Analytical Chemistry

Basics of Titration
2 Basics of Titration METTLER TOLEDO
 Content
1. Definition of titration 4
2. Historical development 4
3. Titration theory 6
3.1 Assay reactions ......................................... 6
3.2 Volumetry / Coulometry............................... 7
3.3 Indication principles ................................... 8
3.4 Endpoint / Equivalence point ..................... 10
3.5 Fields of use ............................................ 12
3.6 Advantages of titration .............................. 13

4. Automated titrators 14
4.1 Definition ................................................ 14
4.2 Working principle of automated titrators ...... 14
4.3 Titrant addition ......................................... 16
4.4 Measured value acquisition ....................... 18
4.5 Evaluation principles ................................ 20

5. Quality management in titration 24

5.1 GLP ........................................................ 25
5.2 Certification of an automatic titrator ............ 25
5.3 Validation of titration methods ................... 28

6. Chemical backgrounds 30
6.1 The mole ................................................ 30
6.2 Equivalent number z* ............................... 32
6.3 Concentration of a titrant ........................... 33
6.4 Chemistry in titration................................. 35
6.5 The ionic product of water ......................... 37
6.6 The strength of acids and bases ................ 38

7. Glossary 39
8. Literature 40

METTLER TOLEDO Basics of Titration 3

 1. Definition of titration
Titration is an analytical technique which allows the quanti-
tative determination of a specific substance (analyte) dis-
solved in a sample. It is based on a complete chemical
reaction between the analyte and a reagent (titrant) of known
concentration which is added to the sample. A well-known
example is the titration of acetic acid (CH3COOH) in vinegar
with sodium hydroxide, NaOH (determination of vinegar):

CH3COOH + NaOH CH3COONa + H2O

Analyte Reagent Reaction Products

The titrant is added until the reaction is complete. In order to

be suitable for a determination, the end of the titration reaction
has to be easily observable. This means that the reaction has
to be monitored (indicated) by appropriate techniques, e.g.
potentiometry (potential measurement with a sensor) or with
colour indicators.
Titration reaction: The measurement of the dispensed titrant volume allows the
1. fast calculation of the analyte content based on the stoichiometry
2. complete
3. unambiguous of the chemical reaction. The reaction involved in a titration
4. observable must be fast, complete, unambiguous and observable.

2. Historical development
The classical way
Titration is a classical analytical technique widely used.
Originally, it was performed by adding the titrant using a
graduated glass cylinder (burette). With a tap the titrant
addition was regulated manually. A change in colour indi-
endpoint
cated the end of the titration reaction (endpoint
endpoint).
At first, only those titrations showing a significant colour
change upon reaching the endpoint were performed. Later
titrations were coloured artificially with an indicator dye. The
precision achieved depended mainly on the chemist's skills
and, in particular, on his different colour perception.

4 Basics of Titration METTLER TOLEDO

 The modern way
Titration has experienced a strong development: manual and
Motorized burette -later- motorized piston burettes allow reproducible and
accurate titrant addition. Electrodes for potential measure-
ment replace the colour indicators, achieving higher preci-
sion and accuracy of the results. Graphical plot of potential
Graphical plots versus titrant volume allows a more exact statement about the
reaction than the colour change at the endpoint. With micro-
Microprocessor processors the titration can be controlled and evaluated
automatically. This represents a relevant step towards com-
plete automation.

Today and tomorrow

Development is not yet complete. Modern autotitrators allow
the definition of complete analysis sequences achieving
maximum flexibility in method development. For each appli-
cation the specific method can be defined by combining
simple operation functions like "Dose", "Stir", "Titrate", "Cal-
Flexible method culate" in a defined sequence. Auxiliary instruments (sample
concept changers, pumps) help reducing and simplifying the work
load in laboratories. A further trend is the connection to
Typical method: computers and Laboratory Information Management Sys-
LIMS
tems (LIMS
LIMS).
Title
Sample
Stir
Titration
Rinse
Calculation
Statistics
Record
Fig. 1: DL77 Titrator.
This instrument can perform
two titrations simultaneously.
Notice the four burettes and
the two titration heads. The
method and the curves are
shown on the display.

METTLER TOLEDO Basics of Titration 5

 3. Titration theory
3.1 Assay reactions
There are several assay reactions which are used in titration:
Acid/Base reactions:
HCl + NaOH NaCl + H2O
Examples: Acid content in wine, milk
Acid content in ketchup
Content of HCl, HNO3 , H2SO4 .
Precipitation reactions:
NaCl + AgNO3 AgCl + NaNO3
Examples: NaCl content in crisps, ketchup and food
Silver content in coins
BaCl2 + Na2SO4 BaSO4 + 2 NaCl
Examples: Sulfate content in mineral water
Sulfate content in electroplating bath
Redox reactions:
2 Cu2+ + 2 I- 2 Cu+ + I2
2 S2O32- + I2 S4O62- + 2 I -
Examples: Content of copper, chromium and nickel in
electroplating baths
Complexometric reactions:
Mg2+ + EDTA Mg2+-EDTA
Ca2+ + EDTA Mg2+-EDTA
Examples: Total hardness of water (Mg and Ca)
Calcium content in milk and cheese
Cement analysis

