Capitulo 1

INTRODUCTION TO ANALYTICAL CHEMISTRY
Analytical Chemistry
Analytical chemistry is concerned with the science of chemical identification and
determination of the composition of substances and materials and their chemical structures. The
main aim of analytical chemistry is to develop scientifically substantiated methods that allow the
qualitative and quantitative evaluation of materials with a certain accuracy. Thus, analytical
chemistry provides the methods and tools needed for insight into our material world.
According to the means by which an analytical aim can be' achieved, the analytical methods
can be divided into the following types :
1. Qualitative Analysis : This includes methods for the identi ficatiol1 or detection methods
for the Wlalysis of an unknown substance. It also includes the study of its qualitative
composition according to which the material is placed in a certain group of the
substances. If the type of substance is known (mineral, salt, alloys, etc.), qualitative
analytical methods are used to establish : .
(i) The substance the analysed material is composed of, e.g., identification of the
grade of an alloy.
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(ii) The presence or absence of certain chemical elements in the material.

2. Quantitative Analysis : This is concerned with the determination of the total contents
of elements, ions or the simplest compounds which constitute the product concerned.
Thus, the quantitative analysis seeks ever improved means of measuring the chemical
composition of natural and artificial materials. The techniques are available which are
used to identify the substances which may be present in a material and to determine
the exact amounts of the identified substances.
3. Phase Analysis : The quantitative molecular composition of products is established
by phase analysis whose methods are specific for an individual kind of material.
Analytical chemistry is related to exact sciences and primarily to mathematics. Analytical
results are usually expressed graphically because mathematical functions are used for estimating
the accuracy of results provided by analytical methods and for revealing errors of determination.
Dielcometry deals with analytical methods based on statistical properties of substances in the
bulk. The relation of analytical chemistry to physics is expressed by the increasing application
of physical methods of analysis based on the processes of inner electronic and nuclear levels of
atoms, e.g., mass s'pectrometry, X-ray analysis, etc. .
Chatwal, Gurdeep R., and Madhu Arora. Analytical Chemistry, Himalaya Publishing House, 2008. ProQuest Ebook Central,
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1-2 Introduction to Analytical Chemistry
Role of Analytical Chemistry

Analytical chemistry emphasizes the development of great diversity of analytical methods
and their various combinations with separations 'a nd concentration methods. These methods and
their practical applications could be evaluated by studying their physico-chemical and chemical
nature taking into consideration the general regul,ariti,es that determine the procedure of measuring.
Analytical chemistry plays an important role in almost all aspects of chemistry, e.g., clinical,
agriculture an.d food science, environmental science, forensic science, industrial chemistry,
metallurgical science and pharmaceutical science.
The v,arious roles of analytical chemistry are qutlined as follows :
1. Clinical Tests : Previously, the doctors made diagnosis c;>f the disease on the basis of
symptoms, qualitative clinical results and/or X-ray examinations. Now sensitive chemical
and instrumental tests have been devised so as to detect abnormal and norinal
components of body fluids because diseases are accompanied by chemical changes
occurririg in the metabolic fluids. These test results are very useful for the doctors in
diagnosis of the diseases. These tests are usually carried out with blood and urine
samples to find out the percentage of glucose, urea, nitrogen, protein, sodium, potassium,
calcium, uri~ acid, etc. in blood and urine.
Clinical analysis is also helpful in the diagnosis of specific metabolic diseases. It is
known that one in 10,000 new born bodies the enzyme phenylalanine hydroxylase is
not present and its absence leads to partial developed brain and mental retardation.
This disease is known as phenyl ketonuria and is because of an excess of phenyl
pyruvate in the urine, In the urine of new born baby, phenyl pyruvate is detected by
treating urine samples will FeCl 3 reagent. The appearance of a green blue coloration
confirms the presence of phenyl pyruvate.
2. Quality Control of Drugs: Analytical chemistry is successfully used 'to ascertain the
quality of the manufactured drug in tablets, solution and emulsion form. The quality
of drug affects the therapeutic value. In pharmaceutical studies, it is important to
establish the properties and therapeutic value of a drug before the drug is approved
and made available to the patients.
3. Role in Industry: Analytical chemistry provides vital role in industry. It provides the
means of testing the raw materials, the intermediate compounds and finished products
as well as the analytical control of the technological process. For example, ferrous
metallurgy requires several analytical tasks such as the control of minerals, concentrates,
charge, molten steel, steels of various grades, refractory materials, fluxes, exhaust
gases, sewage etc. Similarly, non-ferrous metallurgy requi~ .•several analytical tasks.
As a result, it is essential for a metallurgical engineer t~Jlave a clear understanding
- of the modem methods of analysing raw materials and pfbducts as well as *e methods
for the control of technological processes. Similarly, ~~ quality of finished products
such as household products, fuels, paints, etc.; can 9.e analysed by the procedures
developed by analytical chemists before selling to the consumers.
I
Analytical methods in industry are worked out in field research institutes and' plant
laboratories
Chatwal, Gurdeep R., and Madhu Arora. Analyticalfor each type
Chemistry, ofPublishing
Himalaya material. Analytical
House, 2008. control
ProQuest Ebook Central, should be characterised by
Introduction, to Analytical Chemistry 1·3
a short duration of analysis, high selectivity, accuracy and sensitivity, reductionlh

man-power and power saving. It is possible to control all these demands by introducing
the technical means of analytical control i.e., mechanisation, instrumental methods,
automation and computers.
Depending on the material under analytical control and aim of analysis, the marking
analysis and the quick analysis are employed. Marking analysis is used to evaluate
the quality of semi finished and finished products and then- compliance with the accepted
standards. On the other hand, the quick analysis is employed for the routine control
of semi finished and finished products. The quick analysis is carried out by using
.'volumetric, spectrophotometric and some physicochemical methods.
4. Environmental Quality: It is usually evaluated by testing the suspected contaminants
by using the various techniques of analytical chemistry.
5. Food Analysis: The nutritional value of food is found out by chemical analysis for
major components such as proteins, carbohydrates, vitamins and trace minerals. Also,
the calories in food are usually calculated from its chemical analysis.
6. High Purity Materials : It is not possible to obtain high purity materials unless
production processes are provided with analytical control methods at each important
stage.
7. Miscellaneous Applications: An analytic,al chemist also makes important contribution
to fields as diverse as forensics, archaeology and space science.
Classification on Analytical Methods

The classification of analytical methods is done according to the property that is observed
in the final measurement process. On this basis, the analytical methods are divided into two large
classes:
1. Classical or chemical methods
2. Instrumental or physicochemical methods of analysis
Let us discuss these one by one.
1. Classical or Chemical Methods

These depend on analytical chemical reactions. In qualitative analysis identification methods
involve reactions producing external effects, such as formation of precipitates or coloured solutions,
ga'S evolution, change in colour of the material being analysed, etc. In quantitative analysis,
chemical reactions help in measuring the amount of reaction product oTofthe reagent consumed.
Examples of classical methods are as follows :
(i) Volumetric analysis
(ii) Gravimetric analysis
(iii) Gas analysis
1-4 Introduction to Analytical- Chemistry
\ .
Volumetric analysis is known as titrimetric analysis. It involves the measurement of the
volume of reagent of exactly known concentration used up in the titration. The equivalence point
should be detected. Equivalence point is the moment when the amount of standard solution added
IS equivalent to that of the substance being determined. The equivalence point can be determined
by:
(i) A change in the colour of the reactants themselves or indicators which are introduced
into the analytical solutions.
(ii) A change IS some physicochemical properties of the analyt measured instrumentally.
If an indicator is used in volumetric titration, a sharp change in the colour of an
mdicator indicates that the end point is reached. However, the end point and the
equivalence point of the titration may not be identical because the end point depends on:
(i) The indicator used,
(ii) The properties of the titrant and the standard solution, and
(iii) The properties of the reaction products.
A wide variety of the types of chemical reactions can be followed by titration methods such
as neutralisation reactions, oxidation-reduction reactions, precipitation reactions and complex
formation reactions.
-
Gravimetric method depends on the conversion of the substance concerned to an insoluble
reaction product of definite chemical composition and an accurate determination of its mass. This
method is used for the estimation of various cations and anions, e.g., Ba2+, SOl-, Ag+, Cl-, Pb 2+,
Ni2+ , Zn 2+, Mn2+ , Cu2+, CrO42-' etc .
Gas analysis is a special type of quantitative analysis which is based on the measurement
of the volume or mass of the gas driven off from the analysed sample. Gas analysis is used for
controlling many industrial processes such as the analysis of flue gases, original gas materials
and the products of their chemical conversion. This process is also used for determining elements
such as sulphur, nitrogen, phosphorus, arsenic, etc.; which forms persistent gases.
The apparatus needed for classical methods is cheap and readily available in all laboratories.
There is need to calibrate a sample of known composition. The classical methods are suitable for
non-routine and occasional analysis. The classical methods are often simpler because there is no
need in taking the trouble of preparing requisite standard and carrying out the calibration of an
instrument.
Advantages of Classical Methods

(i) Procedure is simple and accurate.
(ii) Equipment needed is cheap and readily available in all laboratories.
(iii) Methods are based on absolute measurement.
(iv) Specialised training is usually not required.
(v) There is no need to calibrate a sample of known composition.
(vi) These methods are suitable for a non-routine and an occasional analysis.
Introduction to Analytical Chemistry 1'5
Limitations or Disadvantages of Classical Methods

(i) Procedure is time consuming.
(ii) There is a lack of versatility.
(iii) There is a lack of specificity.
(iv) Accuracy decreases with decreasing amounts.
(v) Chemical environment is critical.
2. Instrumental or Physicochemical Methods of Analysis

These are concerned with the measurement of certain physical parameters of a chemical
system that are dependable on the nature of the system components and vary in the process of
reaction. These parameters include electric potential, electrical conductance, electrical current,
quantity of electricity, absorption of radiation, emission of radiation, scattering of radiation,
refraction of radiation, rotation of radiation, diffraction of radiation and thermal properties.
Table 1 lists the various instrumental methods used in analysis.
Table 1
Physical property measured 7nstrumental methods based on

measurement of property
1. Electrical potential, electrical conductance, Conductometry, potentiometry voltammetry, chronopoten-
electrical current, quantity of electricity etc. tiometry. Polarography, amperometry and coulometry,
(electrometric or electroanalytical methods).
2. Absorption of radiation. Spectrophotometry (X-ray, UV, Visible, IR, colorimetry,
atomic absorption, nuclear magnetic resonance and electron
spin resonance).
3. Emission of radiation. Emission spectroscopy, flame photometry, fluorescence,

radiochemical methods.
4. Scattering of radiation. Turbidimetry, nephelometry. Raman Spectroscopy.
5. Refraction of radIation. Refractometry, interferometry.
6. Rotation of radiation. Polarimetry, optical rotatory dispersion.
7. I?iffraction of radiation. X-ray electron diffraction methods.
8. "Mass to charge ratio. Mass spectrometry.
9. Thermal properties. Thermal conductivity and enthalpy methods.
Instruments used in instrumental methods are .expensive and their use will be justified if
numerous samples have to be analysed or when dealing with the determination of substances
present in minute quantities (trace, subtrace, ultratrace analysis), with instrumental methods, it
becomes necessary to carry out a calibration operation using a sample of material of known
composition as reference substance. Instrumental m~thods are ideal suited to the performance of
a large number of determinations.
1'6 Introduction to Analytical Chemistry
Advantages of Instrumental l~/ethods
(i) Instrumental methods of analysis are usually much faster than purely classical methods.
(ii) Instrumental methods of analysis are nonnally applicable at much lower concentrations
of the samples than classical methods.
(iii) High sensitivity of instrumental methods can be attained.
(iv) Complex samples can be handled by instrumental techniques.
(v) Instrumental methods have wide applications in industry.
(vi) In most cases a microcomputer can be interfaced to the instrument so that all the
curves can be plotted automatically and whole analytical process may be automated
completely.
Limitations of Instrumental Methods

(i) An initial or continuous calibration is necessary.
(ii) The sensitivity and the accuracy depend upon the ins~ments or wet chemical methods.
(iii) The cost of instrument is large and most of the college labs are unable to purchase them.
(iv) The concentration range is limited.
(v) Sizable space is required.
(vi) Specialised training is required.
Differences between Classical and Instrumental Methods

The various differences between classical and instrumental methods are given in Table 2.
Table 2
Classical Methods Instrumental Methods

1. The apparatus needed for classical methods 1. The instruments needed for instrumental methods
is cheap and readIly available in all laboratories. are expensive.
2. In classical methods, it is not necessary to 2. In the instrumental methods, it is necessary to carry
cahbrate a sample of known composition. out a calibration operation using a sample of material
of known composition as reference substance.
3. The classical methods are suitable for non- 3. The instrumental methods are ideally suited to the
routine as well as occasional analysis. performance of a large number of routine determina-
tions.
From the above differences it could be concluded that classical and instrumental methods
are supplementing each other.
Types of Instrumental Analysis

In instrumental analysis, a physical property of a substance is measured to detennine jts
chemical composition by employing special instruments (potential, current, conductance, absorption
and emission spectra, etc.) .. Physical properties are of two types, namely specific and non-
Introduction to Analytical Chemistry 1-7
specific. A direct measurement is, however, possible if the measured property is specific for the_
substance being measured. If no specific property is available, the measurement of two or more
non-specific properties may allow correction for interfering substances. Instrumental methods are
based on the theory of relations between the content and the corresponding physicochemical and
physical properties of the chemical system being analysed. Changes in the system properties may
be either detected or recorded through the measurement of current, electrode potential, electric
conductance, optical density, refractive index, etc.; with suitable and sensitive instruments.
It is possible to divide instrumental analysis into two types such as direct or indirect,
depending on the procedure of the determination. In direct instrumental analysis, a substance is
determined directly by measuring some property of the system. In indirect instrumental analysis,
a change in property is used for detecting the end point of a chemical reaction, i.e. it serves as
a peculiar sensitive indicator.
Instrumental methods of analysis can be classified into two broad groups: spectral (optical)
and electrochemical methods.
The instrumental optical methods are based on the relation between optical properties of a
system and its composition. The electrochemical methods are based on the interdependence of
electrochemical properties and composition of the system. In addition to these groups, radiometric,
mass spectral and a number of other methods have also been used widely in quantitative analysis,
and. their number is fast growing day by day. Physical and physicochemical methods are highly
sensitive and rapid and so permit the determination of ultrasonic amounts of substances as little
as 10-7 or even 10-9 percent.
Table 3 : Classification of Instrumental Methods of Chemical Analysis
Methods Quantity or Property Phenomenon underlying

measured the method
(A) t<;lectrochemical Methods Mass of the deposited substance. Change in the electrical properties
of they system.
(a) Electrogravimetry Electrolysis Deposition of matter on an elec-
trode under electrolysis conditions.
(b) Coulometry Quantity of electricity. -Same-
(c) Potentiometry Electrode potential. Change in the electrode potentials
of a system in the course of a
chemical reaction.
-(d) Conductometry Electrical conductivity Change in the electric conductivity
Electric resistance. of a solution in the course of a
chemical reaction.
(e) Polarography Current, voltage. Electrode polarisation.
(B) Optical Methods Interaction of matter with electro-

magnetic radiation.
(a) Emission spectroscopy Position and intensity of spectral Appearance of emission spectra
lines. because of high temperatures.,
l·S Introduction to Analytical Chemistry
Methods Quantity or Property Phenomenon underlying

measured the method
(b) Luminescence Analysis Intensity of emission. Emission of electromagnetic energy
by matter caused by UV radiation.
(c) X-ray spectroscopy
,
Position and intensity of Emission of X-ray spectrum by
spectral lines. atoms under the influence of X-rays.
(d) Raman spectroscopy Position and intensity of Absorption of monochromatic
spectral lines. radiation by matter and subsequent
emission of new radiation differing
from that absorbed by the wave-
length.
(e) Atomic absorption Intensity of absorption. Absorption by atoms in the source
spectroscopy of excitation of monochromatic
radiation.
(j) Absorption spectrophoto- Optical density of the Absorption of poly- and monO-chro-
metry (photometry, colori- solution. matic radiant energy by molecules
metry, photoelectron and ions present in solution.
colonmetry)
(g) Turbidimetry Optical density of the medium. Absorption and scattering of a light
beam by non-homogeneous or turbid
media.
(h) Mass spectrometry Position and intensity of signals Ionisation of atoms, molecules and
in mass spectrum. and ions upon a combined action of
of electric and magnetic fields and
the appearance of mass spectra.
(i) Nuclear magnetic resonance Position and intensity of lines Nuclear magnetism (resonance
of the NMR spectrum. absorption of electromagnetic radia-
radiation by matter in a constant
magnetic field).
(j) Nephelometry Optical density of the medium. Scattering and reflection of a light
beam by non-homogeneous media or
colloidal solution.
(k) Refractometry Refractive index. Refraction of light by matter.
(C) Radiometric: Methods Radioactivity. Conversion of stable isotopes of an

element to radioisotopes upon radia-
tion of matter by nuclear particles.
Isotopic Dilution Radioactivity. Change in specific activity of the
compounds labelled with a radio
isotope.
Many instruments, which are used in instrumental methods, are expensive and their use will
only be justified if numerous samples have to be analysed, or when dealing with the determination
of substances present in minute quantities (trace, subtrace, ultratrace analysis).
With instrumental method, it is necessary to carry out a calibration operation using a sample
of material of known composition as reference substance.
Introduction to Analytical Chemistry 1·9
An instrumental method is ideally suited to the performance .-o-~ a large number of routine
determinations.
Various Instrumental Techniques

