Introduction to

Volumetric Analysis
S.Y. B.Sc. Semester – IV
Dr. Ashwini Wadegaonkar
1. Introduction
2. Methods of expressing concentrations
3. Primary and secondary standard solutions
4. Apparatus used and their calibration: burettes, micro-
burettes, volumetric pipettes, graduated pipettes,
volumetric flask
5. Methods of calibration
6. Instrumental & non-instrumental analysis – Principles &
Types
Introduction

 Chemical analysis plays an important role in

study of composition or constituents of
substances or material.

 The chemical analysis is broadly divided into

two types

Qualitative analysis
Quantitative analysis
 The volumetric method involves measurement of
volumes of the reacting substances.

 The weight of the required constituents is indirectly

obtained by measuring the volume of a solution of
known composition required to react with a known
volume of a solution containing an unknown weight of
the desired constituent.

 This is done by a process known as titration which is

divided into four types depending upon the nature of
the chemical reaction. The four types are

a. Acid – base or neutralization methods

b. Precipitation methods
c. Complexometric methods
d. Oxidation – reduction methods
 The quantitative analysis is further classified into
two branches namely
Volumetric analysis
Gravimetric analysis
Volumetric analysis
 Volumetric analysis is also known as titrimetric analysis.
 The reagent (the titrant) is added gradually or stepwise to the analyte
from a burette.
 The key to performing a successful titrimetric analysis is to recognize the
equivalence point of the titration (the point at which the quantities of the
two reacting species are equivalent), typically observed as
a colour change.
 If no spontaneous colour change occurs during the titration, a small
amount of a chemical indicator is added to the analyte prior to the
titration.
 Chemical indicators are available that change colour at or near the
equivalence point of acid-base, oxidation-reduction, complexation, and
precipitation titrations.
 The volume of added titrant corresponding to the indicator colour change
is the end point of the titration.
 The end point is used as an approximation of the equivalence point and is
employed, with the known concentration of the titrant, to calculate the
amount or concentration of the analyte.
https://www.youtube.com/watch?v=Iurzrzwm9Fo

https://www.youtube.com/watch?v=d1XTOsnNlgg

https://www.youtube.com/watch?v=wRAo-M8xBHM

https://www.youtube.com/watch?v=YIYJr6WlfHA
 In volumetric analysis, concentration of
substances are found out by volume
determination.

 The unit used for measurement of volume

of a liquid or solution is “litre”.

 The litre is defined as the

‘volume occupied by one kilogram of water at the
temperature of its maximum density (4oC) and at
normal atmospheric pressure’.
 The millilitre is the thousandth part of a
litre.

 The cubic centimeter (cm3) is the volume

occupied by a cube such that each edge of
the cube is one centimeter in length.

 The relationship between millilitre and

cubic centimeter is
1000 ml = 1000.028 cc

 The term ml is more correct

 The precision of volumetric work depends
upon accuracy with which volume of
liquids can be measured.
 There are certain sources of errors which
must be carefully considered.

◦ Changes in temperature cause change in the

volume of glass apparatus and liquids.
eg. An ordinary glass flask of 1000ml volume
shows an increase of in capacity 0.025ml per
degree centigrade.

◦ There may be errors of calibration of the

apparatus
eg. the volume marked on the apparatus may not
be the true volume.

• Such errors can be eliminated only by

recalibrating the apparatus
 Methods of Expressing Concentration of
solutions

There are many systems of expressing the

contraction of solutions.
 Weight of solute present in a given volume of
solution
 Moles of solute present in one litre of solution,
called molarity
 Gram equivalents of solute present in one litre of
solution, called normality
 Percentage of solute by weight in a solution of
known specific gravity
1. Weight of Solute per Unit Volume of
Solution

In preparation of solution using this system, a

known weight of the solute is dissolved and
diluted to known volume.
If accuracy is required, the solute is weighed
and transferred to a volumetric flask, and
diluted to a known volume.
The concentration is usually expressed as grams
of solute per millilitre of solution.
Any multiple or fractional part of such solution
will contain a known weight of solute.
2. Molarity
a. A mole : The molecular weight expressed in grams
of any substance is called as mole or gram
molecule of the substance. For expamle, sodium
chloride has molecular weight 58.5g of sodium
chloride means one mole of it.
b. Millimole : The mole is very large unit, hence a
smaller unit which is one thousandth of it, known
as millimole is used. Thus 1 mole = 1000
millimoles.
c. Molar Solution : A molar solution is defined as the
solution containing one mole of the solute in a litre
of its solution. For example 40g of NaOH is one
litre of solution is called as 1M NaOH solution

Weight of solute in grams

Number of Moles = --------------------------------
Molecular weight of the solute
Molarity of Solution : It is defined as the number of
moles of the solute present in one litre of its solution. It
can also be defined as number of millimoles of a solute
present in one millilitre of its solution.

