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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. change.
Contrary to gravimetry, no poorly soluble compounds are dried or This end point titration (EP) requires a calibration of the electrode. Other
weighed, but a reagent with a known concentration is added to the titrations are performed as equivalence point titrations (equivalence point,
dissolved sample until the chemical conversion is complete. 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
Even today, titration is widely used in chemical analytics. First, a end point detection can take place in multiple ways using different chemical
titration is very easy and quick to perform, and also, titration yields a and physical methods.
very precise measuring result after only a few minutes - with optimal
conditions. A relative standard deviation of less than one percent is Contrary to wide belief, the measuring value of the titration is neither "pH"
normal. There is a reason why numerous standards still require titration nor "mV" but "ml" for the volume. The accuracy of the volume must be
as the method of choice. proven for each consumption. The consumption at the equivalence point,
end point or color change therefore shews the equivalence of the sample
Titration basics substance and the added reagent.

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.
Fig. 1 Modern titrator with sample changer in use.
1 compares the advantages and disadvantages of the types of use.
Titrations can be differentiated by means of their chemical reaction; these
Manual titration Automatic titration are called different reaction types.
Acid-basic titrations: Here, the pH value changes during the
+ Very fast + Fast titration. This can also be detected via a color change or by means
+ Precise + Very accurate of a pH electrode.
+ Simple + Easy after implementation ORP titrations: Here, the oxidation level in the sample changes. The
titration is performed with an oxidation or reduction agent and the endpoint is
+ Versatile + Versatile
detected via a color change or an ORP electrode (such as a platinum
Many standards and Many standards and regulations electrode). Precipitation titrations: The added reagent leads to
+ +
regulations precipitation. This can be traced with silver nitrate by means of a color
- Traceability + Traceability, documentation change like with a chloride titration or with a silver electrode.
- Comparability + Correctness and comparability Complexometric titrations: Metals are titrated with a complexing
- Automation capacity + Automation capacity agent. Their reaction can be traced by means of ion-sensitive
electrodes or via an indicator.
- Use of many reagents - Use of many reagents
Phase transfer titrations: The detection takes place during a different
Tab. 1: Comparison of manual and automatic titration. phase than the reaction.
Load titrations: The number of loads to the loading neutral point.
During the titration process, the content of the measuring solution is
precisely defined and a correction factor (titer) is determined in order to Often, titrations are differentiated by the type of detection of the titration end:
increase the measuring accuracy. After that, a reagent of known • Chemical detection via color change or precipitation.
concentration is dripped into a sample solution by means of a burette • Potentiometrically by ORP electrodes / pH glass electrodes.
until the equivalence point or end point is reached. • Biamperometrically by double platinum electrodes.
With the automated method, an exact dosing of the titration agent is the • Conductometrically by conductivity electrodes.
core function of the modern titrator. The standard ISO 8655 describes • Thermometrically by temperature changes.
the requirements and testing of the exact dosing and must be used in Titration is usually performed as a direct titration, where the reagent is
certain time intervals. The reaction is usually monitored by added directly. However, there are cases where an auxiliary reagent is
potentiometric sensors; usually, a pH electrode is used for this. In order added and where its surplus is determined via reverse titration.
to create a comparability with formerly manually derived results,
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 The galvanic sample pose a really uncomfortable issue. They often
analysis. For example in the following areas: contain strong acids and different metals. The titration is the most
• Food industry important method and is often used directly in the production area.
• Water and environment
It is a wonder that you can titrate in oil as well. This works in suitable
• Chemical industry
solvents. Acids are determined in order to obtain a measure for the
• Pharmaceutical industry
aging of oil by oxidation and exposure to air. Also, base numbers and
• Coating and metal processing, galvanic
water contents are typically titrated.
• 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 Method overview
products or contents in these products is quantified by means of
In the past 200 years, many different procedures have been developed.
titration. Among other things, the acid content, the sodium content, the
Today, more than 100 titration methods or modifications are known. The
protein content and nitrogen functions are determined on bases or
following describes the most important methods in more detail.
oxidation fragments.
An important area is the determination of moisture or water content Acid-base titrations are widely used. For example, the
in foods. The water content influences various characteristics such determination of the total acid is performed for almost all
as the shelf life, the processability and the taste of foods. Here, the beverages. This method is an end point titration to a fixed pH value.