6 Basics of Titration METTLER TOLEDO

 Colloidal precipitation reaction:
Hyamine + SDS Hyamine-SDS
Examples: Anionic surfactant content in detergents
Anionic surfactant content in washing powders
Anionic surfactant content in liquid cleanser

3.2 Volumetry / Coulometry

The titrant can either be added directly to the sample by a
burette (volumetry) or generated electrochemically in the
titration cell (coulometry).
The coulometric titration is mainly employed for the water
determination according to Karl Fischer when the content is
very low, e.g. smaller than 50-100 ppm (0.005-0.01%).

Titration

Volumetry Coulometry

- Potentiometry - Voltametry

- Voltametry Determination of
low water content
- Amperometry in different sam-
- Photometry ples such as food,
chemicals, phar-
- Conductometry maceutical prod-
ucts, etc.
- Turbidity

METTLER TOLEDO Basics of Titration 7

 3.3 Indication principles
Titrations can be classified according to the indication
principles and the chemical reaction occurring.
Indication Reaction type/Effect Sensor

Potentiometry: Potentiometry Acid/Base (aqueous) DG111

The concentration- DG101
dependent potential
(mV) of a solution is DG114
measured against a Examples: DG115
reference potential.
1. Acid content analysis
2. Acidity in wine

Acid/Base (nonaqueous) DG113

Examples:
1. Acid/Base number AN, BN
2. Epoxide value

Redox DM140
Examples:
1. Copper determination
3. Nickel det. (Electroplating)

Precipitation DM141
Examples:
1. Salt content in ketchup
2. Silver content of alloys
Voltametry:
The concentration-
dependent potential
Voltametry Karl Fischer DM143
of a solution (mV) is Examples: DM142
measured at a 1. Water in butter
constant electric
current. 2. Water in oil and gasoline
Bromine number DM143
Examples:
Bromine number of gasoline

8 Basics of Titration METTLER TOLEDO

 Indication Reaction type/Effect Sensor

Amperometry: Amperometry Amperometric titration DM143

The current flowing Examples: DM142
in a sample solution
(µA) is measured at 1. Iron(II) determination
a constant potential 2. Vitamin C determination

Photometry: Photometry Complexometry DP550

The light
transmission (mV or
DP660
% transmission) of Examples:
a coloured or turbid 1. Total hardness of water
solution is measured
with a photometric 2. Nickel content
sensor.
Turbidimetry DP550
DP660
DN100
Examples:
1. Surfactant titration (DP)
2. Anionic surf. content
in cooling lubricants (DN)

Conductivity: Conductivity Conductometric titration MPC227

The conductivity of a
solution (µS/cm) is Example:
measured by a Alpha acids in beer
conductivity-meter.

Thermometry: Thermometry Temperature measurement Pt100

The temperature of a
sample is measured Example:
by a temperature Boric acid content
sensor.
PS.: Signal conversion:
Resistance -> Voltage
(Ohm) (mV)

METTLER TOLEDO Basics of Titration 9

 3.4 Endpoint / Equivalence point
There are basically two titration modes which can be distin-
guished: endpoint and equivalence point.
Endpoint titration mode (EP)
The endpoint mode represents the classical titration proce-
dure: the titrant is added until the end of the reaction is
observed, e.g., by a colour change of an indicator.
With an automatic titrator, the sample is titrated until a
predefined value is reached, e.g. pH = 8.2.

E [pH]

Endpoint pH = 8.2

V [mL]
Equivalence point titration mode (EQP)
The equivalence point is the point at which the analyte and
the reagent are present in exactly the same concentration.
In most cases it is virtually identical to the inflection point of
the titration curve, e.g. titration curves obtained from acid/
base titrations.

10 Basics of Titration METTLER TOLEDO

 E [pH]

Equivalence point

V [mL]

The inflection point of the curve is defined by the correspond-

ing pH or potential (mV) value and titrant consumption (mL).
The equivalence point is calculated from the consumption of
titrant of known concentration. The product of concentration
and the titrant consumption gives the amount of substance
which has reacted with the sample.
In an autotitrator the measured points are evaluated accord-
ing to specific mathematical procedures which lead to an
evaluated titration curve. The equivalence point is then
calculated from this evaluated curve.