Number of moles of the solute

Molarity = --------------------------------------
Volume of the solution in litre

Number of moles = Molarity x Litre

Number of millimoles of the solute

Molarity = ------------------------------------------
Volume of the solution in millilitre

Number of millimoles = Molarity x MilliLitres

3. Normality
The concentration of solution can also be expressed in terms
of normality.
Various terms involved in it are -

Equivalent Weight :
The equivalent weight of a substance (element or
compound) as:
“The number of parts by weight of it, that will combine with
or displace directly or indirectly 1.008 parts by weight
of hydrogen, 8 parts by weight of oxygen, 35.5 parts by
weight chlorine or the equivalent parts by weight of another
element”.
 Milliequivalent Weight : It is obtained by dividing
the equivalent weight by 1000.

 Gram Equivalent Weight : It is the equivalent

weight expressed in grams

Equivalent weight of a substance = 1 equivalent of a

substance = Equivalent weight of substance in grams

 Milligram Equivalent Weight : It is obtained by

dividing the gram equivalent weight by 1000.
Normality of Solution : Normality is a system of expressing
concentration based on number of equivalents of solute
present in one litre of solution or the number of
milliequivalents of solute present in one millilitre of a
solution.

Number of equivalents of the solute

Normality = -------------------------------------------
Volume of titration in litre

Number of milliequivalents of the solute

= -------------------------------------------------
Volume of the solution in millilitre

Number of gram equivalents = Normality x Litres

 https://www.youtube.com/watch?v=KLjWa9cE2uk
(molarity made easy)
 https://www.youtube.com/watch?v=hQrih9m_nmQ
 https://www.youtube.com/watch?v=QCZMyx_557I
 https://www.youtube.com/watch?v=fDh30u-c0Sc
 https://www.youtube.com/watch?v=0MwIMhcAWLQ
(normality and equivalent weight)
Primary and Secondary Standard Solutions

 The standard solution is prepared by dissolving an accurately

weighed quantity of a highly pure material called a primary
standard and then diluting to an accurately known volume in a
volumetric flask

 If material is not sufficiently pure then solution is prepared to

give approximately the desired concentration and this
standardized by titrating a weighed quantity of a primary
standard.
 https://www.youtube.com/watch?v=xKH2AvS_sOk
 The primary standard should fulfill the below
requirements
◦ It should be 100% pure
◦ It should be stable to drying temperatures and it
should be stable indefinitely at room temperature.
The primary standard is always dried before
weighing.
◦ It should be easily and readily available
◦ Although not necessary it should have a high
formula weight.

 This is so that a relatively large amount of it will

have to be weighed to get enough to titrate.
 The relative error in weighing a greater amount
of material will be smaller than that for small
amount
 Preparation of Standard Solution
◦ In case of volumetric analysis, the final result
depends upon the accuracy with which the
standard solution is prepared.
◦ The concentration of standard solution is
established by direct and indirect method.

 Direct Method of Preparation of Standard

Solution (Primary Standard)
◦ In order to prepare a standard solution, the
substance is weighed accurately equal to an
equivalent, or a definite fraction or multiple of
an equivalent, dissolved in water and diluted to
a known volume.
 Indirect Method of Preparation of
Standard Solution (Secondary Standard)

◦ The process of determining the concentration of a

solution by titrating it against a solution of a pure
substance of known concentration is called as
standardization.

◦ Thus the exact concentration of the secondary

standard solution is determined by titrating it against
a primary standard solution.

◦ The secondary standard solution may be further used

for standardization of other solutions.
Equivalent weight in different types of
reactions

◦ There are various types of chemical reactions. The

equivalent weight varies with the type of reaction.
◦ Same compounds may have different equivalent weights
in different chemical reactions.
◦ Hence normality of a particle solution may also be
different in different chemical reactions.

