods or modifications are known. The
following describes the most important methods in more detail.
Acid-base titrations are widely used. For example, the
determination of the total acid is performed for almost all
beverages. This method is an end point titration to a fixed pH value.
The end points can be pH 7.0, pH 8.1 or pH 8.2. This depends on
the type of acids and the present comparison values. A glass
electrode is used for the pH measurement. This electrode must be
calibrated first, for which the buffers 4.00 pH and 7.00 pH are very
suitable. Because possible problems with alkaline buffers, a good
two-point calibration without alkaline buffers is often more accurate
than the more elaborate three-point calibration. (Please note: buffer
solutions should not be stored in a refrigerator, as this may lead to
the crystallization of components that are difficult to return to the
solution.) The frequency of calibration depends on the condition of
the electrode as well as on the type of sample and matrix.
A special method is the determination of the alkalinity in sea water. In
sea water, a multitude of carbon dioxide of the atmosphere is dissolved.
The pH value of the sea decreases, the temperature increases and
therefore, less carbon dioxide can be dissolved in the sea water. The
exact content is determined by means
of a Gran-Titration - a procedure which can be easily automated with Handling samples and sample
a sample changer. preparation
With the frequent determination of chloride or "salt", a calibration of the It is not always ensured that the content of a sample is homogenously
electrode is not necessary. Silver nitrate is used as a titration agent, and distributed in a material. Therefore it is important to remove plenty of sample
a silver electrode is used as an electrode. Depending of the type of from the material and to homogenize this afterwards. This means that all
sample and the sample matrix, an electro-mechanically created surface components of a sample must be mixed and cut up as evenly as possible, so
of AgCl (silver chloride) is advantageous. The potentials can fluctuate that exactly the same amount (concentration) of content substances is
according to the condition of the electrode, concentration and sample present on 1 g as there is on 1 kg.
matrix. For these reasons, the titration continues until an EQ is
Both parts - the sampling and the homogenization are important
detected. Then, this does not depend on the potential itself, but solely
prerequisites for an optimal result for the titration time. It is important to make
on the change in the potential. Therefore, a "good" titration can be
sure that the sample is distributed homogeneously before part of it is
recognized via a "good" titration curve. During the analysis of the
removed for the titration.
titration curve, the uniformity of the first derivation is evaluated with a
single peak. This type of titration is called precipitation titration. Here, the following points are important:
• Is there a bottom sediment in liquid samples?
Another widely used titration type is the Iodometry. Here, a sample is
• Is there a difference in concentration based on a temperature difference
generally mixed with a surplus iodine so that it oxidizes a part of the sample.
in the vessel?
The non-converted iodine is then titrated with thiosulfate. This is a reverse
• Are these natural samples, which consist of a bowl and an interior
titration, as the reagent iodine (or a mixture of iodate and iodide) must be
part?
precisely dosed and weighed, and because the reverse titration must be
• Are the samples coated?
performed with an exactly defined concentration. While earlier, the blue color
• Does the surface absorb moisture?
of the iodine strength indicator simplified the work, today, this process is left
to the titrator with an ORP or dead stop titration. Another important point is the release of the parameter that is to be
determined. Thus, the chloride content (sodium content) in cheese is an
For drinking and mineral water, the water hardness is an important
important indicator for the shelf life and taste of the food. If the sample
parameter; also calcium and magnesium are relevant for the health care
(approx. 0.5 to 1 g of cheese) is filled into a beaker and filled with water,
industry and are titrated with EDTA (ethylene diamine tetra acedic acid).
nothing will happen. The cheese will swim in the water and the salt will
For the detection, either the calcium ion sensitive electrode (ISE) is
remain in the cheese. Only with increased temperature and a homogenizer,
used to determine both parameters or a copper electrode for the total
the mostly complete release of the salt will take place.
hardness. Instead of the usual combination electrodes, separate
electrodes are often used (ISE indicator electrode with separate A homogenizer is suitable for use during the sample preparation of many
reference electrode) because these a slightly more robust. The calcium samples as it can quickly cut and distribute samples. Here, the analysis
electrode is able to detect the signal from Ca and Mg directly while the components to be determined can be released from water or solvents and at
copper electrode requires copper EDTA for the indication in order to the same, be well distributed. Figure 4 shows the automated use in the
detect the total hardness. sample changer during the preparation of the sample.
In galvanic, many metals in the sample are also determined
complexometrically. Often, EDTA is used as a titration agent and