METTLER TOLEDO Basics of Titration 11

 3.5 Fields of use

Agriculture Medicine
Aircraft Military
Building materials Mining
Car Manufacturing Oil Industry
Ceramics Packing materials
Chemical industry Paints, Pigments
Coal products Paper & Pulp
Coating Petroleum
Cosmetics Pharmaceuticals
Detergents Photo industry
Drugs Plastic products
Electronic industry Printing, Publishing
Electroplating Rail
Energy Rubber
Explosives Soaps
Food Stone (Clay, Cement)
Glass Textile
Government Tobacco industry
Health University, School
Leather Water
Machinery Zeolite

12 Basics of Titration METTLER TOLEDO

 3.6 Advantages of titration

☞ Classical, well-known analytical technique

☞ Fast

☞ Very accurate and precise technique .

☞ High degree of automation.

☞ Good price/performance ratio compared to more

sophisticated techniques.

☞ It can be used by low-skilled and -trained operators.

☞ No need for highly specialised chemical knowledge.

Mettler-Toledo Quality Management:

✓ Printout of the results with all necessary

information according to GLP.

✓ Titrator logbook (Qualification of the instrument).

✓ Complete certification procedure to verify the

technical specifications.
✓ Technical support for complete certification of
the titrators hardware.

✓ Extensive support for validation of titration

methods (application brochures).

METTLER TOLEDO Basics of Titration 13

 4. Automated titrators

4.1 Definition
Automated titrators are microprocessor-controlled instru-
ments which allow the automation of all operations involved
in titration:
1. Titrant addition
2. Monitoring of the reaction (Signal acquisition)
3. Recognition of the endpoint
4. Data storage
5. Calculation
6. Results storage

4.2 Working principle of automated titrators

Automated titrators follow a defined sequence of operations.
This sequence is basically the same for all different models
and brands. It is performed and repeated several times until
the endpoint or the equivalence point of the titration reaction
is reached (titration cycle).
The titration cycle is shown in figure 2. It mainly consists of
4 steps. Each step has different specific parameters (e.g.
increment size) which have to be defined according to the
specific titration application.
More complex applications require more steps, e.g. dispens-
ing of an additional reagent for back titrations, dilution,
adjusting of the pH value. These steps and the corresponding
parameters are resumed in a titration method.

14 Basics of Titration METTLER TOLEDO

 Fig. 2: Titration cycle in a modern autotitrator.
The different steps are performed until endpoint or equiva-
lence point is reached.

1
BURETTE
1, 5, 10, 20 mL

4 2
MICROPROCESSOR 1. Titrant addition TITRATION BEAKER
2. Titration reaction
- Data storage 3. Signal acquisition - Stirring
4. Evaluation
- Data evaluation
- Chemical reaction
- Control

- Calculation - Signal monitoring

3
DETECTION PRINCIPLES
- Potentiometric (DG- and DX-Electrodes)
- Photometric (DP550/660 Phototrode)
- Turbidity (DP Phototrode and
DN100 Infratrode)
- Voltametric (DM142)
- Amperometric (DM142 )
- Conductometric (MPC227)

METTLER TOLEDO Basics of Titration 15

 4.3 Titrant addition
The titrant can be added to the sample as follows:
Incremental titrant addition (INC)
The titrant is added in constant volume increments ∆V:

E [pH]
Incremental addition

V [mL]

Examples: Incremental titrant addition is used in nonaqueous titrations,

-Nonaqueous titrations
-Redox titrations
which sometimes have an unstable signal, and also in redox
-Total hardness of H2O and in photometric titrations, where the potential jump at the
(Photometric titration) equivalence point occurs suddenly.
-Ionic surfactant titr.
(Turbidimetric titr.) Notice that in the steepest region of the curve there are
relatively few measured points.

16 Basics of Titration METTLER TOLEDO

 Dynamic titrant addition (DYN)
A constant pH- or potential difference allows the variation
of the volume increment between minimum and maximum
volume increment.

E [pH]
Dynamic addition

V [mL]

Examples: Thus, the analysis can be speeded up by using big incre-

-Acid/base titrations
-Aqueous titrations
ments in the flat regions of the titration curve. In addition,
-Precipitation titrations more measured points are obtained in the steepest region of
-Redox titrations the curve leading to a more accurate evaluation.

METTLER TOLEDO Basics of Titration 17

 4.4 Measured value acquisition
When should the next increment be added? This question can
be answered with two possible types of signal acquisition.
Timed-increment acquisition (TFIX)
Timed-increment The acquisition of the signal following every increment
acquisition addition is recorded after a fixed waiting time ∆t:

E [pH]

measured value

∆t 1 ∆t 2 ∆t 3

V [mL]

Examples: The timed-increment acquisition is preferable when the

-Base number (BN)
-HClO4-titrations
signal is noisy (e.g., nonaqueous titrations with unstable
signal) and when the titration has to be speeded up.

18 Basics of Titration METTLER TOLEDO

 Equilibrium-controlled acquisition (EQU)
The signal is first acquired when the pH value or the potential
(mV) no longer changes more than a specific value ∆E within
a defined time interval ∆t.
This means that the signal drift of the sensor must be lower
than the ratio ∆E/∆t before addition of the next increment.