◦ Equivalent weight in different types of chemical reactions

is discussed as shown below
 Neutralization Reactions
 Complex Formation and Precipitation Reactions
 Oxidation – Reduction reactions
 Neutralization reactions
◦ In reactions between acids and bases, one equivalent is
the weight of the reagent which contains or reacts with
one gram atom of replaceable hydrogen (1.008g) or with
one gram molecule of hydroxyl (17.008g).
Molecular weight of acid
Equivalent weight of acid = ----------------------------
Basicity of that acid

◦ The basicity is defined as the number of replaceable

hydrogen atoms present in one molecule of that acid.
◦ The term acidity is defined as the number of
replaceable hydroxyl ions present in one molecule of
that base

Molecular weight of base

Equivalent weight of acid = ----------------------------
Acidity of that base
 Complex Formation and Precipitation
Reactions

◦ The equivalent weight of complex

formation and precipitation reactions is
the weight of the substance that contains
or reacts with 1g atom of a monovalent
cation M+, ½ g atom of bivalent cation
M2+, 1/3g atom of a trivalent cation M3+
and so on.
◦ The equivalent weight of cation is equal to
its atomic weight divided by valency.
• The equivalent weight of a substance in complex
formation reaction can be determined by writing
down the ionic equation of the reaction

2KCN + AgNO3  K [Ag(CN)2] + KNO3

i.e. 2CN- + Ag+ [Ag(CN)2]-

 Calibration
 Calibration of measuring instruments

 https://lab-
training.com/2015/01/06/volumetric-
apparatus-use-calibration/

 https://pharmapathway.com/calibration-
procedure-volumetric-glassware/
Instrumental analysis
 Instrumental analysis is a field of analytical chemistry that
investigates analytes using scientific instruments.

 Instrumental chemistry involves the use of complex

machines within the field of analytical chemistry.

 This field uses instruments to analyze particles and

molecules. Part of analytical chemistry is exploring how
these instruments work within the framework of research.

 Two common methods of instrumentation are

spectroscopy and mass spectrometry. Spectroscopy uses
electromagnetic radiation, while mass spectrometry uses
magnetic and electric fields.

 Instrumental chemistry is utilized within the food,

pharmaceutical, medical and environmental industries.
 The instrumental methods of chemical
analysis are divided into categories
according to the property of the analyte
that is to be measured.

 Many of the methods can be used for both

qualitative and quantitative analysis.

 The major categories of instrumental

methods are the spectral, electroanalytical
and separatory.
 The possibility to realise analyses on small and
very small samples is one of advantages of
instrumental methods in comparison with
chemical methods.

 Both chemical and instrumental analysis

methods have a series of limitation, every of
them having advantages and disadvantages
Advantages of Instrumental methods of analysis

 UV visible spectrometry a small amount of the sample is

required for analysis
 Determination by instrumental method is considerably fast
 Complex mixture can be analyzed either with or without their
separation
 Reliability and accuracy of results are obtained by
instrumental method
 When non-instrumental method is not possible, instrumental
method is the only answer to the problem
Limitations of Instrumental methods of analysis

 In general instrumental methods are costly

 Require maintenance
 Also require trained personnel for handling
 The sensitivity and accuracy depend upon the type of the
instrument
 Specialized training for handling instrument is required
 There is frequent need of checking results with other
methods
 In some cases instrumental method may not be specific
List of Instrumental methods of analysis

 UV visible spectrometry  Mass spectometry

 IR spectrometry  Polarography
 Atomic Absorption  Raman spectroscopy
spectrophotometry (AAS)  Flame photometry
 Nuclear magnetic resonance  Radiochemical methods
spectrophotometry
 Potentiometry
 Emission spectroscopy
 Electrogravimetry
 Fluorometry
 Nephelometry
 Turbidimetry
 Refractometry
 Conductometry
 X – ray diffraction
 Polarimetry method
Instrumental methods

Spectral Electro- analytical Separatory

•Absoptiometry •Conductometry •Chromatography

•Nuclear Magnetic Resonance •Voltametry •Mass spectrometry
•Thermal analysis •Polarography
•Infra Red •Electrogravimetry
•UV spectrophotometry •Coulometry
•X-ray absorption •Amperometry
•Turbidimetry •Potentiometry
•Nephelometry
•Refractometry
Non instrumental analysis

 The chemical methods (gravimetric and titrimetric) from

ensemble of quantitative analysis methods are
corresponding to macro scale determinations while
instrumental methods are used for quantitative
determinations starting with semi–microscale.
Chemical methods
(Non instrumental analysis)

The chemical methods have advantages:

 The necessary equipment is very expensive;

 The methods are based on absolute
measurements;
 Procedures are simple and precise
The chemical methods have disadvantages:

 The precision decrease with decrease of sample

amount;
 The realisation of an analysis is realised in a enough
long time period;
 They aren’t flexible;
 They are pollutant for environment;
 Sometimes they aren’t specific