The most important instrumental techniques used in an analytical laboratory are gravimetric,
titnmetric, mass spectral, X-ray spectral, photometric, polarographic and radioactive methods.
The principle of gravimetric methods is based on the measurement of mass by making use
of law of conservation of mass in chemical reactions. By using suitable or ·appropriate reactions,
the required chemical element can be reduced or converted into a compound having known
composition with the desired properties. In gravimetric determination, the composition of the
weighing form must correspond to the chemical formula and the weighing form should be stable
to w:ashing, drying, weighing etc. Gravimetric methods are used for analysing rare elements if
high accuracy is deSIred. The gravimetric methods are, however, time consuming .
. Titrimetric methods are based on oxidation-reduction reactions, precipitation reactions
and 'complex formation reactions. Complexometric methods are of great significance. Accurate
results can be obtained with methods based on stoichiometric reactions which proceed almost to
completion at sufficiently high rates. In order to know the equivalence point, suitable indicators
are used. In the absence of suitable chemical indicator, the equivalence point is found out by
various instruments. When the equivalence point is approached, the concentration of the desired
element sharpy gets decreased and the concentration of the reagent sharply gets increased. At the
same time, the electrode potential, the conductivity of the solution and the diffusion current or
absorption sharply change. These changes can be determined instrumentally and can be used for
detecting the equivalence point during titration. In some cases, the changes in radioactivity,
freezing point, density, surface tension, refractive index or viscosity are also being used.
The instrumental methods used for measuring the equivalence point are potentiometric and
amperometric methods. The amperometric method is used to detect the equivalence point in
precipitation reactions, oxidation-reduction reactions and complexometric reactions.
The conductometric and high frequency titration methods do not find much applications In
the analytical chemistry of rare elements .
•
]\s compared to many gravimetric methods, the titrimetric methods are highly selective.
Furthermore, they are time consuming. However, these methods are less accurate.
The most popular electrochemical method has been polarography with a dropping mercury
electrode or with a platinum wire micro-electrode. The technique finds use'in theoretical research
as well as for practical and rapid analysis. For example, the polarographic method is used for
determining indium in polymetallic ores and in the products of its conversion, titanium and
germanium in various materials, and niobium in tantalum and in tantalum containing materials.
Oscillographic polarography is used for determining niobium in its alloys with tantalum and
yttrium in the pressure of erbium.
The coulometric method is very sensitive and accurate. It is successfully used for determining
uranium and some other elements.
The photometric methods involve the measurement of light absorptions in solutions in the
visible or UV region of the spectrum (colorimetry and spectrophotometry) or in suspensions
1-10 Introduction to Analytical Chemistly
(turbidimetry) or of light scattering in suspensions (nephelometry). Determining the absorption

of a solution on a spectrophotometer is generally the concluding stage of the determination.
Spectrophotometric methods are used for determining traces of elements in different industrial
materials, e.g., in semiconductors, metals and alloys. Photometric methods are used for determining
small amounts of various rare elements like beryllium in tungsten and its alloys, gallium, indium,
thallium, rare earths, and germanium in various objects; titanium in rocks, ores, alloys, tungsten
and zIrconium; vanadium in ores, minerals, alloys, steels and zirconium. For determining large
quantities of rare elements to a high degree of accuracy, differential spectrophotometry is employed.
Titanium, tantalum and rhl!!!!l.'ITl ~an be determined by this method.
X-ray ,spectroscopy is highly selective, yet it is of comparatively low sensitivity. This
method is used for determining elements having similar chemical properties like niobium and
tantalum, zirconium and hafnium, or rare earth elements.
The principle of ordinary spectral analysis is based on the capacity of atoms to emit certain
wavelengths in conditions of constant excitation. The arrangement of lines in the spectrum
reveals the presence of an element in the given material. The intensity of the lines reveals its
concentration. The spectral method is used to determine lithium, beryllium, scandium and rare
earth elements, gallium indium, thallium, germanium, zirconium, hafnium, niobium and tantalum
in rocks, concentrating products, alloys, etc.
Flame photometry is used for determining lithium, rubidium, caesium, strontium in rocks
and minerals, lanthanum, europium, yttrium and ytterbium in rare earth oxides and indium,
gallium and thallium in concentrates and intermediates.
In nuclear absorption or absorption flame photometry, the solution is sprayed in a flame
and the absorption of the radiation from a standard source by the atoms of the sought element
can be determined. The method is used to determine elements which are present in the flame as
free atoms. The sensitivity of this method is more than that of ordinary flame photometry. This
technique is used to determine elements which could not be determined by flame photometry
(e.g. selenium, tellurium, bismuth).

Methods based on measurement of the radioac~ivity of elements with natural radioactivity
(radium, radon, uranium, thorium, potassium, rubidium, samarium, etc.) are used for the measure-
ment of these elements or the products of their redioactive decay in a state of equilibrium with
the original elements (after their separation). The method is effectively used for the measure-
ment of thorium in ores, minerals, rocks and soils. Artificial radioactive isotopes of various
elements (labelled atoms) are used for controlling the separation of substances by precipitation,
extraction, adsorption, electrolysis, and other methods. The labelled atoms are also used as
tracers in various fields, for example.
(a) Measurement of the solubility of salts.
(b) Completeness of precipitation.
(c) Studying adsorption, coprecipitation and extraction.
(d) Measurement of\ stability of complex compounds.
Dilution with radioactive isotopes is also used. Impurities present in various materials, can
be detected by the formation of radioactive isotopes during their bomba{dment mainly with
Introduction to Analytical Chemistry HI
l1eutrons (radioactive method). The method is used to measure the elements for which artificial
radioisotopes could be prepared. The radioactivation method is used for determining impurities
in chemical compounds, metals and alloys, for controlling the purity of materials used in nuclear
reactors, for measuring lithium and rubidium in rocks, beryllium in mineral raw materials and the
products of hydrometallurgy and for measuring rare earth elements. The sensitivity of radio-
activation analysis increases with the intensity of the activating current of neutrons. The sensitivity
of activation analysis is more than that of spectrophotometric, spectrographic, amperometric or
chemical methods based on using coloured reactions.
The principle of adsorption chromatography is based on different adsorbing abilities of
substances. Solvents should be adsorbed much more slowly than the other components of the
mixture. The separating power of the adsorbent will then be used most effectively. The principle
of partition chromatography is based on different distribution coefficients of the substances
which are to be distributed between two immiscible phases, one of which (the stationary phase)
is! the sorbent with pores, whereas the other phase (mobile phase) is the moving solution. The
sorbent, retaining the liquid phase, is a hydrophilic substance of the silica get type (with large
pores to decrease the adsorption effect) or starch. Water, methyl alcohol or nitromethane are
usually used' as the stationary phases. Partition chromatography is being used for separating
niobium and tantalum from titanium.
Paper chromatography is a form of partition chromatography in which paper pulp or sheets
of paper are used. The efficiency of separation by this technique is dependent on the difference
in the rate of movement of the components of the mixture and that of the solvent. Paper
chromatography is being used for the separation of rare earths.
The principle of ions exchange chromatography has been based on the different ability of
ions to exchange for mobile sorbent ions. Synthetic organic ion exchange resins (cation and anion
exchangers) are usually used. Ion exchange chromatography is used for separating zirconium
from hafuium and other elements, rhenium from molybdenum, titanium from molybdenum, thorium
from rare earths, etc. Separation on strongly basic anion exchange resins is also developed and
so indium can be successfully separated from AI, Fe and As by making a hydrochloric acid
solution to pass through a column packed with a strongly basic anion exchanger. Further advances
in the analytical chemistry of rare elements have been found to depend to a great extent on the
successful development of the theoretical principles of analytical method.
Sensitivity and Detection Limits

The sensitivity ~S) of an analytical method or instrument is defined as the ratio of the
change in the response (R) to the change in the quantity or concentration (C) that is measured.
Thus, it can be written as follows :
dR Llli.
s=- or -
dC AC
The sensitivity S, depends upon the various experimental conditions. The maximum sensitivity
<;>f a method is expressed in terms of detection limits. The latter is defined as the quantity or
concentration of a substance for which an analytical signal just disappears when the amount
present tends to approach zero. The relative ultimate sensitivities of different methods of analy~is
can not be generalized due to the fact that data may vary widely from one substance to ~nother.
F W Karasek has compiled detection and identification limits of some analytical procedures.
GH. Morrison has compiled a comparison of the sensitivIties of a number of analytical methods
like absorption spectrophotometry, ultraviolet and visible fluorescence, atomic absorption, flame
emission photometry, neutron activation spark source mass spectroscopy and emission spectroscopy.
This compilation reveals that iron can be detected by activation only to 5 Ilg, but by flame
emission to 3 ng. Similarly, europium can be detected even in 0.5 pg. by using neutron activation,
to I ng by using flame emission and 100 ng by using atomic absorption spectroscopy.
Selection of an Analytical Method

An Important task for the analyst is to select the best procedure for a given determination .
. This will require careful consideration of the following factors :
(i) Type of analYSIS required such as elemental or molecular. routine or occasional.
(ii) Complexity of the materials to be analysed.
(iii) Problems arising from the nature of the material to be investigated, e.g., substances
affected by water, corrosive substances, radioactive substances, etc.
(iv) Concentration range which needs to be investigated.
(v) Accuracy needed.
(vi) Number of samples analysed by the chemist.
(vii) Instruments available in the analytical laboratory.
(viii) Length of time an analytical chemist must spend on the analytical work and quality
of results are mainly dependent on this choice.
(ix) Time required to complete the analysis is particularly relevant when the analytical
results are needed quickly for the control of a manufacturing process. This means that
accuracy has to be a secondary rather than a primary consideration or it needs the use
of expensive intrumentation.
(x) Nature of the sample.
(xi) Magnitude of the sample available.
(xii) Kind of information sought.
(xiii) Number of analyses of similar type which have to be carried out.
Table 4 includes comparison of some common quantitative analytical methods.
Table 4 : Comparison of some Common Quantitative Analytical Methods
Method Concentration Accuracy Speed Relative cost

Range (pC)
Gravimetry 1-2 High Slow Low
Titrimetry 1-4 High Moderate Low
Coulometry 1-4 High Slow-Moderate Low-Moderate
Voltametry 3-10 Moderate Moderate Moderate
Method Concentration Accuracy Speed Relative cost

Range (pc)
PotentlOmetry 1-7 Moderate Moderate-Fast Low-Moderate
Spectrophotometry 3-6 Moderate Moderate-Fast Low-Moderate
Atomic spectrometry 3-9 Moderate Fast Moderate-High
EmissIOn spectrometry 5-9 Moderate Fast High
Chromatography 3-9 Moderate Fast M oderate-h Igh
Neutron activation Moderate Slow High
X-ray fluorescence High Fast HIgh
Selection of analytical technique depends upon the knowledge of analyst who understands
the principles underlying the various instrumental techniques available to him as well as their
advantages and limitations.
An instrument for chemical analysis does not give rise to quantitative data but simply
converts chemical information to a form which is more readily observable. Thus. the instrument may
be considered as a communication device which takes place by involving the following four steps:
(i) Generation of a Sample : The signal used in an mstrument may be generated from
the sample. For example, when sodium atom is heated, the characteristic yellow radiation
it emitted. This constitutes the source of the signal in a flame photometer. However,
in many instruments, the original signal is formed independent of the sample. The
modification of this signal by the species of interest is related to concentratiqn.
(ii) Transducer: The transformation of a signal to one of a different nature is called
transducer. A transducer, which acts to convert the original analytical signal to one that
is more conveniently measured, is also employed in many instrument~. The examples
of transducers are the photo cell, the thermocouple and the photom\lltiplier tube.
These, which convert radiant ener~ into electrical sign~l, ~e us~d ih many instrume~s.
• I
(iii) Amplification of the Transformed Signal: The amplification of the original signal or
its transduced form increases the sensitivity of the instruments. Amplification is usually
achieved electronically.
(iv) Presentation of a Signal: The transducer and all\plifi~d signal from an insuument are
usually presented as a linear or singulall- disp1acement along a scale which IS
accomplished with electroni£ circUItrY.
However, it is not necessary that all of these steps given above are mcorporated in every !
instrument.
LABORATORY OPERATIONS AND PRACTICES

In order to perform quantitative analysis, the following laboratory operations and practices
are used.
1. Filtration
It is the separating process of solid phase from the liquid phase. It uses various types of
filter supports to collect the solid. The various filter. supports are: 1. filter papers, 2. crucibles
3. filter pulp mats, 4. asbestos, 5. filt~r. membranes, etc.
1. Filter Papers : These are available of different pore sizes. The filter paper is selected
according to the size of the particles of the solution being filtered. The best quality of filter paper
is Whatmann filter paper which is found in 3 different grades like: (a) Quantitative grade,
(b) Senu-quantitative grade, (c) Qualitative grade.
The Whatmann filter paper on combustion, leaves no ash or paper residue to be detected
by the balance (Fig. 1).
(a) Quantitative Grade: Whatmann No. 40 filter paper is especially used for carrying out
filtration of quantitative work. This filter paper is made from pure cellulose fibres. It
is also washed with HCl and HF until it becomes free from silica and other inorganic
sources of ash. Whatmann No. 41 filter paper is used for filtering the gelatinous
precipitates like iron hydroxide, aluminium hydroxide or silicic acid. Whatmann No. 42
filter paper is a close texture grade which is used for filtering finely divided precipitates.
Whatmann No. 50 filter paper is acid hardened and is employed special1y with vacuum.
(b) Semi-Quantitative Grade: In order to carryout semi-quantitative work Whatmann
No. 30 filter paper is used. It is used for rapid and fine filtration. It is also acid washed
filter paper. Whatmann No. 31 filter paper is used for separating the gelatinous
precipitates from the solution. Whatmann No. 32 filter paper is used for carrying out
the filtratlOn of fine precipitates. Semi quantitative filter paper is an ashless paper, the
weight of ash of an 11 em circle of these papers is nearly 0.00003 gram.
Glass Rod--+~\
Wash Bottle ~...-v'''