Karl-Fischer titration is the method of choice as it is comparably The end points can be pH 7.0, pH 8.1 or pH 8.2. This depends on
selective in addition to yielding a high accuracy. the type of acids and the present comparison values. A glass
electrode is used for the pH measurement. This electrode must be
Also, in environmental applications, the water analysis is very important.
calibrated first, for which the buffers 4.00 pH and 7.00 pH are very
In addition to the drinking water analysis methods, titrations are used for
suitable. Because possible problems with alkaline buffers, a good
wastewater, surface water and sea water [1], [2].
two-point calibration without alkaline buffers is often more accurate
Many different methods are used in the chemical industry. Mostly codes than the more elaborate three-point calibration. (Please note: buffer
for production raw materials or finished products are determined, but solutions should not be stored in a refrigerator, as this may lead to
wastewater must be examined as well. Numerous methods are the crystallization of components that are difficult to return to the
documented in standards. The ISO standards as well as the ASTM solution.) The frequency of calibration depends on the condition of
regulations are used worldwide. the electrode as well as on the type of sample and matrix.
The pharma industry uses strictly regulated and uniform methods that A special method is the determination of the alkalinity in sea water. In
are defined in pharmacopoeia. These are content measurements of the sea water, a multitude of carbon dioxide of the atmosphere is dissolved.
pharmaceutically effective substances. The moisture content is The pH value of the sea decreases, the temperature increases and
determined by means of the Karl-Fischer titration as well. 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 The samples are often used directly as a solution. In practice, they are
most samples, the methods are well-known or nationally or internationally measured with pipettes. It is obvious that the sample measurement
standardized. Therefore, the basic chemical reaction is known. However, must be especially precise. A titration can never be more accurate than
you must select the titration reagent as well as the suitable electrode. the sample measurement. Measuring by means of an analysis scale is
much more precise. For solids, this is the method of choice, but
The reagents used most frequently here include: 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
• Baking soda (for the determination of acids in waterous systems).
required volume is placed inside the titration vessel and the syringe is
• Hydrochloric acid (for the determination of bases, carbonates and
placed back onto the scale. The scale usually shows the sample weight
hydrogen carbonates in waterous systems).
with four digits after the decimal point. Such a result is then
• Na2EDTA (for the complexometric titration with ion-sensitive
usually displayed in % or mg/g.
electrodes of metals)
• AgNO3 silver nitrate (mostly for the chloride or salt determination, Most titer reagents are commercially available in several concentrations.
halogenides and pseudohalogenides). Some require special attention after opening. Alkaline titration agents such
• Na2S2O3 sodium thiosulfate (for the reverse titration of iodometric as baking soda and alkaline can absorb CO2 from the air. This is
reactions) counteracted by a CO2 absorption agent (e.g. soda lime) in the dry pipe on
• Cer(SO4)2 Cersulfate (oxidation agent for many ORP titrations). the reagent surface, which is replaced after about two weeks. Of course
• (NH4)2Fe2(SO4)2 ammonia iron(II)-sulfate (reduction agent for many ORP water must be kept away for Karl-Fischer reagents. This is achieved by using
reactions, e.g. CSB). a molecular sieve with a pore size of 0.3 nm. The molecular sieve can be
• KOH potassium hydroxide in alcohol (determination of acids in organic dried at about 300 °C over six hours and replaced. The time of use is mostly
solvents). determined by the humidity. The reagents for the Karl-Fischer analysis
• HClO4 perchloride acid in glacial acetic acids (determination of bases in should be replaced at a higher drift. With the electrodes, glass electrodes are
organic solvents). often used for the acid-base titration. An electrode like this consists of a
glass indicator electrode and a silver silver chloride reference electrode.
The following electrodes are part of the standard equipment of a titration lab: Also, other reference systems such as iodine or iodide can be used. The
• Combined glass electrode with platinum diaphragm (for all waterous glass electrode selectively measures the "protons" in a solution. In organic
acid-base titrations). solutions, low ohm glass is often used as well as special ground diaphragm
• Silver combination electrode (for the determination of chloride). for the reference electrodes [5]. This ensures the load transport that is
• Platinum combination electrodes (for all ORP reactions). required for the measurement.
• Platinum double electrode (for reversible ORP reactions with dead stop A silver electrode is used as an indicator electrode and a silver silver chloride
detection). reference electrode is introduced into an electrode body combined. The
• Glass electrode with ground diaphragm with organic electrolyte solvents silver indicator electrode can be coated with AgCl. The silver electrode is
(for the titration in organic solvents). sulfidized for some applications. The sulfide coating is especially durable. In
• ISE electrodes such as the Ca electrode, Cu electrode, fluoride some cases, a glass electrode may also be used as a reference electrode.
electrode as a combination electrode or with separate reference The advantage is the easier
electrode (depending on the task and type of samples).