E [pH]

∆t = 2s

∆t = 2s ∆E = 1mV
∆E =
1mV
∆t = 2s
∆E = 1mV
∆t = 2s
∆E = 1mV

measured value

V [mL]

Examples: The value measured after each increment addition is only

-Aqueous titrations
acquired when an equilibrium has been established in the
-Redox titrations
-Total hardness of H2O solution and the signal has become stable. This equilibrium
(Photometric titration) condition can be achieved at the earliest after the time t(min)
and should be established at the latest at t(max).

METTLER TOLEDO Basics of Titration 19

 4.5 Evaluation principles
Four different curves are observed and evaluated with the
corresponding procedures specified in the titration method.
Symmetric S-curve:
Symmetric curve: E [pH/mV]
The curve has a
symmetric profile and
the equivalence point
is the inflection point
of the curve.

Examples:
Acid/base titrations
Redox titrations
Precipitation titrations

V [mL]
This curve is evaluated by plotting the first derivative ∆E/∆V
versus titrant consumption V. The maximum of the derivative
is at the inflection point and indicates the equivalence point.
Evaluation principle of ∆E/∆V [pH/mV]
symmetric curve:
STANDARD

V [mL]
For the automatic evaluation of the symmetric S-curve the
titrator provides the appropriate procedure ("STANDARD").
20 Basics of Titration METTLER TOLEDO
 Asymmetric curve:
This titration curve shows a different profile than the typical
symmetric S-curve, and thus a different evaluation proce-
dure is needed. This is based on the Tubbs procedure (see
"Fundamentals of titration", ME-704153)

Asymmetric curve: E [mV]

The asymmetry has to
be taken into account
for curve evaluation.
The equivalence point
is shifted towards the
region with the
stronger curvature. In
this case it is located
in the upper part of
the steepest jump.

Examples:
Photometric titrations
Redox titrations
Turbidimetric titrations V [mL]

The curve is fitted with two circles (better: two hyperbolas).

The intersection point of the line connecting the two foci and
the titration curve indicates the equivalence point.
Evaluation principle of E [mV]
asymmetric curve:
ASYMMETRIC

V [mL]

The evaluation procedure to be chosen is "ASYMMETRIC".

METTLER TOLEDO Basics of Titration 21

 Minimum (Maximum) curve:

Minimum curve: E [% T]
The light transmission
is measured versus
titrant consumption. The
signal shows a
minimum at the
equivalence point.

Examples:
Ionic surfactant determ.
(Turbidimetric titrations)

V [mL]
EQP

This curve shows the typical profile obtained from turbidimet-

ric titrations, e.g., determination of the anionic surfactant
content, where a colloidal precipitate is formed by adding the
titrant. This leads to an increased turbidity of the solution. The
profile of the curve is characterized by a minimum in the curve
which indicates the equivalence point EQP.
The precipitate formation is monitored with a photometric
sensor, and the light transmission in the solution is measured
with a phototrode.
Evaluation principle of At the equivalence point, the turbidity reaches its maximum,
minimum curve: i.e. the transmission has a minimum. A special evaluation
MINIMUM
procedure allows the determination of the minimum of the
curve ("MINIMUM").
Evaluation principle of Curves showing a maximum are evaluated with the proce-
maximum curve: dure "MAXIMUM". Example: Content determination of anionic
MAXIMUM
surfactants in cooling lubricants.

22 Basics of Titration METTLER TOLEDO

 Segmented curve:
This profile is obtained when conductometric titrations are
performed (notice the unit of measurement in the graphical
Segmented curve:
The profile of this curve representation: µS/cm, micro-Siemens). The EQP is defined
shows a clear bend at by a sharp change in conductivity. The curve is evaluated by
the equivalence point. determining the maximum of its second derivative.

Examples:
[µS/cm]
E[mS]
- a-Acids in beer
(Conductometric titration)
- Vitamin C
(Amperometric det.)

V[mL]
EQP
∆E/∆V [mS/mL]

V[mL]
EQP
2
∆2E/∆ V

Evaluation principle of
segmented curve:
SEGMENTED.

V[mL]
EQP

METTLER TOLEDO Basics of Titration 23

 5. Quality management in titration
Quality management has become a relevant topic for the user
of analytical instruments. It is mainly based on documenta-
tion of the proven technical specifications, the measurements
and the analytical methods used. The documentation repre-
sents the basics of each quality management system and is
requested by the auditors during periodical checks.
Quality management: why?
1. The customer requires correct results with respect to
accuracy and precision.
2. Pharmaceutical companies and government organiza-
tions (e.g., FDA, EPA) require traceability of the results
and thus qualification of the instruments.