........_---Funnel
II/III
111111
Fig. 1
(c) Qualitative Grade: This grade of filter paper is HCl washed. It is also an ashless filter
paper. Whatmann No. I paper is known as qualitative grade filter paper which is used
for filtering the precipitates of average fineness. Whatmann No.2 paper is thicker than
Whatm~n No.1 and thus it cannot be used for fast and rapid filtration. Whatmann
No.3 paper is used to filter the very fine precipitates although it is a thick filter:paper.
Whatmann No. 4 ijlter paper is used to filter the gelatinous precipitates rapidly.
Whatma!ID No.5 filter paper which is used with a vacuum, is hard, tough and of close
'texture. All these filter papers are used when precipitate is only to be preserved. When
precipitate is to be weighed and ignited, the qualitative grade filter papers are not
recommended.
There are some more types of filter papers such as :
(i) Munktels (Swedish filter paper)
(ii) Carl Schiecher (German paper)
(iii) Schull (German paper)
2. Crucibles: Filter papers cannot always be used for carrying out filtration. For example,
the precipitate might slowly undergo reaction with the cellulose or the precipitate is not stable
at the temperature required for charring the filter paper. In these cases, filtration of a precipitate
is carried out under vacuum in crucibles. There are the following types of filtering crucibles :
(i) Porous glass /ritted disc crucibles: These crucibles are also named as sintered glass
crucibles. Depending upon the pore size these crucibles have been graded as G-l,
G-2, G-3 and G-4. These are made from excellent quantity of resistance pyrex or jena
glass, and are having transparent glass sides and a porous fritted glass bottom. In these
crucibles a sintered ground glass filt~.,diSC" is ~d -at, the bottom of the crucible.
These crucibles can be bro':lght to constant weight readily (Fig. 2).
Flask Porous plate

crucible
Rubber ring
To aspirator
r::===--+
Safety flask
Flask filter
Fig. 2 : Filtration under suction
(ii) Goocl.
I
crucibles : If the precipitates are quickly reduced by the carbon of the filter
paper on ignition they are preferably filtered by Gooch crucibles. The disc of these
crucibles consists oflarge holes which are- covered by an asbestos mat or other filtering
materials.
In place of vacuum, these crucibles consist of a thin layer of acid and alkali washed
asbestos as a filtering medium. It is more difficult to obtain a constant weight of a
Gooch Crucible. These are fitted to either glass funnel with rubber rings or to a Gooch
crucible holder.
Introduction TO Analytical Chemisfl)'
(iii) Other Types of Crucibles :

(a) Aluminium Crucibles: These are mhde from alummium oxide fritted together.
The main drawback of these crucibles 1S that they are having a tendency to lose
uniformity in weight on repeated combustion and ignition.
(b) Porcelain Crucibles: The porcelain crucible is used for heating the precipitate.
(c) Silica Crucible: These crucibles are mainly used for heating and cooling purposes,
without cracking. These crucibles are more safe.
(d) Platinum Crucibles : Platinum crucibles are very expensive but are the best
crucibles for heating the precipitates.
3. Filter Pulp : It is available in the form of small pallets for carrying out qualitative and
quantitative analysis. The gelatinous silica, finely divided barium sulphate and colloidal hydrated
oxides etc., are filtered by using filter pulp with the precipitates.
4. Filter'Membranes : These are synthetic filter membranes which are not used in gravimetric
analysis but in filtering devices and apparatus and consist of uniform micro porous screens with
millions of pores per sq. cm. or surface area. Filter membranes find use in the filtration of dust
from air, high molecular weight proteins and other large molecules.
Factors on which Filtration Depends

The technique of filtration has been found to depend upon the following factors :
(i) Size of the particles to be filtered.
(ii) Chemical reactivity of the particles.
(iii) Aim of filtration.
The rate of filtration of any filter paper decreases because its pores become clogged with
precipitate. Thus it is advisable to make the precipitate or insoluble matter to settle before
carrying out filtration. The process of settling and filtration can be accelerated by adding a slurry
of filter paper in the mother liquor or solution after precipitation.
Drying
For drying chemical substances a desiccator is used. It makes the hot crucible to cool in a
dry atmosphere, because desiccator is having a dry and moisture free atmosphere to store a
sample (Fig. 3).
A desiccator is a glass or aluminium vessel which is having a tightly fitted lid and a large
space to fill the desiccant. The top of the desiccator and the cover are ground flat and a thin layer
of grease or petroleum gel is applied between them which makes an air tight seal. The lid of
desiccator is opened by sliding. The desiccator is used for keeping the hot crucibles to protect
them and their contents from dust, moisture and hot laboratory flames as well as to cool at room
temperature.
In the desiccator, the following drying agents are used : 1. anhydrous calcium chloride,
2. fused NaOH, 3. calcium oxide,,4. sodalime (mixture ofNaOH and CaO), 5. anhydrous CaS04 ,
6. magnesium oxide (MgO), 7. P205' 8. silica gel, 9. conc. H 2S04 etc.
In,troduction to Analytical Chemistry H7
When the hot objects are placed into the desiccator, one must be careful. When hot material
is kept in the desiccator and the lid is tightly closed, the hot object of the desiccator warms the
inner air, which contracts on cooling and causes a partial vaccum which makes removal of the
lid very difficult. Sometimes, when the lid of desiccator is opened, air will immediately rush into
It and spill the sample by blowing it out of its container. Thus it is advisable that hot object
should be first allowed to cool for about 1 minute in air before keeping it in the desiccator.
Fig. 3 : A desiccator
Measuring Volume
Menisclls
In analytical chemistry solutions are usually
measured by using graduated glasswares like
volumetrIC flask; pipette, burette etc. Proper
... Low readi):Jg
handling and use of glassware in volumetric
,"
analYSIS require an accurate reading of the liquid
or solution level. The lowest point of solution level

(bottom of the meniscus) is read as the correct
volume. In order to detect meniscus in coloured ~a:mIJl1l~:';I. • .••...•... Correct position
solutions, a small piece of white paper or card • of eye
board behind the meniscus is generally helpful in
reading. In order to read a level of volume, eye
should be kept at parallel height of the meniscus
(Fig. 4). "High reading
Pipette : Before using a pipette, it is rinsed
with a small portion of the liquid which is to be
pipetted out. If the pipette is wet with water, it is
rinsed with the solution many times. First of all
the flow of the pipette is checked. If it forms beads, . . . .
it shows that pipette is dirty and must be cleaned. Fig. 4 : TechnIque for readmg a memsclls
In a pipette the solution should be filled to a level of about 2-3 cm above the calibration mark.
After filling the pipette its tip and stem should be wiped dry with tissue or filter paper. The
pipette is now held vertically and solution is made to come down until the meniscus reaches the
calibratIOn mark. After complete drainage of the liquid, the tip of the pipette is made to touch
to the wall of the vessel for nearly 10 second (Fig. 5).
\
)
Manipulation of stopcock of a burette. Holding of pipette in vertical position.
Fig. 5
Volumetric Flasks: Volumetric flasks are mainly used for preparing the standard solutions
of known concentration. The exact known weight of the solute should be transferred to the
volumetric flask by using a very short wide stemmed funnel. Now the solvent is added into the
flask and the solution is made to swirl very carefully until the solute dissolves. At the completion
of dissolving of the solute more solvent is added upto the mark, with the last few milliliters of
solvent added very carefully.
In order to prepare a solution of known concentration, another process can be followed.

First the correctly weighed sample is transferred to a large beaker and then dissolved properly
in the solvent. The prepared dissolved solution is then put into the volumetric flask and made
up to the mark by adding a little more solvent. In both procedures it becomes necessary to
dissolve the solute completely before the final dilution is done. The stopper is placed into the
flask, after the complete dilution. Now the flask is inverted back alld forth at least 4-5 times by
keeping the thumb over the glass stopper to ensure the complete mixing of the solution .
Burette : When titration is carried out with the use of a burette, one hand is used for
.l
swirling the titrant container and the other is used for controlling the stop cock. Before using
burette, it is rinsed with the titrant solution. There should be no air bubbles of titrant on the inner
surface of the burette. The tip of the burette should be 2-3 cm.; above the solution surface in the
titration vessel.
Graphs
In analytical chemistry, it is possible to analyse and measure the expet:imental observations
by calibration and titration curves.
Illtroduction to Analytical Chemistry 1-19
l
Calibration Curve: A calibration curve refers to a graphical co-relationship of instrumental
response to concentration. The concentration of an unknown is found out by treating the unknown
in the same way as the standards which are used for preparing the calibration curve. If the
instrument response for the unknown is measured, its concentration can be known directly from.
the calibration curve.
Titration Curve : An end point of titration can be measured by a number of ways. The
fastest observation is its location by inspection. In another method, the rate of change in the
property is made to plot on the Y-axis w.r.t. a small constant increment of titrant. The values,
/).Y/ /). V are plotted against the volume added. This is called differential titration curve.
Stoichiometry
The analytical procedures are mainly of two types: (i) Stoichiometric; (ii) Non-stoichiometric
(i) Stoichiometric : In stoichiometric procedure the constituent whose amount is to be
determined undergoes a reaction with another substance or it is decomposed in accordance with
a well defined equation, such as :
Reactants ~ Products
RA + RB ~ PC+PD
where, RA = Desired constituent, Rn = Reacting Reagent
It is possible to measure the quantity of desired constituent RA by applying the laws of
definite and combining proportions, if the quantity or amount of any of the products (P c or PD)
or of the reagent used is known or can be found out.
(ii) Non-Stoichiometric: Non-stoichiometric analytical procedures have been just opposite
to the stoichiometric analytical procedures. Non-stoichiometric procedures can not be written by
exact well defined reactions and equations. In many cases, non-stoichiometric procedures involve
the measurement of a physical property which changes in the proportion to the concentration of
the desired constituents.
It is known that a large number of physical properties can be determined with great accuracy.
Therefore it is only necessary to calibrate the procedure. The calibration gives the relationship
between the concentration of the desired constituent and the magnitude of the physical property
under specific suitable conditions. In gravimetric and volumetric methods (wet chemical methods),
some separation procedures are stoichiometric whereas most of the instrumental methods are
non-stoichiometric.
Some examples of stoichiometric procedures are gravimetric method, titrimetric method,
gas analysis and coulometric etc. while some examples of non-stoichiometric procedures are
optical, electrical, mass spectrometry, refractrometry, polarimetry and activation analysis etc.
Parts Per Thousand (ppt) and Parts Per Million (ppm)

Percentage concentration of a solution on weight basis may be expressed in parts per
thousand (p.p.t.) or parts per million (p.p.m.). The unit of p.p.t. is milligram per kilogram (mg!
kg) or microgram per gram (11m/g). An example is that 1 p.p.t. Sn in an alloy reveals that the
1·20 Introduction to Analytical Chemistry
alloy is h'aving 1 part by weight of Sn in 1000 parts by weight of alloy. Similarly, a solution of
1 p.p.m. Sn means 1 part Sn by weight in one million parts by weight of sample solution.
Standards
For doing all types of determinations, it becomes necessary to establish a standard or
reference point. In chemistry, a substance whose purity is analysed may be a primary standard
substance. The primary standard (or reference point) is a precisely defined unit of measurement
for determining the physical properties. Primary standards are used in analysing mass, time,
length and wavelength. But primary standards are not always available.
Standards
I
I I
Primary Standards Secondary Standards
Therefore, other reference materials which are closely satisfied with the requirements are
used. These are called secondary standards.
Physical Property Unit Definition of Unit
(i) Wavelength Angstrom 6438-4686° A, which is wavelength for the red
radiation from Cd relative to the metre (adapted
1907).
(ii) Length Centimetre 1/100 the length of mternational prototype
metre at O°C or 1553164.13 times the wave-
length of red <;;d lin¢. ift~air at 760 mm. Hg at
15°C.
(iii) Mass Gram III 000 the quantity of matter in the mter-
national prototype kilogram.
(iv) Time Ephemeris second 1131556825.9747 of the tropical year for 1900
January ael 12h ephemeris time 1 ephemeris
day = 85,400 ephemeris seconds.
Neatness and Cleanliness in Analytical Laboratory
While working in the analytical laboratory, the students (also called analyst) should develop
the habit of neatness and cleanliness in the analytical laboratory. The following facts will be
helpful during handling of the work in the analytical laboratory :
1. Keep the bench and working area of the laboratory as clean as possible. Clean up any
spillage of solid or liquid chemicals by a bench cloth which must be available readily.
2. Do not clutter the working area of the bench with apparatus and reagent bottles. When
(luplicate analysis or determinations are in progress, all the apparatus and chemicals
required for them are grouped together on the bench together. Return the unused
apparatus immediately to the locker.
3. Always use clean glassware. If glassware is not in use for some time, rinse it with
distilled or de-ionised water. Dry the outside of rinsed glassware with lint free glass-
cloth which should be reserved exclusively for this purpose. Launder the glass-cloth
frequentl}T
Chatwal, Gurdeep R., and Madhu Arora. Analytical dD not use
but Chemistry, Himalaya tbe inside
on Publishing 2008.the
House, of 1/essels.
ProQuest Ebook Central,
Introduction to Analytical Chemistry
4. Clean the glassware repeatedly with soap solution and then rinse the glassware with
distilled water. Always use other cleaning solutions'like alc., KOH or sulphuric acid-
potassium dichromate under the direction of the teacher.
5. Label the container vessels or bottles so that the contents can be readily identified.
6. In order to prevent contamination of the contents of the vessels by dust, air and
mOIsture-, cover the vessels immediately after use.
7. Never use bark cocks to cover the vessels because they tend to shed some dust.
8. For Temporary labelling always use a 'chinagraph' pencil or a felt up tip pen (Glass
marker pen) .but not the gummed labels, which are used when more permanent labelling
is reqUIred.
9. All determinations should be carried out in duplicate.
10. Safety procedures must be observed in the laboratory at all times.
11. Handle the poisonous chemicals very carefully.
12. All laboratory workers should familiarise themselves with local safety requirements.
13. In some laboratories, make the wearing of safety spectacles and gloves compUlsory.
14. Use the laboratory time well. Understand the principles and experimental procedure
upon which the experiment is based before entering the laboratory. Organise what has
to be done before and not during the laboratory time.
15. Avoid practical jokes and horseplay alw~ys be avoided in the laboratory.
16. Co-operation is a must and generally required in the laboratory.
17. Be patient if you are not following any thing in the laboratory. Speed will come only
through careful planning and experience. The laboratory work should be performed
patiently and not excessively fast in relation to the amount of experience, otherwise
results may be poor and accidents may occur because of carelessness.
18. Perform experiment in terms of concepts, accuracy, precision and error.

