CH-2 Chemistry Prof.Bharati N.

Gaikwad

2. Introduction to Analytical Chemistry

• Analytical chemistry facilitates investigation of chemical composition of substances. It uses the
instruments and methods to separate, identify and quantify the matter under study.

• The analysis thus provides chemical or physical information about a sample.

• Analysis may be qualitative or quantitative.

• Qualitative analysis is concerned with the detection of the presence or absence of elements in
compounds and mixture of compounds.

• Quantitative analysis deals with the determination of the relative proportions of elements in
compounds and mixture compounds.

Importance of Analytical Chemistry

In agriculture, chemical analysis is used to determine the composition of soils and fertilizers
engineering and industry.

Process control in industry, Industrial process as a whole and the productionof new kinds of
materials are closely associated with analytical chemistry.

Environmental monitoring,

Medical diagnostics, to determine the composition of medicinal preparations. Analytical chemistry

has applications in forensic science,

Drug manufacturing,

Food production,

Forensic surveys.

Analysis
Analysis is carried out on a small sample of the material to be tested, and not on the entire bulk.

It is of two types : Qualitative and Quantitative.

Qualitative analysis methods include

Separations such as precipitation, extraction and distillation,

Identification may be based on differences in colour, odour, melting point, boiling point, and
reactivity.

Quantitative methods consist of volumetric analysis, gravimetric analysis, etc.

1
CH-2 Chemistry Prof.Bharati N.Gaikwad

Chemical methods of qualitative analysis

 Chemical analysis of a sample is carried out mainly in two stages :

Dry method in which the sample under test is not dissolved

Wet method in which the sample under test is first dissolved and then analysed to determine its
composition.

 The dry method is usually used as preliminary tests in the qualititative analysis.

 The semi-micro qualitative analysis is carried out using apparatus such as : test tubes,
beakers, evaporating dish, crucible, spot plate, watch glass, wire guaze, water bath, burner, blow
pipe, pair of tongues, centrifuge,etc.

 The qualitative analysis of organic and inorganic compounds involves different types of tests

 The identification of an organic compound involves tests such as detection of functional

group, determination of melting/ boiling point, etc

 The qualitative analysis of simple inorganic compounds involves detection and confirmation
of cationic and anionic species (basic and acidic radical) in them

Chemical methods of quantitative analysis

Quantitative analysis of organic compounds involves methods such as

 determination of percentage constituent element,

 Concentrations of a known compound in the given sample, etc. Quantitative analysis of simple
inorganic compounds involves methods based on

(i) Decomposition reaction (gravimetric analysis),

(ii) The quantitative analytical methods involve measurement of quantities such as mass and
volume, by means of some equipment/ apparatus such as weighing machine, burette.

Mathematical operation and error analysis

Scientific notation (exponential notation)
Addition and subtraction
Multiplication

• Problem 2.1 : For adding 5.55 x 104 and 6.95 x 103 , first the exponent is made equal.

Thus 5.55 x 104 + 0.695 x 104

Then these numbers can be added as follows : (5.55 + 0.695) x 104

2
CH-2 Chemistry Prof.Bharati N.Gaikwad

= 6.245 x 104

• Problem 2.2 : The subtraction of two numbers can be done as shown below:

3.5 x 10-2 - 5.8 x 10-3

= (3.5 x 10-2) - (0.58 x 10-2)

= (3.5 - 0.58) x 10-2

= 2.92 x 10-2

Problem 2.3 : ( 5.6 x 105 ) x (6.9 x 108 )

= (5.6 x 6.9) (105+8)

= (5.6 x 6.9) x 1013

= 38.64 x 1013

= 3.864 x 1014

Problem 2.4 : (9.8 x 10-2) x (2.5 x 10-6)

= (9.8 x 2.5) (10-2 + (-6))

= (9.8 x 2.5) x (10 -2 -6)

= 24.50 x 10-8

= 2.45 x 10-7

Precision and accuracy of measurement

• Aim of any measurement is to get the actual value called true value or accepted value of a
quantity.

• Nearness of the measured value to the true value is called the accuracy of measurement.

• Larger the accuracy smaller the error.

• Errors may be expressed as absolute or relative error.

Absolute error = Observed value - True value

3
CH-2 Chemistry Prof.Bharati N.Gaikwad

• Relative error is generally a more useful quantity than absolute error. Relative error is the ratio
of an absolute error to the true value. It is expressed as a percentage.

• Relative error = Absolute error / True value x 100 %

• Eg. In laboratory experiment, 10 g potassium chlorate sample on decomposition gives following

data ; The sample contains 3.8 g of oxygen and the actual mass of oxygen in the quantity of
potassium chlorate is 3.92 g. Calculate absolute error and relative error.
Solution: The observed is 3.8 g and
Accepted value is 3.92 g

Absolute error = Observed value - True value

= 3.8 - 3.92
= - 0.12 g
The negative sign indicates that your experimental result is lower than the true value.
The relative error = Absolute error / True value x 100%
= -0.12 / 3.92 x 100%
= -3.06 %
• 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.

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

Absolute deviation = Observed value - Mean

• The ratio of mean absolute deviation to its arithmentic means is called

relative deviation.

Relative deviation = Mean absolute deviation / Mean x 100 %

EX. The three identical samples of potassium chlorate are decomposed. The mass of oxygen is
determined to be 3.87 g, 3.95 g and 3.89 g for the set. Calculate absolute deviation and relative
deviation.

Solution: mean = 3.87 + 3.95 + 3.89 / 3 = 3.90

4
CH-2 Chemistry Prof.Bharati N.Gaikwad

• Absolute deviation = Observed value - Mean

∴ Mean absolute deviation = ± 0.03 g.