Both can be achieved by a complete documentation of:

1. Results, 2. Compliance to technical specifications,
3. Method check. The documentation procedure of analytical
work in the laboratory is regulated by the applied QM-System
(e.g. GLP, see 5.1), while the proof of technical specifica-
tions is resumed in the certification procedure (5.2).
Specific analytical methods have to be tested in order to get
correct results, i.e., the methods have to be validated (5.3).
To resume:
GLP:
Quality of planning, performing, controlling and reporting
of laboratory work
Certification:
Quality of the instrument and of the measured values,
Validation:
Quality of the analytical method and thus of the achieved
results.

24 Basics of Titration METTLER TOLEDO

 5.1 GLP
International bodies have elaborated a set of rules concern-
ing the analytical work in the laboratory in order to achieve
a standard regulation recognized and accepted in all coun-
tries of the world. These rules are commonly known as GLP
rules (GLP, Good Laboratory Practice) [1].
GLP is a formal framework for testing chemicals and consists
GLP Rules:
of 10 specific rules. The goals of GLP are:
1. Organisation and
personnel of test 1. Quality assurance of test data
facilities 2. Mutual acceptance of data
2. Quality assur- 3. Avoid multiplication of tests
ance program
3. Facilities
4. Apparatus, In particular, avoiding the multiplication of tests saves costs
materials, and and time. For instance, a customer does not have to repeat
reagents
5. Test system the same test that the producer performed at the end of the
6. Test and production process of a specific chemical product.
reference
substances
7. Standard
operating
procedures 5.2 Certification of an automatic titrator
8. Performance of
the study The certification is a check of the instrument [2] in order to
9. Reporting of the
study
10. Storage of
1. Verify if the technical specifications are fulfilled
records and 2. Ensure that correct results are achieved.
materials

Comment:
Certification is only a part of a list of measures to guarantee
correct results. Other points that have to be considered are the
system suitability tests, the sensor calibration, the titrant
standardization, and method validation (5.3).

METTLER TOLEDO Basics of Titration 25

 A complete certification of the titrator can be performed by
testing the following hardware:

1. Sensor input and amplifier:

1.1 Potential measurement with certified voltmeter
1.2 Temperature sensor input
(measurement with certified resistors)

2. Dosing accuracy:
2.1 Burette motor drive
Measurement of the piston stroke with a
certified micrometer

2.2 Glass burette

Measurement of the deviations from the speci-
fied diameter value of the glass cylinder.
Different volumes of water are dispensed and
their mass is compared to the dispensing of
a certified reference burette.

26 Basics of Titration METTLER TOLEDO

 Quality management requires the documentation of the
performance over the whole lifetime of the instrument, i.e.,
from the project phase through manufacturing, installation,
operation until disposal of the instrument.

All these steps are resumed in the unique concept of Quali-

fication:

Specification Qualification (SQ)

Requirements, Functions, Design, HW/SW

Construction Qualification (CQ)

End control for each product

Installation Qualification (IQ)

Procedure of installation (checklist) at customer's facility

Operational Qualification (OQ)

Evidence and compliance to specifications (Certification)

Performance Qualification (PQ)

Periodical tests, checks, renew certification, SOP's

Support available:
1. Specially trained MT service engineers can perform the
calibration and certification of the titrator hardware with
specific calibrated and certified tools (CertiCase) to allow
traceability to international standards.
2. The Declaration of System Validation stating that the
titrator has been developed and manufactured following
a strict quality management system.
3. The titrator logbook:
The whole lifetime of the instrument can be documented
and, thus, it represents a strong support during quality
audits.

METTLER TOLEDO Basics of Titration 27

 5.3 Validation of titration methods
The goal of each measurement is to obtain correct results.
This means that the suitable titration method has to be
chosen, in addition to the check of technical specifications
(hardware certification) and the correct documentation pro-
cedure (GLP). In other words: the chemistry of the titration
reaction has to be the "right one".

To check a titration method , a validation has to be

performed. This procedure consists of the verification of the
following principles [3] :

1. Accuracy
The measured value coincides well with the expected
true (theoretical) value.

2. Precision (Repeatability)
The results of a series do not deviate too much from the
mean value obtained, i.e. small standard deviation.

3. Linearity
Correct results over a specified concentration range, i.e.,
no dependence of the results from the sample size.

4. Systematic errors
Disturbing influences due to the method itself or to
solvent blank values.

5. Ruggedness
Inertness against chemical/physical influences likely to
occur (solvents, temperature, CO2 - intake, etc.)

6. Determination limit
The smallest amount of substance that can be titrated
with a good precision.

28 Basics of Titration METTLER TOLEDO

 To resume:

GLP ⇔ Formal framework,

regulations

Certification ⇔ Hardware

Validation ⇔ Chemistry

Qualification ⇔ Whole System

(Titrator, titration method,..)