19. Use common sense in interpretation of the experimental procedures, use of chemicals,
and relationship to the other individuals in the laboratory.
20. Be prepared in case of emergency. Accidents may take place but do not cause them
through your carelessness. Locate the fire extinguishers and other emergency equipments
in the laboratory. Treat burns from hot objects and corrosive acids. This involves a
thorough washing with water under a shower. Fast treatment is necessary when eyes
are involved. The eyes should be protected from accident by safety glasses or goggles.
21. Bring laboratory note book daily in the laboratory and all data should be recorded
while carrying out the experiment, not at' a later time. Do not commit the observation
or other data to memory for later recording.
22. Do not give your, experimental data to your friends especially in the practical
examination. A student may get more marks who works occasionally than one who
works seriously throughout the year. Practical examination is more or less like a
cricket match.
1-22 Introduction to Analytical ChemisllJ'
Analytical Balance
Analytical balance is considered to be the most important tool in an analytical laboratory.
It is used for comparing an unknown mass to a known mass under the same gravitational force.
Therefore, while dealing with analytical balance, it is customary to use the terms mass and
weight interchangeably and it is in this sense that weight is employed in quantitative analysis.
Weighing forms an integral part of almost any analysis, both for measuring the sample and
for preparing standard solutions. In analytical chemistry the analyst deals with rather small
weights, of the order of a few grams to a few milligrams or even less. Standard laboratory
weighing is typically made to three or four significant figures. Analytical balance gives the
accurate measure-ment of weight.
The sensitivity of the analytical balance may be defined as the magnitude of deflection
produced by one umt of weight. Sensitivity of the balance depends upon various factors. Some
of these are :
(i) Sensitivity is directly proportional to the balance arm length. Sensitivity increases as
the arm length increases.
(ii) Sensit1vity is inversely proportional to the mass ofthe system (beams, pans and load).
Sensitivity decreases as the mass increases.
(iii) Sensitivity is inversely proportional to 'the distance between the support point and
centre of gravity of the oscillating beam. An increase in this distance causes a decrease
in sensitivity.
(iv) All moving parts must be as frictionless as possible. An increase in friction causes the
sensitivity to reduce.
In recent years, analytical balance has undergone radical changes. The design of the balance
has been altered, and the conventional free-swinging, equal-arm, two pan chemical balance
together with its box of weights is now an uncommon sight. The following types of balances are
described as follows :
1. Electronic Balance
2. Single-pan Balance
3."- Semimicro and Micro Balance
Let us describe these one by one :
. .1- Electronic Balance

This balance provides convenience in weighing and is subject to lesser errors or mechanical
failures than the classical mechanical balance. The 'operation of dialling weights, turning and
reading micrometres, and beam and pan arrest of mechanical balances are eliminated, thereby
speeding the measurement.
Electronic balance uses the principle of electromagnetic force compensation, first described
by Angstrom.
Fig. 6 : Electronic analytical balance

Figure 7 depicts a digital-display electronic balance whereas Figure 8 depicts the operating
principle of an electronic balance. Electronic balance does not have weights or knife edges as
in mechanical balances. Here (1) is an electrical position scanner which brings the weighing
system back to zero position. The pan sits on the arm of a movable hanger, (2) and this movable
system gets compensated by constant electromagnetic force. The electrical position scanner
monitor the position of the hanger, and brings the system back to the zero position. The magnitude
of the compensation current depends upon the weight placed on the pan. The compensation
current is sent in digital form to a microprocessor which is able to convert it into the corresponding
weight value which appears as a digital display.
- -.... (OJl--Position scan
Hanger
Coil Temperature
sensor
Fig. 7 : Operating principle of electronic balance
Chatwal, Gurdeep R., and Madhu Arora. Analytical Chemistry, Himalaya Publishing House, 2008. ProQuest Ebook Central, " (
}'24 Introduction to Analytical Chemistry
Electronic balance uses the principle of comparing one weight with another. It is zeroed or
calibrated with a known weight. If the sample is kept on the pan, its weight is electronically
compared with the known. This is a form of self-calibration.
A single control bar IS used for switching the balance on and off, for setting the display to
zero and for tracmg a contamer automatically on the pan. But results are available as an electric
signal. Therefore. they can readily be processed by a personal computer and stored. WeIghi1).g
statJstJcs can be automatically calculated.
In the market. the different electronic analytical balances are available which are havmg
different weighing ranges and readiabilities, e.g.,
(i) A microbalance is having a range of the order of 160 g, readable to 0.1 mg.
(ii) A semi-mIcrobalance is having a range of about 30 g, readable to 0.01 mg.
(iii) Microbalances are available which weigh upto 1 /-lg.
(iv) Ultramicrobalances are available which are sensitive to 0.1 /-lg or less.
Electrochemical quartz balances are available having 100-Jlg range which can detect I ng
(10--9
g) changes. The balance utilizes a thin quartz crystal disk oscillating at, for example, 10
MHz. The frequency of oscillation changes with any change in mass, and the frequency change
measured by the instrument is converted to mass units. A film of gold is evaporated on the quartz,
and the gold substrate can be coated with the material of interest. Mass changes as small as a
few percent of a monolayer coverage of atoms or molecules on the gold surface can be measured.
Mass changes WIth tJme can be recorded.
Modern mIcrobalances may be having such features as compensating for wandering from
true zero and averaging variations due to the building vibrations.
2. Single-pan Mechanical Balance
It is a first-class lever which compares two masses. Fig. 8 depict0uch a balance in which
the fulcrum A lies between the points of application of forces B, and C. MI represents the
unknown mass and M2 represents the known mass. The principle' of operation is based on the
fact that at balance, MILl = M2L2. If LI and L2 are made to be as nearly equal as possible, then
at balance, MI = M2. A pointer is kept on the beam of the balance to indicate on a scale at the
end of the pomter if a state of balance is attained. The operator adjusts the value of M2 unless
the pointer returns to its original position on the scale if the balance is unloaded. Though mass
is determined, yet the ratio of masses remains the same as the ratio of weights if an equal-arm
balance is used. It is customary, then, to use the term weight instead of mass and to speak of the
operation as weighing. The known/masses are known as standard weights.
Most of the analytical weighings using mechanical balances are carried out on a singlepan
balance. A schematic diagram of a typical mechanical' single-pan balance is depicted in Figure 8.
A first-class (unsymmetrical) lever is pivoted on a knife edge, and a pan is placed at one
end in which the object is kept. However, no pan is at the other end for keeping weights. When
the balance is not in use, a series of weights totaling 160 to 200 g are on the pan end of the beam.
These are counterbalanced by a single weight on the other end of the beam, which also acts as
part of a damping piston. If an object is kept on the pan, individual weights are removed from
this end of the beam to restore it to equilibrium. This is carried out by means of. knobs on the
.Introduction to Analytical Chemistry 1·25
front of the balance which lift weights or combinations of weights from the beam. Hence the
weights are never handled. These weights would be equal to the weight of the object on the pan.
I I
, I
1
:;::,:J~ \
~
1\
Ii
! 11
I tI
1'1"1
\\I~==.==:::=:D:::=J8~==+~~===========~!
c::=__''----<!-- - - - -----
-- - --- - - - _.- - - - - - - -
~
Fig. 9 : A typical single pan balance. I. Balance pan. 2. Balance weight. 3. Damping weight.
4. Pan release. 5. Weight setting. 6. Sensitivity adjustments.
The beam is not brought completely to balance,

but weights are removed only to the nearest whole gram
or 0.1 g, depending on the balance. The imblance of the
beam is registered optically and automatically on an
illuminated vernier scale by a light ray reflected from an
engraved optical scale on the beam. The last digits
(nearest 0.1 mg) are read from this scale. Alternatively,
tl:1e imbalance can be read on a digital counter.
The original no-load reading or position is known
as the zero point, and the position under load is known
as the rest point. In operation, the rest point is made to
coincide with the zero point. The zero point is usually
adjusted to read zero by adjusting the vernier by means
of a knob.
Single-pan balances are under constant load of160
to 200 g, a required feature because they are not brought
back to a, state o(balance. The sensitivity of a balance Fig. 10: Typical single-pan
varies with the load since it is governed by the center of gravity of the beam; the beam bends
slightly under load, giving rise to a change in the center of gravity and the sensitivity. Calibration
of the vernier or digital readout of a single-pan balance to read the amount of imbalance is carried
out at a given sensitivity, that is, at a given load. Hence, the load must remain constant.
All weights of a single-pan balance are concealed and are removed by using control knobs
qn the front of the balance: one for tens (e.g., lO to 90 g), one for units (1 to 9 g), and, if
applicable, one for 0.1 units (0.1 to 0.9 g). The weights removed are registered on a counter on
the front of the balance. The beam is brought to rest rapidly by using an air piston damper.
Care is taken not to damage the knife-edges w:hereas the balance is not in operation and
while objects are being placed or removed from the pan. A three position beam-arrest knob is
used for protecting the knife-edges and beam. The center position arrests the pan and beam; a
second position partially releases the pan for use whereas finding the approximate weight of the
object on the pan and third position completely releases the pan to allow the balance to c9me
to rest.
A typical single-pan balance is shown in Figure 10. Weighings can be done in less than a
minute with these balances.
Single pan balances are now more common than equal arm balances due to the following
three advantages :
(i) The weights can be found faster.
(ii) The sensitivity remains constant over the entire weight range.
(iii) A separate set of weights is not required because the weights in balance are never
touched.
3. Semimicro and Microbalances

Semimicro balance is sensitive to about 0.01 mg, and the microbalance is sensitive to about
0.001 mg (l J.l.g). The load limits of these balance are correspondingly less than conventional
balance, and greater care must be taken in their use.
Care and Use of Analytical Balance: Irrespective of the type of analytical balance used,
the following precautions should be followed in their use :
(i) Never excl!ed the stated maximum load of the balance.
(ii) Always keep the balance clean. By using a camel-hair brush, remove the dust from the
pan as well as from the pan compartment.
(iii) Never handle the objects to be weighed with fingers. Always handle them by using
tongs or a loop of clean paper.
(iv) Before weighing, allow the objects to be weighed to attain the temperature of the
balance. If the object has been heated, allow it to cool for sufficient time. The time
needed to attain the temperature of the balance depends upon the size of object to be
weighed but as a general 30-45 minutes time is sufficient.
(v) Never place the chemical substance directly on the balance pan because this chemical
will injure the balance pan. Weigh the chemical substances in the suitable containers
like weighing bottles, crucibles, small beakers or watch glass. Weigh liquids and
volatile or hygroscopic solids in tightly closed vessels such as stoppered weighing
I
bottles. Do the addition of chemicals to the receptacle outside the balance case.
(vi) When weighing gets completed, do not leave anything on the pan.
(vii) Avoid the exposure of the balance to corrosive atmosphere.
(viii) When balance is at rest, keep the object on the pan.
(ix) When the balance is connected to a printer, then confirm that the printed result.agrees
with the digital display.
(x) When all weighings are completed, remove the object which has bean weighed, clean
the pan and close the pan compartment.
Techniques of Weighing Samples

The material is usually dried at 105-11 O°C before analysis. After cooling in a desiccator,
the weighed samples are usually obtained by the two general techniques.
1. Weighing by Difference : The material, placed in a weighing tube, is weighed.
Subsequently the weighing tube is taken out from ~he balance pan and sattlple is taken with a
spatula and transferred to a container so as to prepare a solution. The weighing tuIre is, again
weighed and the sample weight is found out by the difference. This procedure can be rc;peated
for additional samples.
2. Weighing a Specific Amount of Sample: The sample is directly weighed on the balance
pan. Sample is added or removed by spatula' repeatedly so as to get a desired weight. Weighing
paper or watch glass is used to hold the sample. Once the sample is weighed, it is transferred
to a container so as to prepare a solution.
Weighing Errors
There may be errors in weighing even when carried out very carefully because of the
following reasons :
1. Defective Balance : Errors due to defective balance construction or operation of the
weights are possible. It is difficult to discover these errors in single pan balance where
the working parts are enclosed. Defects may also occur because of corrosion, chipped
knife edges, dust and magnetic damping errors.
2. Static Errors: These are imparted to the balance from the working analyst or from
the objects kept on the pan. Especially, semimicro and microbalances are susceptible
to this type of error.
3. Temperature Effects: These are caused by temperature gradient in the balance case,
since convection currents will be present' because of temperature gradient. Small
temperature gradient may give rise to draft against the pan and give rise to erroneous
weights, while large temperature gradient may cause the beam lengths to change .
because of expansion and thus give rise to an error. Hence hot objects should never
be weighed and balance should be protected from sources of heat or draft or sunlight.
."
Fig. 11 : Protection of sample during drying in an oven
4. Operative Errors: These errors arise as a result of carelessness and improper handling
of the balance and they can readily be corrected and controlled. For example,
,
(i) Spillage of chemicals may cause the etching of the pan or other parts of the balance.
(ii) Sudden jarring or adding or removing weights or the sample from the pan can
be able to damage the knife edges in the balance.
(iii) Mlsreading the weight scale, spilling of weighed samples, poor handling of the
object during weighing are also operative errors.
These kinds of errors given above may permanently influence the accuracy as well as
sensitivity of the balance.
5. Volatile Contaminant Errors: The volatile contaminants may also cause errors. For
example, objects may absorb H20 or CO 2 from the atmosphere during weighing.
Because of this, the objects will change weight during weighing. Even containers
holding the sample may be capable of this action.
This error may be m)nimised by keeping the balance in a low humidity, controlled
temperature room or in a dry box. Sometimes a small amount of desiccant is kept in
the balance. It is also desirable to dry the sample in an oven before weighing at a
temperature that is high enough to remove' water, but not high enough to cause sample
decomposition. Before weighing the sample and its container are cooled to room-
temperature in a desiccator containing a suitable drying agent.
6. Changes in the Conditions of the Containing Vessels : These cause change in
weight of the containing vessels. Some of these are as follows :
,
(i) By electrification of the surface caused by rubbing: The electrification may be

removed by subjecting the vessel to the discharge from an antistatic gun.
(ii) By its temperature being different from balance case: This error may be removed
by wiping the vessel gently with a linen cloth and allowing it to stand at least
for 30 minutes in proximity to the balance before weighing.
7. Errors in Recording the Weights: The correct reading and recording of weights is
best achieved by checking weights when they are added to the balance and when they
are removed from the balance. In the case of electronic balances any digital display
should be read at least twice.
8. Effect of Buoyancy of the Air: If a substance is immersed in a fluid, its true weight
IS diminish~d by the weight of the fluid which it displaces. If the object and the
weights are having the same density, and the same volume, then no error will be
introduced on this account. If the density of the object is different from that of the
weights, the volume of air displaced by each will be different. If the substance is
having a lower density than the weights, as is usual in analysis, the former will
dier>:lace a greater volume of air than the latter, and it will, therefore, weigh less in air
than in vacuum. Conversely, if a denser material (e.g., one of the precious metals) is
weighed, the weight in vacuum would be less than the apparent weight in air.
Cleaning of Glass Ware
In the chemical laboratory, one should use glass ware which should be perfectly clean and
free from grease. It you do not use such glass ware, the results will be unreliable.
A very simple test for cleanliness of glass ware is to fill this with distilled water and then
it is withdrawn. If only an unbroken film of water is left, this indicates that glassware is perfectly
clean and free from grease. On the other hand, if the water collects in drops, glass ware is dirty
and requires cleaning.
The cleaning of glass ware is carried out by the following methods :