The relative deviation,
= Mean absolute deviation / Mean x 100 %
= 0.03 / 3.9 x 100%
= 0.8%

Rules for deciding significant figures

1. All non zero digits are significant;
e. g. 127.34 g contains five significant figures which are 1, 2, 7, 3 and 4.
2. All zeros between two non zero digits are significant
e. g. 120.007 m contains six significant figures.
3. Zeroes on the left of the first non zero digit are not significant. Such a zero indicates the position
of the decimal point.
For example, 0.025 has two significant figures
0.005 has one significant figure.
4. Zeroes at the end of a number are significant if they are on the right side of the decimal point.
For example 0.400 g has three significant figures.
4.0 × 102 g has two significant figures,
4.00 × 102 g has three significant figures.
5. In numbers written is scientific notation, all digits are significant.
For example, 2.035×102 has four significant figures,
3.25 × 10-5 has three significant figures.
• EX: How many significant figures are present in the following measurements?

5
CH-2 Chemistry Prof.Bharati N.Gaikwad

Sr.No. measurements significant figures (Ans)

1 4.065 m 4

2 0.32 g 2

3 57.98 cm3 4

4 0.02 s 1

5 4.0 x 10-4 km 2

6 604.0820 kg 7

7 307.100 x 10-5 cm 6

Calculations with significant figures

Rounding off: The final result of a calculation often contains figures that are not Significant. When this

occurs the final result is rounded off. The following rules are used to round off a number to the

required number of significant figures

• If the digit following the last digit to be kept is less than five, the last digit is left unchanged.
e.g. 46.32 rounded off to two significant figures is 46
• If the digit following the last digit to be kept is five or more, the last digit to be kept is increased
by one.
e.g. 52.87 rounded to three significant figures is 52.9.

EX. Round off each of the following to the number of significant digits indicated :

S.N number of significant digits Round off ( Ans)

1 1.223 to two digits 1. 2; the third digit is less than 5, so we drop it all the others to its
right.
2 12.56 to three digits 12.6 ; the fourth digit is greater than 5, so we drop it and add 1 to
the third digit

3 122.17 to four digits 122.2 ; the fifth digit is greater than 5, so we do it and add 1 to the
fourth digit.

4 231.5 to three digits 232; the fourth digit is 5, so we drop it and add 1 to the third digit.

6
CH-2 Chemistry Prof.Bharati N.Gaikwad

Percent composition and empirical formula

• Percent composition : The Percentage composition of a compound is the percentage by weight
of each element present in the compound
• Quantitative determination of the constituent element by suitable methods provides the percent
elemental composition of a compound.
• If the percent total is not 100, the difference is considered as percent oxygen
• the ratio of the atoms of the constituent elements in the molecule is calculated
• Empirical formula: The simplest ratio of atoms of the constituent elements in a molecule is
called the empirical formula of that compound.
Eg. – The empirical formula of benzene is CH
• Molecular formula : Molecular formula of a compound is the formula which indicates the
actual number of atoms of the constituent elements in a molecule.
Eg. – Molecular formula of benzene is C6H6
• Molecular formula can be obtained from the empirical formula if the molar mass is known.

( Molecular formula = r / empirical formula )

r = molar mass of the compound
(Solve Numericals)

Stoichiometric problems
Generally problems based on stoichiometry are of the following types :
a. Problems based on mass-mass relationship;
b. Problems based on mass-volume relationship and
c. Problems based on volume-volume relationship.

Steps involved in problems based on stoichiometric calculations :

1. Write down the balanced chemical equation representing the chemical reaction.
2. Write the number of moles and the relative masses or volumes of the reactants
and products below the respective formulae.
3. Relative masses or volumes should be calculated from the respective formula
mass referring to the condition of STP.
4. Apply the unitary method to calculate the unknown factor/s as required by the
Problem
( Solve Numericals)

7
CH-2 Chemistry Prof.Bharati N.Gaikwad

Concentration of solution :
• The concentration of a solution or the amount of substance present in given volume of a solution
can be expressed in any of the following ways :
1. Mass percent or weight percent (w/w %)
2. Mole fraction
3. Molarity (M)
4. Molality (m)
Mass percent: It is obtained by using following relation:

Mass percent = Mass of solute / Mass of solution × 100 %

Mole fraction : It is the ratio of number of moles of a particular component of a Solution to the
total number of moles of the solution.
If a substance ‘A’ dissolves in substance ‘B’ and their number of moles are nA and nB ,
respectively, then the mole fraction of A and B are given as :

Mole fraction of A= No. of moles of/ A No. of moles of solution

∴ Mole fraction of A = nA/ nA + nB

Mole fraction of B = No. of moles of / B No. of moles of solution

∴ Mole fraction of B = nB /nA + nB
Molarity : It is the most wideley used unit and is denoted by M.
It is defined as the number of moles of the solute present in 1 litre of the solution .
Thus,

Molarity (M) = No. of moles of solute / Volume of solution in litres

Molality It is defined as the number of moles of solute present in 1 kg of solvent.
It is denoted by m.

Molality (m) = No. of moles of solute / Mass of solvent in kg

8
CH-2 Chemistry Prof.Bharati N.Gaikwad

Use of graph in analysis

A set of experimentally measured values of volume and temperature of a definite mass of a gas upon
plotting on a graph paper appeared as in the figure (a)

When the points are directly connected, a zig zag pattern results (Fig. (b). from this pattern no
meaningful result can be deduced.

A zig zag pattern results due to many types of errors that incur in many

Measurements involved an experiment. Figure (c) shows a smooth curve which may be called an
average curve passing through these points

The perpendicular represents deviation of each point from the curve (Fig (d). The positive deviations
are shown in red and negative deviations are shown in blue.