METTLER TOLEDO Basics of Titration 29

 6. Chemical backgrounds
More information about chemical reactions can be found in
"Fundamentals of Titration" (ME-704153).
6.1 The mole
In chemical calculations, specific units are used to describe
a reaction. This is necessary since the number of atoms,
molecules or ions in 1 g of sample for example is ca. 1020.
This means that 1 atom weighs approximately 10-20 g, a
quantity with 20 decimal digits, i.e. a number on the
twentieth digit after the comma! Thus, chemical calculations
need more convenient units to calculate the amount of
reagents and products involved in a reaction.
The mole is the The base unit of chemical calculations are associated with
fundamental unit of the base quantity amount of substance and its base unit
chemistry mole of the International System of Units (SI) [4]. These
concepts are defined in [5].

Basic property Base Unit Symbol

Name
Length Meter m
Mass Kilogram kg
Time Second s
Electric current Ampere A
Temperature Kelvin K
Amount of substance Mole mol
Luminous intensity Candela cd

The mole is the amount of substance of a system that

contains just as many elementary chemical entities as there
are atoms in 12 g of the carbon 12C isotope. In addition, the
exact nature of the entities must be specified, e.g. atoms,
One mole contains
6.025•1023 elemen- molecules, ions, electrons. One mole of a substance con-
23
tary chemical entities tains 6.025 •10 elementary entities.

30 Basics of Titration METTLER TOLEDO

 Examples: n(HCl) = 2 mol
n(Ca2+) = 0.35 mmol

1 mole = The result of a titration is usually given in a more convenient

how many grams ? unit than moles, e.g. in grams or %. Thus, a conversion
factor is necessary to translate the result in grams. In
particular, the mass of 1 mole of elementary entities has
to be known. This is the molar mass M(X) of substance X.

Molar mass The molar mass of substance X is the mass of 6.025 • 1023
elementary chemical entities (1 mole) of this substance.
The unit is g/mol.

The atoms are the For instance, all chemical elements are composed of atoms
elementary entities of
chemical elements which are listed in the periodic table of elements. Each
element is given with its atomic mass, i.e. the mass of 1 mole
Atomic mass of atoms - the atomic mass - :

Iron (Fe) M(Fe) = 55.85 g/mol = 6.025 • 1023 atoms

Sodium (Na) M(Na) = 22.99 g/mol = 6.025 • 1023 atoms

Molecular mass The molar mass of 1 mole of molecules (molecular mass)

is calculated from the atomic mass of the components
according to the molecular formula:

Sulfuric acid (H2SO4 ) :

Atom Atomic mass Share Molecular mass
H 1.01 g/mol 2 x 1.01 g/mol = 2.02 g/mol
The sum of the
atomic masses gives S 32.06 g/mol = 32.06 g/mol
the molecular mass O 16.00 g/mol 4 x 16 g/mol = 64 g/mol

M(H2SO4) = (2.02 + 32.06 + 64) g/mol = 98.08 g/mol

METTLER TOLEDO Basics of Titration 31

 6.2 Equivalent number z*
In some reactions, e.g. HCl + NaOH, 1 equivalent of analyte
(HCl) reacts exactly with 1 equivalent of the titrant (NaOH):
HCl + NaOH H2O + NaCl

The ratio between HCl and NaOH is 1:1.

This is not always the case:

H2SO4 + 2 NaOH 2 H2O + Na2SO4

The ratio between 1 mole of H2SO4 reacts with 2 moles of NaOH, i.e. the ratio
the reagents is 1/2 . To get the same number of molecules of H2SO4 and
involved in the NaOH which react together completely, 1/2 mole of H2SO4
reaction is
not always 1:1 is needed for 1 mole of NaOH.

For this reason, it is useful to refer to fractions of amount of

substance. The fraction 1/z* is called the equivalent of the
amount of substance.

The number of equivalents z* - equivalent number -

indicates how many particles of titrant react with the analyte.
In the previous example, z* = 2 for sulfuric acid since it
releases 2 protons H+. The importance of the equivalent
number is illustrated in the next example:

K+ + MnO4- + 5Fe2+ + 8H+ K+ + Mn2+ + 5Fe3+ + 4H2O

Redox reaction: In this redox reaction, the permanganate ion MnO4- receives
reduction and 5 electrons from 5 iron ions Fe2+ (i.e. it is reduced by iron
oxidation reaction
ions). This means that the equivalent number of MnO4- is 5,
while z* = 1 for iron ion Fe2+ :

MnO4- : z* = 5 Fe2+ : z* = 1

32 Basics of Titration METTLER TOLEDO

 6.3 Concentration of a titrant
Based on the previous paragraph, the concentration of a
titrant should be specified as equivalent concentration.

Since 0.1 N KMnO4 could apply equally well to 1/3 KMnO4

and 1/5 KMnO4 a complete specification taking into account
the equivalent 1/z* of substance X is needed for an unam-
biguous concentration value.