1. Decon 90 : There are many commercial detergents which are used for cleaning glass
ware. Some manufactures market special formulations which are suitable for cleaning
laboratory glass ware. A specific example is Decon 90 which is manufactured by
Decon Laboratories, Portslade. This formulation is specially effective in removing
contamination because of radioactive materials.
2. Teepol: It is relatively mild and inexpensive detergent and is mainly used for cleaning
glass ware. Its 10 per cent stock solution is prepared in distilled water. In order to
clean a burette, 2 mL of the stock solution diluted with 50 mL of distilled water is
poured into the burette. After allowing it to stand for 30-60 minutes, detergent is run
off, the burette is rinsed three times with tap water and then several times with
distilled water. Similarly, it is possible to clean a pipette with 1 mL of the stock
solution diluted with 25-35 ml of distilled water.
3. Chromic Acid Cleaning Mixture (CARE) : It is a nearly saturated solution of
powdered sodium dichromates or potassium dichromate in concentrated sulphuric
acid. Potassium dichromates is less soluble (about 5 g per litre) than sodium dichromate
'1'30 , dntroduction to Analytical Chemistry
(about 70 g per litre) in concentrated sulphuric acid. At the same time, sodium dictromate
is cheaper than potassium dichromate. Because of these, reasons, sodium dichromate
is preferred for the preparation of cleaning mixture (CARE). From time to time, it is
advisable to filter sodium dichromate-sulpuric acid mixture through glass funnel which
is having glass wool in its apex. This filtration removes small particles of sludge
which often blocks the tips of the burettes.
The glass ware to' be cleaned is filled with CARE. This is allowed to stand for several
hours, preferably overnight. The CARE is then poured off from treated glass ware.
Then this glass water is thoroughly rinsed with distilled water. Finally, this glass ware
is allowed to drain off water until dry.
CARE must be handled with great care.
4. Mixture of Sulphuric Acid-Fuming Nitric Acid: This mixture is an efficient cleaning
liquid. It is used for cleaning such glass wares which are very greasy and dirty and
cannot be cleaned by the reagents described earlier. Like CARE, this mixture must be
handled with extreme caution.
5. Mixture of KOH-Spirit : This mixture is obtained by dissolving 100g of potassium
hydroxide in 50 mL of water and after coolling, making upto 1 litre with industrial
methylated spirit. This mixture is very effective and decreasing agent.
Calibration of Glass Ware

For majority of the analytical purposes, volumetric apparatus of class A standard will be
satisfactory, but for carrying out work of the highest accuracy it is advisable to calibrate all
apparatus. The calibration procedure involves measurement of the weight of water contained or
delivered by the particular piece of apparatus. The temperature of water is recorded and from the
known density of water at that temperature, the volume of water can be found out.
The volume of 19 of water at various temperatures is given in the table, which is used for
calculating the relevant volume directly from the observed weight of water.
Temperature (0C) Volume (mL)
10,00 1.0013
12.00 1.0015
14,00 1.0017
16,00 1.0021
18.00- 1.0023
20.00 1.0027
22.0 1.0033
24.0 1.0037
26.0 1.0044
28.0 1.0047
30.0 1.0053
Introduction tD. Ary,alytical Chemistry 1:31'
In ca1ibrati~opc1'ations, apparatus to be calibrated is first of all carefully cleaned and the~'

allowed to stand adjaceftt to the bala.w-e which is to be used, together with the supply of distilled
or de-lOnised water, so that they aC£}1.lire the room temperature. Flas~ will also have to be dried,
and this can be carried out by rinsing twice with a little acetone and then blowing a current of
air through the flask for removing the acetone.
Graduated Flask : Ailee making the clean dry flask to stand in the balance room for an
hour it is stoppered and weighed. A sman filter funnel, the stem of which is drawn out so that
it reaches below the graduation mark of the flask, is then inserted into the neck and distilled
water which is also standing in the balance room for an hour, is added slowly until the mark gets
reached. The funnel is then carefully removed, taking precaution not to wet the neck of the flask
above the mark, and then, using a dropping tube, water is added dropwise until the meniscus
stands on the graduation mark. The stopper is replaced, the flask is reweighed, and the temperature
of water is recorded. The true volume of the water filling the flask to the graduation mark can
be calculated by using the data given above.
Pipette: The pipette is filled with distilled water (which is standing in the balance room
for at least an hour) above the mark. Now the excess of water is removed and the meniscus is
brought at the mark. There should be no droplets on the surface, if they are blotted with tissue
paper. The pipette is then made to discharge into a clean weighed stoppered flask and held so
that the tip of the pipette remains in contact with the side of the flask. The pipette is allowed
to drain for 15 seconds after the out-flow is ceased. The receiving flask is rerp.oved from contact
with the tip of the pipette. The receiving flask is weighed and the temperature of the water is
recorded. The capacity of the pipette is then calculated by using the data given above. At least
two determinations of the whole process should be carried out.
Burette : The procedure for the calibration of a burette has been similar to the procedure
followed for a pipette, except that several volumes will be delivered.
In order to calibrate a burette, first satisfaction is made about its (a) leakage and (b) delivery
time.
(a) Leakage: In order to test the leakage, the plug is first of all removed from the barre1
of the stop cock. Then both parts are carefully cleaned of all grease, after wetting well
with distilled water the stop cock is reassembled. The burette is kept in the holder,
filled with distilled water, adjusted to the zero mark, and any drop of water adhering
to tip is removed with the tissue paper or filter paper. The burette is then made to stand
for 20 minutes, and if the meniscus does not fall by more than one scale division, the
burette may be considered as satisfactory as far as leakage is concerned.
(b) Delivery Time: In order to test the delivery time, again the components of the
stopcock are separated. They are dried, then greased and reassembled, then the burette
is filled upto zeromark with distilled water, and is placed in the holder. The stopcock
is opened fully and the time taken by the meniscus to reach the lowest graduation
mark of the burette is noted, this should agree with the time marked on the burette.
-After-passing the above two tests, the burette is ready for calibration operation. First the
burette is filled with distilled water (which is kept in the balance room to acquire room temperature).
A'~lean dry stoppered flask of 100 mL capacity is weighed. The burette is adjusted to the,zero
1'32 Introduction to Analytical Chemistry
mark, any water droplet adhering to the tip of burette, is blotted the flask is placed in position
under the tip of the burette, the stopcock is opened fully, and allow the water to flow into the
flask. When the meniscus approaches the desired calibration point on the burette, the rate of flow
is reduced until eventually it is discharging dropwise and the meniscus is adjusted exactly to the
required mark. This procedure is repeated for each graduation to be tested. For a 50 mL burette,
this will usually be every 5 mL. The temperature of the water is noted and then using above data,
the volume delivered at each point can be calculated from the weight of water collected. The
calibration results will be more conveniently used by plotting a curve for the burette.
Sampling
Sampling constItutes an important operation in analysing a material or substance. It is a
difficult task to obtain a proper and homogeneous sample because actual samples are more or less
heterogeneous one i.e., improper samples and they require much time and effort to get good
analysis of such samples i.e., improper samples. Sampling is mainly of two types:
1. Statistical Sampling : In this type of sampling, the portions from every section of the
sample are first removed, then mixed well and finally resampled to get laboratory size sample.
In this type of sampling, every particle or portion of the substance gets an equal chance of
appearing in the sample.
2. Random SalPpling : This type of sampling is quite difficult because at involves operational
techniques such as ct~Shing, grinding, labelling and storage of the samples. Any of these operational
techniques may alter the composition and properties of the original sample.
There are two types of sample mixtures.
(i) Homogeneous: In homogeneous samples, all the particles of the sample are mixed
thoroughly and uniformed. The handling of homogeneous samples is quite easy.
(ii) Heterogeneous : Examples of heterogeneous samples are emulsions, powders,
suspensions, aerosols, etc. Such samples are usually handled by statistical plan.
On the basis of physical state, there are three types of samples : (i) Solids (ii) Liquids
(iii) Gases.
Sampling of gases, liquids and solids are carried out by different techniques.
1. Sampling of Solids : In the sampling of solids, the particle size is taken into consideration
because composition of particles of different size may vary. Large particle samples are converted
into small and suitable for analysis in accordance to the following scheme :
(i) First of all, the sample is reduced to uniform particle size. This is obtained by first
passing the sample through crushers, mills, mortars and pulverizers and then sieving.
(ii) Then, the mass of the sample is reduced.
The sampling of large mass may be carried out either by hand or by mechanical sampling
machi,nes.
2. Sampling of Liquids : The pure and homogeneous liquid may be sampled by using any
sampling device which does n~t destroy the purity or homogeneity of the liquid. Sampling of
heterogeneous liquid mixtures depends on whether the mixture is a suspension, an emulsion, a
Introduction to Analytical Chemzstry .1·33
mixture of immiscible liquids or a liquid containing solid residue. Additional complication may
be introduced when the liquid mixture is unstable, is having volatile components or dissolved
gases.
Hence, in general, samples are withdrawn from various depths and from all locations in the
liquid sample. They are either analysed separately or combined and a composite sample, IS
obtained which may be statistically planned.
3. Sampling of Gases : Sampling devices for gases are usually made from glass and are
fitted with stop cocks at both ends. Contaminations from previous samples are removed by
extensive flushing of the container with the gas to be sampled. The gases may be collected by
expansion into an evacuated container, flushing and displacement of a liquid.
Atmospheric sampling is much more difficult, due to the presence of wind, pollution or rain
as variables and they can neither be controlled not overcome. In general, the atmospheric sample
is, therefore, made to pass through a series of fine filters, where the filtering action is controlled
by the porosity of the filtering device or through a trapping solution, where the chemical reaction
traps the sought for components. The atmospheric air samples should be passed into the filtering
or trapping system at a controlled flow rate.
Sampling on Moon Surface: A recent difficult task is the sampling of moon, since statistical
selection of the moon s surface is not possible. The sampling is, therefore, based partly on size
and partly on physical state of limited quantity of moon rocks.
The important part of the analysis of moon rock or of any material from beyond the earth
is to know whether or not there is organic matter present.
However, it is not possible to describe a set of general methods for sampling all substances
under all conditions. Almost in all cases the aim involves statistical sampling and the use of
chemical common sense.
Drying
After getting sample, the next step is whether the sample is used as it is or it is to be dried.
Samples contain varying amounts of moisture, either because they are hygroscopic or because
water is adsorbed on the surface. Hence, there are two types of analysis :
1. Received Basis: When analysis is carried out on, "received basis" then water happens
to be a part of the sample composition and thus there should be no loss or gain of
water by the sample before analysis.
2. Dried Basis: Analysis on dried basis implies that water is removed from the sample
by heating in an oven, a muffle furnace or by Bunsen or Meeker Burners. There
should be careful heating, otherwise sample may get decomposed or may rem<?ve
volatile components. In most cases a dried basis, however, means that only water is
removed. The dried sample should be stored in absence of water and heated sample
should be cooled in a desiccator before weighing. The material is usually dried at
105-110°C before analysis:
Weighing
Before analysis, the sample is dried at 105-1 10°C and then cooled in a desiccator. After this
1-34 Introduction to Analytical f;hemistlY
the dried sample is transferred to a weighing bottle. which is stoppered and stored in a desiccato.
Samples of desired size are withdrawn from the weighing bottle, the bottle is weighed before and
after the withdrawl, so that the weight of the sample is obtained by difference. Each weighing
of bottle is usually carried out in triplicate. An alterrtative technique is to weigh one sample and
dIssolve it in a volumetric flask to a known volume. Aliquots of this solutio~ are then used for
quantitative analysis.
Dissolving of Sample
After weighing the sample, the next step is to dissolve it in a suitable solvent. Most
inorganic salts are soluble in water, whereas organic compounds are soluble in most organic
solvents or mixtures of organic solvents and water. Occasionally, samples may slowly undergo
hydrolysis in water to yield insoluble hydrous oxides.
In most cases water finds use as a solvent. In wet chemical and instrumental methods,
specific solvent compositions are used, whereas in some cases, e.g., in atomic emission, a solid
or liquid sample can be used directly and no solvent is used. The solubility of some inorganic
salts in water is given as follows :
1. Ac~tates are soluble, except AgC2H30 2 and Hg2(C2H 30 2)2' which are sparingly soluble.
2. Arsenates, borates and carbonates are insoluble except those of NH;, Na+ and K+ ..
The bicarbonates of these three and of Ba2+; Ca2+, Fe2+, Mg2+, Mn2+ and sr2+ are soluble.
3. Chlorides and bromides of Ag+ and Hg~+ and iodides of Ag+, Hg;+ and Pb2+ are
insoluble. PbCI 2. PbBr2 and HgBr2 are slightly soluble.
4. Chromates are insoluble, except those of Na+, K+, NH;, Cu2+, Mg2+, Zn2+ and Fe3+.
5. Fluorides are insoluble, except those of Na+, K+, NH;, Ag+ and Sn2+. FeF3 is sparingly
soluble.
6. Nitrates are soluble, except BiON03.
7. Nitrites are soluble, except AgN0 2, which is slightly soluble.
8. Oxalates are insoluble, except those of Na+, K+, NH;, and Fe3+.
9. Phosphates are insoluble except those Na+, K+, and NH;.

10. Sulphates are soluble except BaS04, SrS04, Hg2S04, PbS04, Ag2S04 and CaS04
which are partly soluble.
11. Sulphides are insoluble except Na2S, K 2S and (NH4)2S,' BaS, SrS, CaS and MgS are
slightly soluble.
12. Sulphites are similar to carbonates. MgS0 3 is partly soluble.
Decomposition of Organic Matter

Although various procedures are available to bring about decompos~ion of organic matter
in samples, yet the following two methods are widely used and preferred.
Introduction to Analyti~dl Chemistry 1·35
(i) Wet ashing

(ii) Dry ashing
The choice of method (either (i) or (ii) depends upon the following two factors :
(a) Only organic mater is to be removed, or
(b) Analysis of organic matter is required.
(i) Wet Ashing : This method is used for quantitative analysis of organic matter present
In the sample. In this method, nitric acid is added first, heated, cooled and then
HN0 3-HCl04 mixture is added. Here nitric acid acts as, a moderate agent by oxidising
the more reactive compounds at lower temperature. The HN03-HCl04 mixture should
be handled with great care otherwise it causes a violent explosion.
(ii) Dry Ashing : In this method, the sample having organic matter is made to heat In an
open crucible in presence of air or oxygen to red hot until all the carbonaceous
material is oxidised. In this method, the loss of sample by sputtering and volatilization
should be avoided.
Solutions of Samples
Some organic substances dissolve readily in suitable organic solvents and some dissolve
directly in water or can be dissolved in aqueous solutions of acids (basic materials) or of alkalis
(acidic materials). Some inorganic substances can be dissolved directly in water or in dilute
acids, but materials like minerals refractories: and alloys must usually be reacted with various
reagents so as to find out a suitable solvent.
If a substance dissolves readily, the sample is made to weigh out into a beaker and the
beaker is immediately covered with a c10ckglass of suitable size whose diameter should not be
more than about 1 cm larger than that of the beaker with its convex side facing downwards. The
beaker should have a spout so as to provide an outlet for the escape of steam or gas. The solvent
is then added by pouring it carefully down a glass rod, the lower end of which is made to rest
against the wall of the beaker, the clockglass is displaced carefully during this process.
When a gas is evolved during the addition of the solvent (e.g., acids with carbonates,
metals, alloys, etc.) the beaker must be kept covered during the addition. The reagent is then
added by a pipette or a funnel with a bend stem inserted beneath the clockglass at the spout of
the beaker; loss by spurting or as spray is thus prevented. If the evolution of gas gets ceased and
the substance is completely dissolved, the under side of the c10ckglass is rinsed with a stream
of water from a wash bottle, care should be taken that the washings should fall on the side of
the beaker but not directly in the solution.
When warming becomes necessary, it is usually preferred to carry out the dissolution in a
conical flask with a small funnel in the mouth, loss of liquid by spurting is thus prevented and
the escape of gas is not hindered. When volatile solvents are used, the flask is fitted with reflux
condenser.
In order to reduce the volume of the solution or sometimtls to evaporate completely to
d~ryness, ~de and shallow vessels are preferred, ,bec~use a large surface is thus exposed and
evaporauon is/thereby accelerated. Evaporation should be'done on the steam bath or upon a low
temperature hot plate. During evaporation, the vessel should be covered by a pyrex clock glass
which should be slightly larger in diameter than the vessel. At the end of the evaporation, the
sides of the vessel, as well as the lower side of the clockglass must be rinsed with distilled water
into the vessel. . .~.
Dissolving Inorganic samPlt