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 the
Verification of titration results
diaphragm could become plugged. However, the pH values must be Analytical methods require that the results are reviewed, or subjected
constant during the titration with these electrodes. Depending on the to a "validation" [6]. This process is the same for all analysis methods. Fig. 6
switching, such titration curves do not run ascending as usual, but shows the validation elements as per the USP, the American
descending. Pharmacopoeia.
The proper titration parameters are preconfigured in the titrator and can The two most important features during quality assurance are precision and
simply be adjusted for certain samples. Many pH titrations are performed as linearity. Figure 7 shows the linearity test of a Karl-Fischer reagent with
end point titrations. The end point is fixed on the pH value where the certified reference material. The median value that is accepted within a
indicator for the manual titration changes its color. Typical end points include spanning range (e.g. 4.5 to 5.5) is determined. The relative standard
e.g. pH 8.2 (change of phenolphthalein), pH 4.3 (change from methyl red or deviation provides us with information about the precision. The balance
methyl orange) and pH 7.0 (change from neutral red). This also ensures a straight must run through the zero point with a tolerance of one drop (= 0.05
good comparability between modern potentiometric titrations and the earlier ml) and the certainty measure (or the correlation coefficient) must be better
manually titrated results. 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 left. A clear evaluation is not ensured on the right side; the titration
should be smooth and the first derivation should deliver a clear peak for the parameters should be adapted. In this example, an enlargement of the
calculation of the equivalence point. Figure 8 shows an easily evaluative smallest step width would solve the problem.
jump with a clear first derivation on the

1.34 ml
248.5 mV

ml ml
1.2 1.4 3.75 4.375 5.0

The shape of the The shape of the first derivation is not


derivation is OK OK; the wrong peak can be evaluated.
Fig. 8 Shape of the first
derivation.

Summary
This article offers an overview of the basics of titration, the different chemical analytics, which you cannot imagine this industry without.
methods and describes the execution of the titration. In addition to Titration can be learned quickly and performed with the simplest means.
overview information, there are several practical tips on how to make the Based on its robustness and very high accuracy, it is used in every lab
titration more accurate and safer. It becomes clear that titration is still a and is part of many standard regulations.
widely used method today for the measurement of content in

Literature
[1] Peters, J., Lab&more (2012), Heft 8, S.2. [4] W.Gernand, K. Steckenreuter, G. Wieland, „Greater analytical accuracy
[2] Langer G., Peters J. (2011), Bestimmung der Alkalität im through gravimetric determination of quantity“, Fresenius Z. Anal. Chem.
Meerwasser durch Gran-Titration Whitepaper (1989) 334:534-539
www.laborpraxis.vogel.de/fachwissen/whitepaper/downloads/17429/ [5] Iris Sound und Helmut Becker, „Grenzen der pH Messung in
J.Peters, Bestimmung der Alkalinität in Meerwasser durch Granberech- nichtwässrigen Lösungsmitteln“
nung, GIT Labor-Fachzeitschrift 4/2012, S. 240–242, WILEY-VCH Verlag www.si-analytics.com/downloads/publikationen/elektrochemie.html
GmbH & Co. KGaA, GIT VERLAG, Weinheim [6] S. Kromidas, Handbuch Validierung in der Analytik,
[3] Beispielmethoden auf der Homepage von SI-Analytics: 2014 Wiley-VCH Verlag, ISBN-13: 978-3527329380
www.si-analytics.com/downloads/publikationen/elektrochemie.html