Chapter - 2

INTRODUCTION TO ANALYTICAL CHEMISTRY

Topics to be Learn :
• Introduction
• Analysis
• Mathematical analysis
operation and error
• Determination of molecular formula
• Chemical reactions and stoichiometric calculations
• Limiting reagent.
• Concentration of solution
• Use of graph in analysis

Introduction:
Analytical chemistry : The branch of chemistry which deals with the study of separation,
identification, qualitative and quantitative determination of the compositions of different
substances, is called analytical chemistry.
Uses of Analytical chemistry
• Analytical chemistry helps to determine the chemical composition of substances.
• It involves separating, identifying and determining the relative amounts of the components
in a sample of matter.
• It uses instruments and methods to separate, identify and quantify the matter under study.
• The analysis thus provides chemical or physical information about a sample.
Applications of analytical chemistry:
• Analytical chemistry has applications in the field of forensic science, engineering and
industry such as the pharmaceutical industry and food industry.
• Besides these fields, it is useful in bio-analysis, clinical analysis, environmental analysis
and material analysis.
Chemical analysis: Chemical analysis is the study of the chemical composition and structure
of substances.
It is of two types : Qualitative and Quantitative.
• Qualitative analysis: Qualitative analysis deals with the detection of the presence or
absence of elements in compounds and of chemical compounds in mixtures.
• Quantitative analysis : Quantitative analysis deals with the determination of the relative
proportions of elements in compounds and of chemical compounds in mixtures.

Importance of chemical analysis :

Analysis:
Semi-microanalysis:
Analysis is usually carried out on a small sample of the material to be tested. When the
amount of a solid or a liquid sample taken for analysis is a few grams, the analysis is called
semi-microanalysis.
Semi-microanalysis is of two types : Qualitative and Quantitative.
Apparatus used to carry out semi-micro qualitative analysis.
The semi-micro qualitative analysis is carried out using apparatus such as, test tubes,
beakers, evaporating dish, crucible, spot plate, watch glass, wire gauze, water bath, burner,
blow pipe, pair of tongs, centrifuge, etc.
Classical methods of analysis :
Classical methods are subdivided into two methods : qualitative and quantitative methods of
analysis.
• Classical qualitative methods of analysis include separation methods such as precipitation,
extraction and distillation. In these methods identification may be based on differences in
colour, odour, melting point, boiling point and reactivity.
• Classical quantitative methods of analysis is achieved by measurement of volume or
weight. These methods consist of volumetric analysis, gravimetric analysis, etc. Volumetric
analysis is the process which involves measurement of volumes, while gravimetric analysis
involves measurement of weight.
Chemical methods of qualitative analysis :
The chemical analysis of a sample is carried out mainly in two stages- by the dry method
and the wet method.
• Dry method of chemical analysis: The dry method is usually used as the preliminary
tests in the qualitative analysis.
• Wet method of chemical analysis: In this method, the sample under test is first dissolved
and then analyzed to determine its composition.

The qualitative analysis of organic and inorganic compounds involves different types of tests.
Tests involved in the qualitative analysis of organic compounds:
• In organic compounds, the elements commonly occurring are carbon, hydrogen, oxygen,
nitrogen, sulphur, halogen, phosphorus.
• The detection of the presence of these elements in an organic compound is called the
Elementary qualitative analysis. Specific tests are available for each of the individual
elements.
• The identification of an organic compound involves tests such as detection of functional
group, determination of melting/ boiling point, etc.
Qualitative analysis of inorganic compounds
The qualitative analysis of simple inorganic compounds seeks to find the elemental
composition of inorganic compounds. It mainly involves detection and confirmation of
cationic (basic) and anionic (acidic) species in them.

Tests involved in the quantitative analysis of organic compounds :

The quantitative analysis of organic compounds involves methods such as-
• Determination of the percentage of the constituent elements in the organic compound.
• Determination of the concentration of the known compound in the given sample, etc.

Quantitative analytical methods :

Quantitative analytical methods involve measurement of quantities such as mass and
volume. Mass can be measured using an apparatus such as weighing balance, while volume
can be measured using a burette.
Quantitative compounds :
analysis of inorganic
The quantitative analysis of simple inorganic compounds involves methods based on
• Decomposition reactions.
• The progress of the reaction between two solutions till its completion.

Mathematical operation and error analysis:

The accuracy of measurement is of a great concern in analytical chemistry.

Accuracy of measurement: Accuracy refers to the nearness of the measured value to the
true value or accepted value. It is expressed by the error. Larger the accuracy smaller is the
error.
Accuracy depends upon the sensitivity or least count ie the smallest quantity that can be
measured on the measuring equipment.
Data report: The numerical data, obtained experimentally, are treated mathematically to
reach some quantitative conclusion. Therefore, an analytical chemist has to know how to
report the quantitative analytical data,

Care should be taken by an analytical chemist while presenting data:

• The numerical data that is obtained experimentally is first treated mathematically so as to
obtain the quantitative conclusion.
• Therefore, an analytical chemist before reporting the quantitative analytical data, should
indicate the extent of the accuracy of measurement and then properly express the
quantitative error in the result.