Strong mineral acids fin use as good solvents for many inorganic samples. Hydrochloric
acid behaves as a good generhl solvent for dissolving metals, which lie above hydrogen in the
electromotive series. Nitric acid behaves as a strong oxidizing agent and is able to dissolve most
of the common metals, nonfen-ous alloys, and the "acid insoluble" sulphides.
Perchloric aCId, when heated to drive off water, behaves as a very strong and efficient
oxidizing acid in the dehydrated state. It is able to dissolve most of the common metals and
destroys organic matter. It must be used with extreme care because it will undergo reaction
explosively with many readily oxdizable substances specially organic matter. Some inorganic
materials do not dIssolve in acids, and fusion with an acidic or basic flux in the molten sate must
be used to render them soluble.
I
The vanous factors which are taken into consideration while using an acid are as follows:
1. Whether an oxidising or non-oxidising acid is needed?
2. Which kind of anion is suitable or most appropriate in solution?
3. What are the chemical properties of the sample?
4. In what way excess of acid is removed from the sample?
These facts can be readily understood if we are having some idea of inorganic reactions
alongwith chemical common sense. For example, if sample is having barium metal or ion, then
the sample cannot be dissolved in H 2S04 , Similarly, HCI is not used to dissolve a silver metal
or silver salt sample. Acid treatment of carbonate and sulphide samples may cause the loss of
CO 2 and H 2S, provided these gases are not trapped. In some cases acid may make a part of the
sample to become passive, due to an oxide coating;
All samples are neither pure metals nor metal oxides or alloys. Therefore it is not easy to
describe the acid conditions to dissolve inorganic samples. In general, acid conditions may be
classified according to wh~ther the acid is oxidising (HN03 , conc. H2 S04 , hot conc. HCI04 ) or
non-oxidising (HCI, dil H 2S04 , dil HCI0 4).
If metals are made to dissolve in non-oxidising acids, a process of hydrogen replacement
is said to take place. Metals below hydrogen in the series of reduction potentials dissolve in non-
oxidising acids. Exceptions because of the presence of passive condition, oxide film formation
or insoluble salt formation may, however, take place. HCI dissolves metals above hydrogen, salts
of weak acids and many oxides. Dilute H2 S0 4 and HCI0 4 dissolve metals above hydrogen. Hot
and cone. H2S00( dissolve metals below hydrogen.
Nitric acid dissolves metals below and above hydrogen, due to the fact that its oxidising
power varies according to whether the acid is dilute or concentrated. In general, metal gets
oxidised to its highest oxidation state. Some limitations to these rules are that some metals (AI
and Cr) become passive, whereas Sn, Sb and W form insoluble acids. RNO} dissolves sulphide
/flTroduction to Analytical Chemistry 1·37
salts and salts of oxidisable anions whereas hot conc. HCI0 4 is able to dissolve almost all
common metals.
In some cases, acids in combination are advantageous. For example a mixture of conc.
HN03 and conc. HCI in the ratio 1 : 3 is known as aquaregia, in which RN03 provides oxidising
power and HCI complexing properties and strong acidity. Solubility of many metal ions can be
maintained only in the presence of complexing agent. In some cases the solvent action of mineral
acids may get increased by addition of bromine or hydrogen peroxide.
Hydrofluoric Acid Behaves as a Weak as well as Non-oxidising Acid. It readily decomposes
silicate samples and silica is volatilised as SiF4 , HF is better than Hel in that it furnishes a good
complexing anion F-. As HF can cause serious injury to skin, it may be prepared in lieu by adding
NaF to an HCI solution of the sample. Hot and conc. HCI04 is a potent oxidiser and it is also
a dehydrating agent. It readily oxidises organic materials.
Minerals and rocks, like silicates, sulphides, phosphates, carbonates, sulphates, refractory
minerals and oxides need special treatment.
Sample Decomposition and Dissolution

Majority of the analytical determinations are carried out in aqueous solutions of the analyte.
Some samples dissolve rapidly in water or aqueous solutions of the common acids or bases while
other samples need strong reagents and treatment to dissolve them. For example:
(a) In order to destroy the silicate structure of a siliceous mineral and to free the ions for
analysis, the sample needs high temperature and pressure, and many other drastic
conditions.
(b) The compounds of halogen and sulphur are heated at high temperatures with powerful
reagents to break the strong bonds between elements and carbon atom. In this way it
is possible to determine the contents of sulphur and halogen elements in that organic
compound.
The following are four types of common methods of decomposing ancYaissolving an analytical
sample.
1. By heating with aqueous strong acids or bases in open vessel.
2. By microwave heating with acids.
3. By high temperature ignition in air or oxygen.
4. By fusion in molten salt media.
These methods differ in the temperature at which they are performed and the strength of
the reagents used.
A very difficult task is to select a proper reagent and technique for decomposing and
dissolving an analytical sample especially when refractory substance is involved or the sample
may be present in trace quantity.
1. Decomposing Samples with Inorganic Acids in Open Vessels

The mineral acids are usually used for decomposing the inorganic samples in open-vessel.
In some cases ammonia and aqueous solutions of the alkali metal hydroxides are used. A suspension
of the inorganic sample is fir~t of all prepared in the mineral acid. Then it is heated by flame
or a hot plate until the dissolution is confirmed to be complete by the total disappearance of a
solid phase. In this process the temperature of decomposition is maintained at the boiling point
of the used acid reagent.
The following acids are used for the purpose 1
(a) Hydrochloric Acid

(b) Nitric Acid
(c) Sulphuric Acid
(d) Perchloric Acid
(e) Oxidising Mixture of acids
(f) Hydrofluoric acid.
(a) Hydrochloric Acid: Concentrated HCI acts as an excellent solvent for inorganic
samples. It is widely used for dissolving the metals which are more readily oxidized
than hydrogen as well as many metal oxides. Hydrochloric acid is having limited
applications in decomposition of organic' substances. The molarity of concentrated
HCl is about 12 M.
(b) Nitric Acid: In order to dissolve all common metals except aluminium and chromium
(due to surface oxide formation), hot concentrated nitric acid is used as a potent
oxidant. For the measurement of the trace'metal contents in samples, hot nitric aid is
used as such or in combination with other acids and oxidizing agents. In order to
decompose organic samples, hot nitric acid is used with hydrogen peroxide and bromine.
In this process organic sample is converted into CO2 and water. This decomposition
process is called wet ashing process.
(c) Sulphuric Acid: There are many materials which are decomposed and dissolved by
hot concentrated H 2S04, But the boiling point of sulphuric acid is very high (about
340°C). Therefore most of the organic compounds are dehydrated and oxidized at this
temperature and hence eliminated from the sample as CO2 and H 20 by this wet ashing
process.
(d) Perchloric Acid: Perchloric acid is a very strong acid. It can attack iron alloys and
stainless steel (which are not attacked by other mineral acids). Because of its high
explosive nature, perchloric acid is handled with great care. Although the dilute heated
-acid and cold concentrated acid is not explosive in nature, violent explosion takes
place when hot concentrated perchloric acid comes in contact with organic materials
or easily oxidised inorganic substances. Due to this property, this acid is heated in a '
special hood lined with glass or stainless steel and its own fan system. The hood for
perchloric acid must be independent of all other systems. Commercially perchloric
acid is usually marketed as 60% to 72% acid.
(e) Oxidising Mixture of Acids: In order to decompose the samples, some oxidising
agents are used as the mixture of acids, like :
(i) Aquaregia is a mixture having 3 volumes of concentrated HCI and 1 volume of

nitric acid.
(ii) The addition of bromine or hydrogen peroxide to mineral acids usually increases
their solvent action.
(iii) Mixtures of nitric acid and perchloric acid are also used for this purpose. The
main advantage is that they are les~ dangerous than perchloric acid alone.
(f) Hydrofluoric Acid: This acid is mainly used for the decomposition of silicate rocks
and minerals in the analysis of elements other than silica. This acid finds occasional
use with other acids in dissolving steel which is difficult to dissolve in other so~vents.
But hydrofluoric acid is extremely toxic. Therefore dissolution of samples and
evaporation to remove excess reagent should always be done in a well-ventilated
hood. Hydrofluoric acid brings about serious damage and painful injury when come
in contact with skin. When the acid comes in contact with skin, the affected area
should be immediately washed with huge quantity of water.
2. Microwave Decomposition
The microwave ovens are being used for the decomposition of organic and inorganic
compounds. Microwave digestions can be performed in both closed as well as open vessels, but
closed vessels are often preferred because higher pressure and temperature can be attained in
them.
The decomposition of compounds in microwave
oven happens to be very fast and speedy. Even in case
of typical and difficult samples it needs only 5 to 10
minutes. In contrast, the same results need several hours
when sample is made to heat over a flame or a hot
plate.
In conventional methods, the heat transfer takes

place by conduction. The vessels used in conductive
heating are usually poor conductors. Therefore, Safety valve
sufficient time is required to heat the vessel and then
transfer the heat to the solution by conduction.
In microwave oven, the transfer of energy takes
place directly to all the molecules of the solution almost
simultaneously without heating up the vessel. Hence,
~"" .."".. I body
boiling temperatures are reached throughout the whole
$olu!ion very quickly.
The main advantage of using closed vessels fpr
microwave decomposition is the higher temperature
which develops because of increased pressure. One Fig. 12 : ~ moderate-pressur.e.vessel
more advantage of micro-wave decomposition is that for microwave decompositlOn
loss of volatile components of samples is virtually eliminated. Closed vessel microwave decompo-
sition is usually easy to automate, thereby reducing operation time needed to prepare samples for
analvsis.
Moderate Pressure Vessels: Microwave digestion vessels are transparent, thermally stabl~,
resistant to chemical attack by various acids used for decomposition. The best material fo1' .
mICrowaves is teflon which is transparent, inert against sulphuric acid and phosphoric acid,
havmg a melting point about 300°C. Quartz or borosilicate glass vessels are also used in place
of teflon containers. A closed digestion vessel of teflon body consists of a cap and a safety relief
valve to operate at 120 ± 10 Psi pressure. At this pressure, the safety valve might open and is
then resealed (Fig. 12).
High Pressure Microwave Vessels: In order to dissolve highly refractory materials which
are not completely decomposed in the moderate pressure vessels, the microwave bomb is especially
useful. In this bomb, the heavy-wall body is made from a polymeric material which is transparent
to microwaves. The decomposition of the material is ,done in a teflon cup supported in the bomb
body. It is having a teflon O-ring in the liner cap which seats against a narrow rim on the exterior
of the liner. The O-ring distorts, and the excess pressure then compresses the sealer disk, which
makes the gases to escape into the surroundings. The internal pressure in the bomb can be
guessed by the distance to which pressure screw protrudes from the cap. A commercial microwave
bomb is designed to operate at 80 atm or about 10 times the pressure which can be tolerated by
the moderate pressure vessels as described above (Fig. 13).
Pressure screw
Screw cap
Inner cover
O-ring
SampJecup
Bomb body
Bottom plate
Fig. 13 : A bomb for high pressure microwave decomposition

Atmospheric Pressure Vessels : Atmospheric pressure vessels are open-vessel systems.
These systems are not having an oven but use a focussed microwave cavity. They are having
tubing for the insertion and removal of reagents. There is no safety due to the formation of gas
during the reaction of digestion process because the systems operate at atmospheric pressure.
Microwave Ovens: A microwave oven consists of 12 moderate pressure vessels which can
be heated at a time. It is designed as shown in Fig. 14. The vessels can rotate continuously
through 360 degrees so that the average energy received by each vessel is almost the same.
Microwave Furnaces : In microwave furnance an organic material is fused before acid
dissolution. The furnace is having a small volume chamber which is able to accommodate only
an ordinary-sized crucible. This small cavity-like chamber is made up of silicon carbide which
is surrounded by quartz insulation. The advantage of this type of furnace over a conventional
muffle furnance is the speed, at which the high temperature (1000°C) is attained in 2 minutes.
In contrast, the muffle furnaces are generally operated continuously because of the time required
to get them upto required temperature. In a microwave furnace there is no burnt out heating coils
as frequently found in the conventional furnaces.
Turn table
Digesting vleeiss~e:ilttt;~~~~~~~
Digesting vessel Turn table

Fig. 14 : A microwave oven designed for use with 12 vessels

Applications of Microwave Decomposition : The applications of closed vessel decompo-
sition in microwave oven can be grouped into two categories :
(i) Oxidative decomposition of organic and biological samples.
(U) Decomposition of refractory inorganic materials in industry.
In bddl tQt: above cases, the new microwave technique has been replacing older conventional
methods due to the large economic gains which result from significant saving in time.
,
3. Combustion Methods for Decomposing Organic Samples
(a)Combustion Over an Open Flame (Dry Ashing) : In order to determine the.
constituents of an organic sample, it is heated till red hot in an open dish or crucible
over a flame so that all the carbonaceous matter is oxidized and converted into
carbondioxide. Analysis of the non-volatile components is followed by dissolution of
the residual solid. In addition, volatile metallic compounds may get lost during the
ignition process. Although dry ashing is the simplest method of decomposing organic
compounds, it is usually the least reliable.
(b) Combustion-Tube Method: Several elemental components of organic compounds

get converted into gaseous products when a sample is pyrolyzed in the presence of
oxygen. The heating is usually carried out in a glass or quartz combustion tube through
which a stream of carrier gas is allowed to pass. The stream transports the volatile
products to the, parts of the apparatus where they get separated and retained for
meas~ement. Elements subjected to thjs type of treatment have been carbon, hydrogen,
nitrogen, sulphur, halogens and oxygen.
Automated combustion-tube analyzers are now being used for the determination of
either carbon, hydrogen, and nitrogen or ~arbon, hydrogen and oxygen in a sample.
This analysis is complete in less than 15 minutes. In this analyzer, the sample is made
to ignite, in a stream of helium and oxygen and allowed to pass over an oxidation
catalyst consisting of a mixture of silver vandate and silver tungstate. In this process
the halogens and sulphur are removed with a packing of silver salts. A packing of hot
copper is situated at the end of combustion train to remove oxygen and convert
nitrogen oxides to nitrogen. The exit gas is a mixture of H20, CO 2, nitrogen and
helium and is collected in a glass bulb.
(c) Combustion with Oxygen in a Sealed Container: The decomposition of many
organic materials is carried out in a sealed container. Before the reaction vessel is
opened, the reaction products are absorbed in a proper solvent. Schoniger suggested
an apparatus (Fig. 15). It consists of a heavy-walled flask of 300-1000 mL capacity
fitted with a ground glass stopper. Attached to the stopper is a platinum gauze basket
which is able to hold 2 to 200 mg of sample. The solid is wrapped in a piece of low-
ash filter paper. The liquid samples are made to weigh in a gelatin capsule which is
then wrapped in a s'imilar manner. A small volume of an absorbing solution is put in
the flask. The tail of the paper is ignited, the stopper is fitted immediately into the
flask, and the flask is inverted to prevent the escape of the volatile oxidation products.
The entire reaction is calayzed by the platinum gauge surrounding the sample. This
procedure is used to determine the halogens, sulphur, phosphorus, fluorine, boron,

carbon, arsenic, and various other metals present in organic compounds.
SamPle-ti]
Sample in hold~r
~
Sample wrapped in
paper holder
Absorption liquid
Stopper with T ground joint
Fig. 15 : SchOniger combustion apparatus
Introduction to Analyucal Chemistry )'43
4. Decomposition of Inorganic Material by Fluxes