Example: c(1/5 KMnO4) = 0.1 mol/L

c(1/z* X) is calculated as follows:

1. Concentration: c(1/z* X) = n(1/z* X) / V

2. Amount of substance : n(1/z* X) = z* · n(X)

of equivalents

3. Amount of substance : n(X) = m / M(X)

4. By inserting 2. and 3. in 1. :

c(1/z* X) = z* · n(X) / V = z* · m / M(X) / V

c(1/z* X) = z* · m
M(X) · V

m: mass of substance X
M(X): molecular mass of substance X

METTLER TOLEDO Basics of Titration 33

 Example: How large is the concentration c(1/6 K2Cr2O7)
of 1 g of K2Cr2O7 in 50 mL water ?

z* = 6
m= 1g
M(K2Cr2O7) = 294.185 g/mol
V= 50 mL = 0.05 L

z* · m
c(1/6 K2Cr2O7) =
M(X) · V

6 ·1
c(1/6 K2Cr2O7) =
294.185 · 0.05

c(1/6 K2Cr2O7) = 0.408 mol/L

Example: Preparation of 100 mL of a titrimetric solution

of sulfuric acid with a concentration of c(1/2
H2SO4) = 0.1 mol/L. What is the mass m of
sulfuric acid required?

z* = 2
c(1/2 H2SO4) = 0.1 mol/L
M(H2SO4) = 98.08 g/mol
V= 100 mL = 0.1 L

From c(1/z* X) = z* · m we obtain

M(X) · V
c(1/z* X) · M(X) · V 0.1· 98.08 ·0.1
m= =
z* 2

m = 0.4904 g

34 Basics of Titration METTLER TOLEDO

 6.4 Chemistry in titration
In this chapter, more information is given about the chemical
See also:
reaction occurring during titration of a sample.
"Fundamentals of
Titration"
(ME-704153) The law of mass action
Every chemical reaction proceeds to an exactly defined
equilibrium condition. During reaction, educts (reagents)
react to products and products react to educts until stability
Forward:
(equilibrium) between "forward" and "backward" reactions is
A, B --> X, Y reached. This status is called the chemical equilibrium:
v1
Backward: a··A + b··B x··X + y··Y
A, B <-- X, Y v2

a, b, and x, y are the numbers of moles of substances A,

B, and X, Y participating in the reaction in well-defined
proportions: The ratios of the substances involved in the
chemical reaction are defined by these numbers.

At equilibrium, the rates of forward and backward reactions

are equal (v1 = v2). It is described by the law of mass action:

Law of mass action [X]x · [Y]y

K = [A]a · [B]b (6.1)

The constant K is known as the equilibrium constant. [X]

and [Y] are the concentrations of X and Y, respectively.

In titration, the reaction has to proceed quantitatively and to

completion. This is fulfilled when K is very large so that the
equilibrium concentration of sample A (i.e., [A]) is infinitely
small compared to its concentration before starting analysis.

METTLER TOLEDO Basics of Titration 35

 The solubility product of salts
Salts like KCl, NaCl, KBr, ... dissolve in water and dissociate
in their respective ions (K+, Na+, Cl- , Br- ).

AB(solid) A+ + B- (6.2)

Sparingly soluble Many salts are only slightly soluble, e.g. barium sulfate
salts: (BaSO4) or silver chloride (AgCl). If solutions of the corre-
silver chloride, AgCl
silver bromide, AgBr
sponding ions are mixed in a glass beaker, precipitates are
silver iodide, AgI formed. The solid salt accumulates on the bottom of the
lead sulfate, PbSO4 glass. Ions from the salt constantly pass into solution, and
ions from the solution are incorporated in the solid salt.
For this equilibrium the following constant applies:

[ A+ ] · [ B- ]
K= (6.3)
[ AB ]

As long as solid salt AB is present as precipitate, the

concentration of AB remains constant and thus it can be
included into the equilibrium constant K.

Solubility productThis gives the solubility product Ksp :

Ksp = K ⋅ [ AB ] Ksp = [ A+ ]·[ B- ] (6.4)

The constant Ksp characterizes the solubility of a salt. The

lower the value of Ksp , the more insoluble the salt. Ksp shows
a large temperature dependence. In general, at higher
temperatures you can dissolve a larger quantity of salt.

Precipitation The low solubility of salts like AgCl, BaSO4 , and PbSO4 can
titration be used to perform precipitation titration.
Examples:
1. Salt content in food by titration with AgNO3
2. Sulfate determination by titration with BaCl2.

36 Basics of Titration METTLER TOLEDO

 6.5 The ionic product of water
When the conductivity of water is examined by very sensitive
instruments, even ultrapure distilled water has a conductivity.
This is due to the dissociation of water: a proton (H+) is
transferred from one water molecule to another.