the Cu-ISE is titrated as an electrode. The detection takes place as
a complex displacement reaction by adding Cu-EDTA.
In the pharma industry, complex bases are often titrated. The most
important method here is the titration with per chloride acid in glacial
acetic acid. As many bases are present as hydrochloride, an indirect
determination is possible as well. Free hydrochloric acid is added and
the free HCl is first titrated with baking soda, and then to the HCl bound
to the nitrogen. This results in two equivalence points, whose difference
equals the number of amino groups.
It is difficult to imagine that an acid base titration is possible with a glass
electrode in black oil. However, one of the most important titration
parameters in oil in addition to the Karl-Fischer titration for the
determination of water are the TAN (Total Acid Number) and the TBN
(Total Base Number) determinations. With TAN. the titration takes place
in Toluol / Isopropanol with KOH in Isopropanol, with a glass electrode
and a reference electrode with ground-joint diaphragm, frequently as a
combination electrode.
These are merely some examples in order to show the bandwidth
of how titration methods are used for quantification. The link to the Fig. 4 Automatic cutting and distributing of samples in the sample changer.
finished application works and example methods can be found in
the literature references [3].
The Titration
The titration can be simply inserted in a lab with a burette or a titrator. For
most samples, the methods are well-known or nationally or internationally
standardized. Therefore, the basic chemical reaction is known. However,
you must select the titration reagent as well as the suitable electrode.
The reagents used most frequently here include:
• Baking soda (for the determination of acids in waterous systems).
• Hydrochloric acid (for the determination of bases, carbonates and
hydrogen carbonates in waterous systems).
• Na2EDTA (for the complexometric titration with ion-sensitive
electrodes of metals)
• AgNO3 silver nitrate (mostly for the chloride or salt determination,
halogenides and pseudohalogenides).
• Na2S2O3 sodium thiosulfate (for the reverse titration of iodometric
reactions)
• Cer(SO4)2 Cersulfate (oxidation agent for many ORP titrations).
• (NH4)2Fe2(SO4)2 ammonia iron(II)-sulfate (reduction agent for many ORP
reactions, e.g. CSB).
• KOH potassium hydroxide in alcohol (determination of acids in organic
solvents).
• HClO4 perchloride acid in glacial acetic acids (determination of bases in
organic solvents).
The following electrodes are part of the standard equipment of a titration lab:
• Combined glass electrode with platinum diaphragm (for all waterous
acid-base titrations).
• Silver combination electrode (for the determination of chloride).
• Platinum combination electrodes (for all ORP reactions).
• Platinum double electrode (for reversible ORP reactions with dead stop
detection).
• Glass electrode with ground diaphragm with organic electrolyte solvents
(for the titration in organic solvents).
• ISE electrodes such as the Ca electrode, Cu electrode, fluoride
electrode as a combination electrode or with separate reference
electrode (depending on the task and type of samples).
The samples are often used directly as a solution. In practice, they are
measured with pipettes. It is obvious that the sample measurement
must be especially precise. A titration can never be more accurate than
the sample measurement. Measuring by means of an analysis scale is
much more precise. For solids, this is the method of choice, but
solutions can also be measured easily with a scale. The sample is filled
into a single use syringe, placed on the scale and tared. Now, the
required volume is placed inside the titration vessel and the syringe is
placed back onto the scale. The scale usually shows the sample weight
with four digits after the decimal point. Such a result is then
usually displayed in % or mg/g.
Most titer reagents are commercially available in several concentrations.
Some require special attention after opening. Alkaline titration agents such
as baking soda and alkaline can absorb CO2 from the air. This is
counteracted by a CO2 absorption agent (e.g. soda lime) in the dry pipe on
the reagent surface, which is replaced after about two weeks. Of course
water must be kept away for Karl-Fischer reagents. This is achieved by using
a molecular sieve with a pore size of 0.3 nm. The molecular sieve can be
dried at about 300 °C over six hours and replaced. The time of use is mostly
determined by the humidity. The reagents for the Karl-Fischer analysis
should be replaced at a higher drift. With the electrodes, glass electrodes are
often used for the acid-base titration. An electrode like this consists of a
glass indicator electrode and a silver silver chloride reference electrode.
Also, other reference systems such as iodine or iodide can be used. The
glass electrode selectively measures the "protons" in a solution. In organic
solutions, low ohm glass is often used as well as special ground diaphragm
for the reference electrodes [5]. This ensures the load transport that is
required for the measurement.
A silver electrode is used as an indicator electrode and a silver silver chloride
reference electrode is introduced into an electrode body combined. The
silver indicator electrode can be coated with AgCl. The silver electrode is
sulfidized for some applications. The sulfide coating is especially durable. In
some cases, a glass electrode may also be used as a reference electrode.
The advantage is the easier