Some inorganic substances can not decompose easily like mineral oxides, silicates and
some iron alloys. In such cases flux is mixed with the sample and then this combination forms
a water-soluble product called melt.
Flux is an alkali-metal salt. It is used to decompose the substances which are attacked by
the reagent very slowly.
For a sample having a small fraction of substance which dissolves with difficuity, is made
to mix with a liquid reagent, the undecomposed residue is then separated by filtration and is
fused with a small quantity of proper flux. After cooling the above combination, the melt is
dissolved and combined with the major fraction of the sample.
Procedure of Fusion : Firstly, the sample is grinded to get fine powder. It is mixed with
a suitable flux. The quantity of flux should be 10 times of the sample. Mixing of flux and sample
is done in a crucible. The fusion is carried out in the crucible for a few minutes to a few hours.
The formation of a clear melt reveals the completion of decomposition. After completing the
fusion, the mass is allowed to cool, before solidification.
Types of Fluxes : The common fluxes used in analysis are compounds of the alkali metals.
The fluxes are of following types :
(a) Basic Fluxes: These include alkali metal carbonates, hydroxides, peroxides, and
borates. The basic fluxes are used to attack acidic materials.
(b) Acidic Fluxes: These include pyrosulphates, acid fluorides, and boric oxide.
(c) Oxidizing Fluxes: e.g., sodium peroxide.
The properties of some common fluxes are given as follows :
(i) Sodium Carbonate: When fused with sodium carbonate the samples having silicates
and some other refractory materials are decomposed by heating at lOOO°C to 1200°C.
By this fusion, the cationic constituents of the substance (sample) are generally converted
into acid-soluble carbonates or oxides while non-metallic constituents are converted
into soluble sodium salts. Carbonate fusion is usually carried out in platinum crucible.
(ii) Potassium Pyrosulphate : It is a strong acidic flux. It is used for attacking the more
intractable metal oxides. With it flux fusion is performed at 400°C.
Potassium pyrosulphate is prepared by heating potassium hydrogen sulphate, in thIS way:
2KHSO4 ~ K2 S20 7 + H 20
(iii) Lithium Metaborate : LiB02 [lithium metaborate], mixed with lithium tetraborate,
is fused with refractory silicate and alumina minerals. This fusion is performed in
platinum or graphite crucible at 900°C.
Table 6 : Common Fluxes
Flux Crucible Applications

Non-oxidising
Na 2C03 Pt Silicates, phosphates, sulphates
NaOH Au, Ni, Ag, Silicates, silicon carbides
KOH Au, Ni, Ag Silicates, silicon carbides
SPJ Pt Silicates, oxides
CaC03 + NH 4CI Ni Silicates
Oxidising
Na20 2 Fe, Ni Sulphides, acid insoluble alloys, like ferro-
chromium, ferrotungsten, Ni, Mo, W, Pt
alloys. Insoluble oxides, iron ore, Zr.
Pt. Porcelain Hf and Th phosphates.
Advantages of Using Fluxes

Fusion with a flux is more potent than acid treatment due to the following important reasons: 1
1. As a flux is a fused salt media, the temperatures needed for creating the condition
(300°C to lOOO°C) are much higher than-possible by the acid treatment.
2. There exists a greater concentration of reagent in contact with the sample.
3. Fluxes may yield oxidising as well as non-oxidising conditions. Therefore, the advantage
of these conditions is also maintained.
Difficulties in Using Fluxes

1. Special containers made of Pt, Ag, Ni, Au and Fe are needed which are able to
withstand the temperature and reacting conditions.
2. It is desirable to know the reactivity of flux before a crucible is selected.

3. Impurities introduced by flux, voltalization because of high temperature, spattering
losses due to reaction are some other difficulties.
Selecting and Handling of Reagents

For carrymg out quantitative analysis in the analytical laboratory, always use the analytical
reagent (AR) quality. There are certain manufacturers who market chemicals of high purify and
each package of these analytical chemicals is having a label stating manufacturers, limits of
certain impurities. When the reagents are handled, the following points should be kept in mind:
(i) Always pour liquid reagents from the bottles. Never ip.sert a pipette into the reagent
bottle.
(ii) Always take particular care to avoid contamination of the stopper of the reagent bottle.
When pouring a liquid from a reagent bottle, never place the stopper on the shelf or
on working bench but always keep a clean watch glass. Immediately return the stopper
to the bottle immediately after the reagent has been removed.
Introduction <to Analytical Chemistry 1·45
(iii) Keep all reagent bottles scrupulously clean, especially around the neck or mouth of
the bottle.
(iv) Test the purity of the reagents by following the standard methods for the impurities
which may cause errors in the determinations.
(v) Always use Analytical Grade (A.R.) Reagents in analytical laboratory. If A.R. reagents
are not available, then select the best grade of chemicals available for analytical work.
(vi) Always use special grades of solvents for special purpose, e.g., spectral grades or
chromatographic grades.
(vii) Always try to pick the smallest bottle that will supply the desired quantity.
(viii) Unless specifically directed, never return any excess reagent to a bottle. The returning
excess may be contaminating the entire bottle.
(ix) Unless directed otherwise, do not insert spatul~s, spoons or knives into a bottle that
is having a solid chemical. Instead shake the capped bottle vigorously or tap it gently
against a wooden table to break up encrustation, then pour out the desired quantity.
If these measures are ineffective, in such cases use a clean porcelain spoon.
(x) Keep the reagent shelf and the laboratory balance clean and neat. Clean up' spills
immediately, even though some one is waiting to use the same chemical or reagent.
(xi) Follow the local regulations concerning the disposal of surplus reagents and solutions.
Gravimetric Analysis or Gravimetry or Gravimetric Techniques

It refers to the process of isolating and weighing an element or its compound of definite
composition in as pure a form as possible. The element or compound is separated from the weighed
portion of the substance which is to be examined. It is possible to calculate the weight of the
element from the formula of the compound and relative atomic masses of the constituent elements.
Gravimetric analysis may be carried out in a number of ways such as :

(i) Precipitation method
(ii) Volatilisation or evolution method
(iii) Electrodeposition methods
In conventional laboratories, Gravimetric analysis by precipitation is gen~rally carried out.
In this method, the constituents of the substances in solution are determined by the measurement
of weight of the corresponding precipitate. The various operations in obtaining a pure sample by
precipitation are as follows :
(i) Precipitation of the desired constituent
(ii) Filtration
(iii) Drying
(iv) Weighing of precipitate.
111 electrodeposition, the desired constituent is deposited or isolated at an electrode by the
passage of an electric current. The weight of the desired constituent is then calculated by the
difference
Chatwal, Gurdeep in weight
R., and Madhu of theChemistry,
Arora. Analytical electrode before
Himalaya andHouse,
Publishing after
2008.the electrodeposition.
ProQuest Ebook Central,
1'46 Introduction to Analytl~al Chemistry
In volatilization. the sample is decomposed by a ~own stoichiometric reaction in which

one of the products is volatilized. The amount of vapourized constituent is then calculated by the
,difference m weight before and after volatilization. In this respect the process is similar to the
electrodeposition method.
The main disadvantages of gravimetry are as follows :
(i) If modern analytical balances are used, then gravimetry is precise and accurate.
(ii) The possible sources of errors in gravimetry can be readily checked.
(iii) Filtrates can be tested for completeness of precipitation.
(iv) The precipitates can be examined for the presence of impurities.
(v) It is an absolute method.
(vi) It can be carried out with relatively inexpensive apparatus. However, the most expensive
requirement being a muffle furnace and in some cases, platinum crucibles.
(vii) It can be used for the analysis of standards which are used for the testing and calibration
of instrumental techniques.
The main disadvantage of gravimetry is that it requires high accuracy and time consuming.
These limit its applications to small number of determinations.
Precipitation Method
Introduction : The constituent to be determined is precipitated from solution in a form
which is slightly soluble and the precipitate is separated by filtration and weighed. For example,
in the determination of silver a solution of the substance having Ag+ is treated with an excess
of sodium chloride or potassium chloride, the precipitate of AgCI is filtered off, well washed to
remove soluble salts, dried at 130-lsoac and weighed as silver chloride.
AgN0 3 + KCI -----t AgCI + KN0 3
Sometimes, the constituent being determined is, weighed in a form which is different from
the form III whIch it was precipitated. For example, magnesium is precipitated as ammonium
magnesIUm phosphate Mg(NH4) P04 , 6H20 but after ignition is weighed as magnesium pyrophos-
phate, Mg2P2 0 7 •
The factors stated below decide a successful analysis by precipitation method :
(i) The solubility of the precipitate must be so low that no appreciable loss occurs when
it is collected by filtration.
(ii) The physical nature of the precipitate should be such that it could be readily separated
from the solution by filtration and could be washed free of soluble impurities. From
these factors it is evident that particles are of such size that are unable to pass through
the filtering medium and the particle size is not altered by the washing process.
(iii) The precipitate might be converted into a pure substance of definite chemical
composition. This might be achieved either by ignition or by a simple ch~mical operation
(e.g., evaporation) with a suitable liquid.
lJItroduction to Analytical Chemistry 1·47
It is generally assumed that the precipitate separated from the solution is chemically pure
but this is not true in all cases. The purity of the, precipitate depends more or less upon the
substances present in solution before and after the addition of the r~agent and also upon the exact
experimental conditions of precipitation.
Types of Precipitating Reagents

Many organic and inorganic precipitating reagents are used for precipitation, but the type
of charactenstics that a particular precipitating reagent and precipitate itself have, depends upon
the application. The most important characteristics of precipitating reagents are as follows :
1. Solubility
2. Ease of filtering
3. Stoichiometry
4. High formula weight
5. Non-hygroscopic, and
6. Selectivity.
There first three characteristics are very clear' cut and need no discussion. The precipitate
must have high formula weight or molecular weight, because a precipitate is actually a small
amount of the cation or anion being determined. If it is stable and non-hygroscopic, special
handling techniques are not needed. As a result, errors in weighing are greatly reduced. Precipitating
agent should precipitate only one cation or one anion. Similarly at least one reagent should be ,
avallable for each cation and for each anion. All these characteristics are rarely encountered.
Hence a compromise is made.
Orga?ic precipitating reagents are having several advantages over others:
(a) Very low solubility of many precipi~ates because of the stable bond between the metal
ion and the reagent anion. '

(b) Sensitivity of precipitation reactions is increased due to the low solubility.
(c) There is a wide choice of new reactions 'of separation of elements from complicated
mixtures.
(d) The weighing form can be obtained without igniting the precipitate.
The extent of completeness of precipitation largely depends upon the pH of the solution,
temperature, and the presence of interfering ions.
Depending on precipitation conditions, precipitates formed may be coarsely crystalline
(> 0.1 mm crystals) and finely crystalline (about 0.01 mm crystals). Finely crystalline precipitates
are unwanted because they may pass through the pores of the filter paper, causing loss of
precipitate. They can also clog the filter pores. They are readily contaminated because of their
large relative surface area and imperfection of crystals. Coarsely crystalline precipitates are,
therefore, preferred.
The requirements for suitability of a reaction for use in gravimetric analysis are as follows:
(a) The reaction should be stoichiometric.
(b) -·The chemical reaction should proceed fast, otherwise extra and excessive time would
be required for the reaction to complete.
(c) The reaction should be quantitative and must be complete by 99.9%.
(d) After completing the reaction, it is necessary to know a convenient method to follow
the progress of the reaction.
The reaction is assumed to be complete when 'one of the following takes place:
(i) Formation of undissociated molecules.
(ii) Formation of precipitate.
(iii) Formation of chelate.
(iv) Formation of gas.
Procedure Involved in Gravimetry

It involves the following steps :
1. Precipitation : The sample to be analysed is weighed accurately. Then, the weighed
sample is dissolved in a suitable solvent. The species which may interfere with actual measurements
are usually removed by suitable separation methods. Experimental environment is adjusted, e.g.,
pH adjustment by addition of buffer solution, change of oxidation state, concentration or dilution
of the sample or adding masking agents. A suitable precIpitating regent is added. Precipitation
is usually carried out in hot dilute solution. This will minimise the errors due to co-precipitation.
During precipitation, the reagents should be mixed with constant stirring. This will keep the
degree of supersaturation small and will assist the growth of large crystals.
Precipitation tends to be effective in hot solutions provided the solubility and the stability
of the precipitate allow. Either one or both of the solutions must be heated to just below the
boiling point. At the higher temperature, (i) the solubility of precipitate gets increased with
reduction In the degree of supersaturation, (ii) coagulation is increased while sol formation
decreases, and (iii) the rate of crystallisation is increased.
If the precipitate is still appreciably contaminated as a result of co-precipitation or other
causes, the error may be reduced by dissolving it in a suitable solvent and then re-precipitating it.
2. Digestion: This is carried outby keeping the precipitate to stand for 12-24 hours at room
temperature or by warming the precipitate for some time in contact with the liquid from which
it was formed. The net result of digestion is to reduce the extent of co-precipitation and to
increase the size of the particles causing filtration easier.
Crystalline precipitates should be digested overnight except in those cases where post-
precipitation may take place. It is to be remembered that digestion of precipitate on the steam
bath is preferable because this lowers the effect of co-precipitation and produces more readily
filterable precipitate. Digestion is having little effect upon amorphous precipitates.
3. Filtration : Precipitate is separated from the mother liquor by filtration by using Whatmann
filter paper or sintered crucible.
4. Washing the Precipitate : The precipitates are usually formed in the presence of one
or more soluble compounds. The washing of precipitate removes these soluble substances as
completely as possible. Only surface impuries will be removed by this process.
This precipitate should be washed with appropriate dilute solution of an electrolyte. Pure
water may cause peptisation.
If, permissible, hot solutions are to be preferred because of the grater solubility of the
foreign substances and the increased speed of filtration.
It is possible to divide wash solutions into there types :
Type I This includes solutions which do not allow the precipitate to become colloidal and do
not allow the precipitate to pass through the filter. The wash solution should contain
an electrolyte. Ammonium salts are widely used as electrolytes.
Type II This includes solution which reduce the solubility of the ·precipitate. The wash solution
may be having a moderate concentration of a compound with ion common with the
precipitate.
Type III This includes solutions which prevent the hydrolysis of precipitates provided they
(precipitates) are salts of weak acids and bases. If a precipitate is a salt of weak acid,
the wash solution must be basic. If a precipitate is a salt of wake base, the wash
solution must be acidic.
5. Drying : The precipitate is dried as such or it is ignited to get some suitable precipitate
product.
6. Weighing: The dried precipitate or some suitable precipitate product formed as a result
of jgnition is weighed finally. Then, the per cent of substance in the sample is calculated.
Laboratory Note Book

Laboratory note book is the permanent record of the experimental data. It is a record of the
work of an analytical chemist. It is the source for reports, publications and regulatory submissions.
It is a record of original ideas. If the note book is properly maintained, then it becomes possible
to know the original data taken and the results for the analysis with a minimum effort. Sufficient
details should be recorded in the note book so that it b~comes possible to trace the course of
analysis. If an error is suspected, then note Look becomes valuable. Note book should, therefore,
have all data, observations and conclusions recorded in ink on bound pages. In a laboratory note
book, loose sheets of paper should never be used. While carrying out the experiment all data
should be noted immediately in the note book but not at a later time. One should not erase
erroneous data but should cross out because sometimes these data may be found to be useful at
a later time.
The success or failure of a company's product or service may depend on how well it is
documented.
The various advantages of recording experimental data in the laboratory note book are as
follows:
(i) First advantage is the saving of time in not having to recognize and rewrite the data
and the chances for a mistake will be reduced.
Introduction to Analytical Chemistry
'(ii) Second advantage in an immediate record is to be able to detect possible errors in the
measurements or calculations.
(iii) Third advantage is that the data will not be lost or transferred illCGrrectly, if they are
recorded directly in a note book instead of collecting on scraps of paper.
In order to maintain a note book, the rules given below are followed.
(i) Use a hardcovered note book of A4 size for recording experimental observations as
they are made.
(ii) Do not use loose leafs.
(iii) Write the name of project on the proper place.
(iv) Number the pages consecutively.
(v) Do not tear out pages. If page is not used, put a line through the page.
(vi) Put date on each page and sign properly.
(vii) Always record the observations in ink immediately as soon as these are obtained.
(viii) Always devote a double page for each detj;lrmination. Indicate the title of experiment.
Reserve one page for the experimental observations while reserve the other page for
a brief description of the procedure followed and a full account of any special features
associated with the determination.
(ix) Divide the page on which the experimental observations are to be recorded into two
halves by a vertical line and then to half the right hand column thus created by a
second vertical line. Now use the left-hand side of the page to indicate the observations
to be made and record the data for duplicate determinations side by side in the two
right-hand columns.
(x) Conclude the record with the calculation of the result ofthe analysis. Also, write down
the equations and reactions involved in the determination.