H2O + H2O H3O+ + OH- (6.5)

This equilibrium is present in all aqueous solutions and can

be described according to eq. (6.1). In diluted solutions, the
concentration of water molecules remains constant. Thus,
the equilibrium constant K is simplified to:

Kw = K ⋅ [ H2O ]2 Kw = [H3O+]·[OH-] (6.6)

Kw is known as the ionic product of water. It depends on the

temperature and is constant in diluted solutions. Its value is
10-14 mol2/L2 at 25°C. This means that in a neutral solution
the concentrations [H3O+] and [OH-] are equal:

[H3O+] = [OH-] = 10-7 mol/L (6.7)

If one of the concentrations is known, the other can be

calculated from the ionic product since Kw is constant (10-14).
For instance, if [H3O+] is increased to 10-2 mol/L by addition
of acid, [OH-] decreases to 10-12 mol/L: 10-2 x 10-12 = 10-14
pH = - log [H3O+]
The measurement of one concentration H3O+ and its calcu-
Acidic: pH < 7 lation as pH = - log [H3O+] enables to determine whether a
Neutral: pH = 7 solution is acidic or basic. In acidic solutions, the pH is less
Basic: pH > 7 than 7, whereas in basic solutions it is over 7. The pH of a
neutral solution is 7.

Note that the presented concept of pH is defined only for

aqueous solutions. Thus, it is useless to calibrate the
electrode in organic solvents.

METTLER TOLEDO Basics of Titration 37

 6.6 The strength of acids and bases
An acid is a substance which donates H+ , whereas a base
accepts H+. Not every acidic solution dissociates its protons
completely. Each acid has a specific dissociation strength.

Examples:
1. strong acids: HClO4 , H2SO4 , HCl
2. weak acids: CH3COOH (acetic acid)

The reaction of weak acids (= weak dissociation) with water

is described by the equilibrium:
Equilibrium constant:
+ -
K = [H3O ] · [A ] HA + H2O H3O+ + A- (6.8)
[HA] · [H2O]
In dilute solutions, [H2O] is constant and the equilibrium
constant K can be simplified to:

[H3O+]·[A-]
Ka = (6.9)
[HA]

The constant Ka is known as the acidity constant of acid HA

and characterizes the acid strength. Strong acids have a
large acidity constant, weak acids a small one. The negative
logarithm of Ka is frequently employed:

pKa = – logKa

Polyprotic acids dissociate more than 1 proton:

for instance, phosphoric acid (H3PO4) dissociates 3 protons,
and sulfuric acid (H2SO4) dissociates 2 protons.This has to
be considered when choosing the correct value for z* in the
titration method:

H3PO4 z* = 3
H2SO4 z* = 2

38 Basics of Titration METTLER TOLEDO

 7. Glossary
Titration Quantitative chemical analysis. The amount of titrant is
determined which reacts quantitatively with the sample
compound to be analysed. From this volume (titrant con-
sumption) the amount of sample compound is calculated.
The calculation is based on the stoichiometry of the assay
reaction (Synonyms: volumetry, titrimetry).

Titrant Solution of a certain chemical reagent. Its concentration is

accurately known by standardization.

Primary Certified high purity substance which is used for the accurate
standard determination of the titrant concentration.

Indication Procedure to follow the reaction and to detect the end of the
titration, e.g. potentiometry (electrodes), or use of colour
indicators.

End of titration A titration is terminated when the desired endpoint or the

equivalence point is reached. The consumption of titrant to
this point is evaluated. Depending on the chemistry, more
than 1 equivalence point may occur during the same titration.

Equivalence The point at which the number of entities (equivalents) of the

point added titrant is the same as the number of entities of sample
analyte.

Analyte Specific chemical species of which the content in the sample

can be determined by titration.

Standardization Determination of the titrant concentration by using a highly

pure reference chemical substance (standard).

Stoichiometry Mole/mass relationships between reagents and products.

The reagents always react according to fixed relationships.

METTLER TOLEDO Basics of Titration 39

 8. Literature

[1] "Good Laboratory Practice in the Titration Lab"

Mettler-Toledo Titration Applications Brochure 14
ME-51724908, 06/97.

[2] "Guidelines for Result Check, Method Validation and

Instrument Certification"
Mettler-Toledo Titration Applications Brochure 15
ME-51724910, 05/97.

[3] "Validation of Titration Methods"

Mettler-Toledo Titration Applications Brochure 16
ME-51724908, 09/96.

[4] Bureau international des poids et mesures, le système

international d'unités (SI),
5th French and English Edition, BIPM, Sèvres 1985

[5] IUPAC Compendium of Analytical Nomenclature,

Pergamon Press, 1978,
page 175 ff. See also DIN 32625

40 Basics of Titration METTLER TOLEDO

 Notes

METTLER TOLEDO Basics of Titration 41

42 Basics of Titration METTLER TOLEDO
METTLER TOLEDO Basics of Titration 43
Subject to technical changes
© 1998 Mettler-Toledo GmbH, Analytical
P&D MarCom Schwerzenbach
Printed in Switzerland, 51725008

44 Basics of Titration METTLER TOLEDO