Formula for the content determination Formula for the titer determination
1000 * weight [g]
(EQ [ml] - blind value [ml])* titer * mol weight * conc. titration agent * 100 Titer =
%=
1000 * weight [g] (EQ [ml] * conc. titration agent * mol weight

EQ [ml] equivalence point in ml reagent EEQ [ml] equivalence point in ml reagent

blind value [ml] Possible consumption of a blind value titration in ml, Titer nominal value/actual value of a separate titer
otherwise "0" position, usually a value around 1.000
Titer nominal value/actual value of a separate titer mol weight [g / mol] mol weight, e.g. 35.45 for chloride
position, usually a value around 1.000 conc. titration agent [mol / l] concentration, e.g. 0.1 mol / l
mol weight [g / mol] mol weight, e.g. 35.45 for chloride 1000 conversion g -> mg
conc. titration agent [mol / l] concentration, e.g. 0.1 mol / l weight The weight in g
100 conversion in %
1000 conversion g -> mg
weight The weight in g
EQ * 0.998 * 35.45 * 0.1 * 100 Example
Chloride [%] = Titer AgNO3 [0.1 mol / l] Titer - chloride =
1000 * 0.0584
Example chloride in [%] 1000 * 3.1235
EQ * 0.1 * 58.443
Fig. 5 Sample formulas for a content and titer determination.
handling. An electrolyte must be filled into the reference electrode and
diaphragm could become plugged. However, the pH values must
constant during the titration with these electrodes. Depending on
switching, such titration curves do not run ascending as usual,
descending.
The proper titration parameters are preconfigured in the titrator and can
simply be adjusted for certain samples. Many pH titrations are performed as
end point titrations. The end point is fixed on the pH value where the
indicator for the manual titration changes its color. Typical end points include
e.g. pH 8.2 (change of phenolphthalein), pH 4.3 (change from methyl red or
methyl orange) and pH 7.0 (change from neutral red). This also ensures a
good comparability between modern potentiometric titrations and the earlier
manually titrated results.
the
Verification of titration results
be Analytical methods require that the results are reviewed, or subjected
the to a "validation" [6]. This process is the same for all analysis methods. Fig. 6
but shows the validation elements as per the USP, the American
Pharmacopoeia.
The two most important features during quality assurance are precision and
linearity. Figure 7 shows the linearity test of a Karl-Fischer reagent with
certified reference material. The median value that is accepted within a
spanning range (e.g. 4.5 to 5.5) is determined. The relative standard
deviation provides us with information about the precision. The balance
straight must run through the zero point with a tolerance of one drop (= 0.05
ml) and the certainty measure (or the correlation coefficient) must be better
than 0.99. All these requirements are fulfilled in the example shown.