(xi) Finally, make appropriate comments upon the degree of the accuracy and the precision
achieved.
(xii) Interface modem analytical instruments with a computer and a printer. A print out
provides a permanent record of experimental data and final results. Attach the print
out permanently to the observation page pf the laboratory note book.
(xiii) Also perform a rough calculation to confirm that the printed result is of the right order
or not.
Chemical Standards
All analytical methods need a chemical standard. In volumetric titration, the measured
volu~e of a reagent of known concentration is added to a solution of an unknown concentration
or to a solution of the substance to be analysed. Addition is done continuously upto stoichiometric
end point at which amount added- is stoichiometric to the quantity of substance to be analyzed.
In order to find out the amount of unkrlown substance in the solution, it is essential to know the
concentration of the reagent solution accurately and such a solution is termed as standard solution.
Standard Solution : The solution of a primary chemical standard is prepared directly by

exactly weighing the substance by using an analytical balance and then dissolving it into a known
volume in a volumetric flask. In this way the prepared solution is known as standard solution of
the known concentration. It is possible to express the concentration of this solution in terms of
molarity, molality, normality, or formality as the case may be.
A standard solution of known acidity can be prepared when primary standard is acidic. A
standard solution of known basicity is obtained, when primary standard is basic.
A substance whose standard solution can not be prepared directly by weighing is called
secondary chemical standard and its solution is prepared by standardizing against a standard
solution of a primary standard.
It is not possible to prepare the standard solution of sodium hydroxide (NaOH) directly by
weighing NaOH pallets, because it is a secondary standard and it is unable to meet the requirements
of a primary chemical standard. Therefore, a solution having the approximate concentration of
NaOH is first prepared and it is then standardized by titrating against acidic primary standard
solution of known concentration (standard solution).
The prepared NaOH solution is made to titrate against standard acidic solution to the
stoichiometric point and the concentration of the unknown NaOH solution can be calculated from
the amount of primary standard used, because reaction stoichiometry is known. The NaOH
solution is now standardized and is known as a secondary standard solution.
Essential Requirements of a Primary Chemical Standard

The various essential requirements of a substance to act as a primary chemical standard are
as foHows :
(a) The price of primary standard should be reasonable.
(b) It must be highly pure (e.g., upto 99.99%).
(c) It should be stable in nature.

(d) It should be non-hygroscopic.
(e) It should undergo stoichiometric reactions.
if) It should be completely soluble in the desired solvent.
(g) Its molecular weight should be high.
Safety in the Analytical Laboratory

Before starting any experiment, the student should be familiar with the laboratory safe!;
rules. The better house-keeping practices will ensure the safety working conditions in the laboratory.
General Safety Rules in Analytical Laboratories,

(i) In the laboratory, always clean up spill che'mtcals onto the banch or the floor or
rendered harmless with the suitable reagents. Neutralise the acid spills with sodium
carbonate and alkali spills with boric acid.
(ii) Prohibit drinking water and eating food in chemical laboratories.
(iii) Never taste or inhale chemical substances.

(iv) Before pouring alkali solutions in the sink, dilute them with tap water.
(v) Before pouring concentrated acids and chromic acid in the sink, dilute them with tap
water.
(vi) Do not remove dry alkalies such as NaOH, KOH, etc., and fluorides by hand because
they may cause scalds. Always remove them by using forcaps or a spatula.
(vii) Do not carry the vessels containing acids; alkalies or poisonous substances over the
heads of working students. Always put a towel under the bottom of the vessel.
(viii) Heat the test tubes and other glass vessels with caution. Do not face the vessel mouth
towards your colleagues in case the liquid is ejected.
(ix) Never look into the vessel from above where dissolution or melting is carried out.
(x) Do not leave broken or chipped glassware on the bench or shelves.
(xi) Place reagent bottles and apparatus properly after use.
(xii) Use the fume hood when working with volatile chemicals as when heating acids or
when using organic solvents.
(xiii) Use a safety shield when working with potentially dangerous compounds.
(xiv) Use the protective goggles when the work may cause bums, irritation or contamination
of eyes.
(xv) There are many chemicals which are inflammable. Also, there are many chemicals
which have been identified as acute or chronic toxic substances, frequently carcinogenic.
Always use rubber gloves and avoid breathing in fumes.
(xvi) While working with organic solvents, take special care.
(xvii) Allow the student to perform only the authorised experiments. Do not allow the
student to work alone in the laboratory. '
(xviii) In an analytic laboratory, locate fire extinguishers, fire blankets, safety showers, eye
fountains, and emergency exits.
(xix) Bring any dangerous or potentially dangerous laboratory situation immediately to the
notice of the laboratory supervisor.
(xx) Always plug electric devices such as heaters and ovens in a circuit with dry hands.
Rules of Working with Harmful Substances

(i) Never suck poisonous liquids or solutions with a pipette. Always use a pipette with
a rubber bulb for transferring such liquids or solutions.
(ii) Never leave bottles having poisonous substances on a bench.
(iii) Always use gloves when working with poisonous substances.
(iv) Always discharge solutions containing poisonous reagents, after being discharged, irito
a sink in 'a· fume cupboard. Wash the glass ware and sink thoroughly.
(v) Use a safety shield when working with potentially dangerous reactants.
(vi) When working with liquefied gases use only those cylinders which are coloured with
certam code shades and possess an appropriate level. ~
(vii) Do not keep vessels having inflammable substances near a flame.
Safety Rules for Fire Prevention

(i) Do not leave gas burners and heaters without care.
(ii) When fire originates, cut off the gas cock.
(iii) If a smell of gas is detected, do not light a fire or use an electric heater.
(iv) If the clothing catches fire, immediately cover the victim with felting over which water '.
is poured.
(v) If inflammable liquid is spilled accidently, first cutoff the gas cock or tum off hot
plates and other heaters and then remove the liquid.
(vi) Fire extinguishers should be readily available and reachable. Fire extinguishers should
be regularly checked.
First Aid in Laboratory

Before starting work in analytical laboratory, the student must be well acquainted with the
safety rules In the laboratory. He should have training in first medical aid so that he could render
first medIcal aid to himself and his friends or class fellows in case of accidents.
(i) In case of water vapour burns, flame bums and those caused by hot objects, wash the
burn with ethyl alcohol or 3-10% KMn04 and then put a sterile bandage on it.
(ii) If hot oil falls on the skin, first treat the bum with benzene and then apply on ointment
against bums.
(iii) When the liquid bromine gets on the skin, the cloths or on the bench, first treat the
site immediately with 20-40% sodium thiosulphate solution, then wash off with plenty
of water, and finally treat the skin with vaseline.
(iv) If acids or alkalies fall on the clothes or skin, first wash them immediately with plenty
of water and then with 3% NaF03 solution (in case of acid) or 1% CH 3COOH (in
case of alkali). In case of severe bum, place a pad of cotton wool and gauge soaked
with solution used for h~at bums on the affected site.
(v) If some drops of a chemical substance get into the eyes, wash the eyes immediately
with plenty of water.
(vi) If acid or alkali get into the eyes, first wash the eye with plenty of water and then with
2% NaHC0 3 solution (for acid) or saturated boric acid solution (for alkali). Wash the
eye for atleast is minutes. Finally consult the eye specialist.
(vii) When the mouth cavity is burnt with acid or alkali, rinse the mouth with 5% NaHC03
(in case of aci.d}-i5f 2% acetic acid (in case of alkali).
(viii) If the skin is injured with broken glass, first of all remove its fragments with forceps,
then treat the wound with rivanol (1 : 5) and finally apply a bandage. Fasten it with
adhesive tape.
(ix) In the case of a cut with glass, be sure that no glass piece or fragment remain in the
wound. Treat the edges of the wound with tincture of iodine and put on a sterile
bandage. If a wound is wide and bleeds strongly, pour 10% FeCl 3 or 3% H20 2 over
the wound repeatedly and then bandaged.
(x) In case a noxious gas (CI 2, Br2 , etc.) is inhaled, go to fresh air. To breathe in a dilute
solution of ammonia is also useful in this case.
(xi) When an inflammable liquid takes flame inside a vessel, tightly close it with a glass
plate, porcelain or metallic object, or a wet towel, or even with a wooden plate. In this
manner the flame is expected to be extinguished. Never try to blow off the flame or
extinguish it with water. If the burning liquid is split on the floor, extinguish the flame
with dry sand. If the fire is in the hood, first close the shutter or the door and then
proceed as already mentioned.
(xii) When fire happens to be in the laboratory, tum off the burners and electric heaters and
use fire extinguishers to control the fire. Fire extinguishers should be regularly checked.
(xiii) Use a woollen blanket to fight fire on a man. Wrap the victim tightly and hold for
1-2 minutes. The time is sufficient to extinguish the flame.
(xiv) Treat slight bums with glycerol or with cotton wool soaked in alcohol. In case of
stronger bums, place cotton wool or gauze soaked with saturated aqueous solution of
picnc acid or 1-2 percent KMn04 or tannin solution. Thi~ treatment removes pain and
prevents vesication. Now treat the affected site with vaseline. It must be noted that
never wet the burned skin with water. If the pain is strong, give the victim a tablet of
aspirin before advising or carrying him to the doctor.
(xv) Hang the safety instructions and also the means to fight incipient fires and to render
first medical aid in conspicuous and easy to get place.
(xvi) A wall mounted cabinet should contain all nece~sary medicines, solutions, small scissors,
bandaging and other materials that may be required in accidents.
(xvii) Do not be panicky. Report each accident, even very slight, to the instructor. Consult
the doctor in each case.
Prevention of Accidents in Analytical Laboratory

Some important points for preventing accidents in the laboratory are given below :
(i) Do not keep sodium metal, bromine, acids, and inflammable organic solvents, such as
benzene, ether, etc.; in the laboratory in large amounts. Residual quantities of metallic
sodium should not be thrown into the water sink, bu~ collected in special bottles
having liquid pataffin or kerosene oil.
\
(ii) Handle smaller vessels with solutions and substances holding the entire vessel in your
hand rather than the neck only. Handle large bottles usua]ly by their necks., These
vessels
Chatwal, Gurdeep R., and Madhu are carried
Arora. Analytical on the
Chemistry, palm
Himalaya of the
Publishing House,other hand.Ebook Central,
2008. ProQuest
Introduction to Analytical Chemistry I-55
(iii) Heat test tubes and other glass containers very carefully and gradually. The test tube
or glass containers should be wiped dry before putting them over a naked flame or on
a gauze.
(iv) Do not lean over the reaction vessel or look at its content through the neck. When
heating any liquid, direct the vessel mouth away from yourself and your mates in the
laboratory. When heating concentrated acids or alkalies, wear goggles.
(v) Ether, benzene, lower alcohols, acetone and other inflammable liquids should be care-
fully handled away from the open flame'. Try also not to inhale their vapours. Heat
them on baths with closed heater elements.
(vi) In the organic laboratory, handle the organic compounds like phenyl hydrazine, aniline,
nitro compounds, aromatic hydrocarbons, and other noxious substances, (which are
harmful to the respiratory ducts, the skin and the whole body) with great care trying
not to inhale their vapours. When some substance gets on the hands, wash it thoroughly
with soap and brush.
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INTRODUCTION TO ANALYTICAL CHEMISTRY

(ii) The presence or absence of certain chemical elements in the material.

Role of Analytical Chemistry

a short duration of analysis, high selectivity, accuracy and sensitivity, reductionlh

Classification on Analytical Methods

1. Classical or Chemical Methods

Advantages of Classical Methods

Limitations or Disadvantages of Classical Methods

2. Instrumental or Physicochemical Methods of Analysis

Physical property measured 7nstrumental methods based on

3. Emission of radiation. Emission spectroscopy, flame photometry, fluorescence,

Advantages of Instrumental l~/ethods

Limitations of Instrumental Methods

Differences between Classical and Instrumental Methods

Classical Methods Instrumental Methods

Types of Instrumental Analysis

Table 3 : Classification of Instrumental Methods of Chemical Analysis

Methods Quantity or Property Phenomenon underlying

(B) Optical Methods Interaction of matter with electro-

Methods Quantity or Property Phenomenon underlying

(C) Radiometric: Methods Radioactivity. Conversion of stable isotopes of an

Various Instrumental Techniques

(turbidimetry) or of light scattering in suspensions (nephelometry). Determining the absorption

(e.g. selenium, tellurium, bismuth).

Sensitivity and Detection Limits

Selection of an Analytical Method

Table 4 : Comparison of some Common Quantitative Analytical Methods

Method Concentration Accuracy Speed Relative cost

Method Concentration Accuracy Speed Relative cost

LABORATORY OPERATIONS AND PRACTICES

Wash Bottle ~...-v'''

Flask Porous plate

(iii) Other Types of Crucibles :

Factors on which Filtration Depends

or solution level. The lowest point of solution level

In order to prepare a solution of known concentration, another process can be followed.

Parts Per Thousand (ppt) and Parts Per Million (ppm)

day = 85,400 ephemeris seconds.

Neatness and Cleanliness in Analytical Laboratory

18. Perform experiment in terms of concepts, accuracy, precision and error.

. .1- Electronic Balance

Fig. 6 : Electronic analytical balance

weight value which appears as a digital display.

- -.... (OJl--Position scan

Fig. 7 : Operating principle of electronic balance

The beam is not brought completely to balance,

3. Semimicro and Microbalances

Techniques of Weighing Samples

Fig. 11 : Protection of sample during drying in an oven

(i) By electrification of the surface caused by rubbing: The electrification may be

The cleaning of glass ware is carried out by the following methods :

Calibration of Glass Ware

In ca1ibrati~opc1'ations, apparatus to be calibrated is first of all carefully cleaned and the~'

9. Phosphates are insoluble except those Na+, K+, and NH;.

Decomposition of Organic Matter

(i) Wet ashing

Dissolving Inorganic samPlt

Sample Decomposition and Dissolution

1. Decomposing Samples with Inorganic Acids in Open Vessels