Scientific notation (exponential notation) :

A chemist often has to deal with very large numbers or very small numbers.
For example, he may have to use a number as large as 602,200,000,000,000,000,000,000,
which is the number of molecules of 2 g of hydrogen gas.
He may also have to use a number as small as 0.00000000000000000000000166 g, which
is the mass of a H atom.
To avoid the writing of so many zeros in mathematical operations, scientific notations i.e.
exponential notations are used.
Here, any number can be represented into a form N × 10h where 'n' is an exponent having
positive or negative values and N can vary 1 < N s10. Thus, we can write the above values
as 6.022 x 1023 and 1.66 × 10-24 g.
The number 123.546 becomes 1.23546 × 102 in scientific notation.
Note that while writing it, we have moved the decimal to the left by two places and same is
the exponent (2) of 10 in the scientific notation.
Similarly, 0.00015 can be written as 1.5 × 10-4.

Precision and accuracy of measurement:

Least count: It is the smallest quantity or value that can be measured on the measuring
equipment or instrument.
• A quantity measured with an instrument of smaller least count will have more significant
figures and will be more accurate than when measured with an instrument of larger leas
count.
Accuracy : Accuracy refers to the nearness of the measured value to the true value or
accepted value.
Accuracy of a measurement is expressed in terms of either absolute error or relative error.
Absolute error : Absolute error of a measurement is a measure of how much exactly the
observed value or the measured value differs
from the true value.
• The absolute error is expressed as the difference between the observed value or
measured value and true value.
• Absolute error = Observed value-True
value
• It may be noted that the absolute error is reported in the same units as the measurement.
Relative error : Relative error is generally a more useful quantity than absolute error.
• The relative error of a measurement tells us, whether the error of the observed value is big
or small compared to the true value.
• Relative error is the ratio of an absolute error to the true value. It is expressed as a
percentage.
. Relative error = Absolute error X 100
/True value

Precision: Precision is defined as the closeness between two or more measured values to
each other.
Multiple readings of the same quantity are noted to minimize the error. If the readings match
closely, they are said to have high precision.
Generally, the precision
of a measurement can be readily determined by simply repeating the measurement.

High precision is a prerequisite for high accuracy.

• Precision describes the agreement between a result and its true value.
• High precision implies reproducibility of readings.
• Precision is determined by simply
replicating a measurement.
• Smaller the difference between the individual values of repeated measurements, greater is
the precision.
• Precision is expressed in terms of deviation.
Absolute deviation: An absolute deviation is the modulus of the difference between an
observed value and the arithmetic mean for the set of several measurements made in the
same way.

Absolute deviation = Observed value - Mean!

It is a measure of absolute error in the repeated observation.

Mean absolute deviation :

The arithmetic
mean of all the absolute deviations is called the mean absolute deviation in the
measurements.
Relative deviation: It is the ratio of the mean absolute deviation to its arithmetic mean.
• Relative deviation = Mean absolute deviation/ mean X 100

Significant figures : The significant figures in a measurement or result are the number of
digits known with certainty plus one uncertain digit.

Determination of molecular formula:

Molecular formula of a compound is the formula which indicates the actual number of atoms
of the constituent elements in a molecule.
It can be obtained from the experimentally determined values of percent elemental
composition and molar mass of that compound.
Percent composition and empirical formula:
Compounds are formed by the chemical combination of different elements. The per cent
elemental composition of a compound is the mass percentage of each element present in
the compound.
If the per cent total is not 100, the difference is considered as per cent oxygen.
• Percentage composition : The percentage by mass of each element in a compound is
called per cent composition.

• Empirical formula: The simplest ratio of atoms of the constituent elements in a molecule is
called the empirical formula of that compound.
• Molecular formula: Molecular formula of a compound is the formula which indicates the
actual number of atoms of the constituent elements in a molecule. Chemical reactions.

stoichiometric calculations :
Stoichiometry: The study of quantitative relations between the amount of reactants and
products is called stoichiometry.
Stoichiometric calculations : Calculation based on a balanced chemical equations are known
as stoichiometric calculations.
Balanced chemical equation:. A symbolic representation of a chemical reaction is a balanced
chemical equation.
Stoichiometric problems :
Generally problems based on stoichiometry are of the following types:
• Problems based on mass-mass
• Problems based on mass-volume
• Problems based on volume-volume

Limiting reagent :
Limiting reagent : The reactant in a chemical reaction that limits the amount of product that
can be formed is called the limiting agent. The reaction will stop when all of the limiting
reactant is consumed.
• A balanced chemical equation gives the ideal stoichiometric relationship among reactants
and products. However, when a chemist carries out a reaction, reactants for the experiment
are not necessarily present in exact stoichiometric amounts. This is because, the goal of the
reaction is to produce the maximum quantity of a useful compound or product from the
starting material.
• Many a times, a large excess of one reactant is supplied to ensure that the more expensive
reactant is completely converted into the desired product. Thus, the reactant which is
present in lesser amounts gets consumed after some time and subsequently, no further
reaction takes place.

Excess reagent: The reactant taken in excess which remains unreacted in a chemical
reaction is called the excess reagent.

Concentration of solution:
Concentration of solution: The concentration of a solution or the amount of the substance
present in a given volume of a solution can be expressed in different ways as follows :
• Mass per cent or weight per cent (W/W %)
• Mole fraction (x)
• Molarity (M)
• Molality (m).

Stock solution : The solution of higher concentration, using which solutions of desired
concentration are prepared by dilution is called the stock solution.

Use of graph in analysis:

Graphs are useful tools that can elucidate relationships between two physical parameters.
In Analytical chemistry, graphs are plotted when the relation between two properties of
matter under study have to be deduced.
• Example: The relation between temperature and volume of a given amount of gas can be
studied by plotting a graph of (V) versus (T).