Category I Category II Category II Category III Such a linearity test is only possible if different volumes are
Feature Content Limit Quantitative Quantitative prescribed instead of the same standard or sample volume. In this
determination check determination determination
example, three values between 1 g and 2 g are weighed in exactly
to four digits following the decimal point. This way, the most
Precision + - + +
important validation elements can be monitored easily and without
Correctness + (+) + + much effort already with a titer position or during a trial titration.
Detection limit - + - +
Determination
- - + +
limit
Selectivity + + + +
Area + (+) + +

Linearity + - + +
Robustness + + + +

USP XXII regulations for validation:

• Category I: Main components
• Category II: Side products
• Category III: Performance parameters (drug release)
Fig. 6: Validation diagram

If the comparability is not as important, the titration is often performed

dynamically to one or more equivalence points. Here, only the change
of the potential is important. The dynamic parameters determine the
step size during the titration depending on the ascension of the titration 5
y = 2.0656x + 0.0055
curve. Here, the steep part of the curve has small titration steps and the = 1.0000
flat part of the curve has large titration steps. The "medium" parameters 4.5
often yield reasonable curves. If the step size is too large in the steep
part, the dissolving capacity is reduced; if the step width is too small, the 4
curve becomes "jerky". This can easily be seen from the first derivation,
Consumption [ml]

which then often shows several "peaks" (see Figure 8). This often leads 3.5
to incorrect evaluations and therefore fluctuation results. The titration
3
speed is also very much determined by the drift parameters. These
determine which drift criteria (mV/min) are used to accept a stable
2.5
signal from the electrode. The reasonable drift criterion depends on the
application and is between 10 and 50 mV/min.
2
After the titration, the titration curve is created and the titrator - or the
user himself in case of a manual titration - calculates the result based 1.5
on a defined formula. This is always based on the rule of three. Only 0.5000 1.0000 1.5000 2.0000 2.5000
two different formulas are necessary: One for the determination of the
titer (here, the weight is in the numerator) as well as a formula for the Weight [g]
determination of content (weight in denominator). The formulas are Fig. 7 Linearity test.
shown in Figure 5.
The quality of a single titration can also be evaluated. The titration curve
should be smooth and the first derivation should deliver a clear peak for the
calculation of the equivalence point. Figure 8 shows an easily evaluative
jump with a clear first derivation on the
1.34 ml
248.5 mV
ml
1.2 1.4
The shape of the
derivation is OK
Fig. 8 Shape of the first
derivation.
Summary
This article offers an overview of the basics of titration, the different
methods and describes the execution of the titration. In addition to
overview information, there are several practical tips on how to make the
titration more accurate and safer. It becomes clear that titration is still a
widely used method today for the measurement of content in
Literature
[1] Peters, J., Lab&more (2012), Heft 8, S.2.
[2] Langer G., Peters J. (2011), Bestimmung der Alkalität im
Meerwasser durch Gran-Titration Whitepaper
www.laborpraxis.vogel.de/fachwissen/whitepaper/downloads/17429/
J.Peters, Bestimmung der Alkalinität in Meerwasser durch Granberech-
nung, GIT Labor-Fachzeitschrift 4/2012, S. 240–242, WILEY-VCH Verlag
GmbH & Co. KGaA, GIT VERLAG, Weinheim
[3] Beispielmethoden auf der Homepage von SI-Analytics:
www.si-analytics.com/downloads/publikationen/elektrochemie.html
left. A clear evaluation is not ensured on the right side; the titration
parameters should be adapted. In this example, an enlargement of the
smallest step width would solve the problem.
ml
3.75 4.375 5.0
The shape of the first derivation is not
OK; the wrong peak can be evaluated.
chemical analytics, which you cannot imagine this industry without.
Titration can be learned quickly and performed with the simplest means.
Based on its robustness and very high accuracy, it is used in every lab
and is part of many standard regulations.
[4] W.Gernand, K. Steckenreuter, G. Wieland, „Greater analytical accuracy
through gravimetric determination of quantity“, Fresenius Z. Anal. Chem.
(1989) 334:534-539
[5] Iris Sound und Helmut Becker, „Grenzen der pH Messung in
nichtwässrigen Lösungsmitteln“
www.si-analytics.com/downloads/publikationen/elektrochemie.html
[6] S. Kromidas, Handbuch Validierung in der Analytik,
2014 Wiley-VCH Verlag, ISBN-13: 978-3527329380