BASIC CONCEPTS

CLASS XI
Introduction

A dynamic environment of matter and material surrounds man. Since birth

he has been exposed to these changing surroundings. The curiosity to
understand his surroundings and the events that occur around him, has led
him to systematically enquire and collect information through experiments
and observations. This knowledge is referred to as Science. Science may thus
be defined as systematized knowledge gained by mankind through
observations and experimentation.

Science is further classified into different branches due to its enormous

expansion and diversified fields. Chemistry is one of its most important
disciplines and refers to the study of the materials that make up the
universe.

Importance of Chemistry

The branch of science, which deals with the study of matter, its composition,
its properties and the changes that it undergoes in composition as well as in
energy during various processes, is defined as chemistry. It is further divided
into different branches depending upon specialized fields of study.

The major branches of chemistry are:

Branches of chemistry

Organic chemistry

This branch deals with study of carbon compounds especially hydrocarbons

and their derivatives.

Inorganic chemistry

This branch deals with the study of compounds of the elements except
carbon. It largely concerns itself with the study of minerals found in the
Earth's crust.

Physical chemistry

Physical chemistry is basically concerned with laws and theories of the

different branches of chemistry. The explanation of fundamental principles
governing various chemical phenomena is the main concern of this branch.

Industrial chemistry
The chemistry involved in industrial processes is studied under this branch.

Analytical chemistry

This branch deals with the qualitative and quantitative analysis of various
substances.

Biochemistry

This branch deals with the chemical changes going on in the bodies of living
organisms; plants and animals.

Nuclear chemistry

Nuclear reactions, such as nuclear fission, nuclear fusion, transmutation

processes etc. are studied under this branch.

In addition, with new developments emerging in recent years, more branches

of chemistry are being added. These include, pharmaceutical chemistry,
geochemistry, agricultural chemistry, medicinal chemistry, solid-state
chemistry, etc.

Scope of chemistry

As chemistry concerns itself with matter and materials of the universe, it

obviously plays a very significant role in almost all walks of life. Modern daily
life involves the use of many chemical products and many chemical changes,
although we are unaware of them.

Fuels burn, food cooks, leaves turn in the fall, cells grow, medicines cure.
One material can be changed into another by a chemical reaction. A complex
substance can by made from simpler ones. Chemical compounds can break
down into simpler substances. Chemists use the exhaustive, scientific
method and well-defined techniques to study these existing or new organic
and inorganic substances. Chemistry is therefore concerned with the
essential processes that make these changes happen.

Chemistry use atoms and molecules to explain properties and behaviors of

matter; Chemists answer questions like, "What kind of stuff is a sample
made of? What does the sample look like on a molecular scale? How does the
structure of the material determine its properties? How do the properties of
the material change with increase of temperature, or pressure, or some other
environmental variable?"

Contemporary chemistry offers exciting employment opportunities in rapidly

growing technical fields, such as materials science, polymers, biochemistry,
biotechnology, pharmaceutical and medicinal chemistry, and environmental
science. Many predict a growing role for chemistry as one confronts the
major issues gripping the world in the 21st century: providing energy,
protecting the environment, improving health, meeting the growing demands
of food and shelter the world, responding to regulations etc.

The major contributions of chemistry to the different walks of life in modern

world are as given below:

Chemistry in medicine

The eradication of a number of diseases and major contributions to

improving human health, have been made by modern chemical discoveries.
Some important contributions in this field are:

Life saving drugs and prophylatics, i.e., disease preventing serum and
vaccines

Anaesthetics and antiseptics

Disinfectants and germicides

Chemistry in industry

Chemistry plays an important role in most industrial processes. Some

important process include the manufacture of:

Basic chemicals like sulphuric acid, hydrocarbons etc.

Synthetic fibres like rayon, nylon, dacron, orlon etc.

Plastics like bakelite, teflon, polythene etc.

Paints, varnishes, enamels, dyes etc.

Cement, glass and ceramics and extraction of metals like silver, magnesium,
gold, iron etc.

Chemistry in agriculture

Significant contributions towards securing enough food grains and protecting

crops have been made by the use of chemistry. This has been activated by
the use of:

Chemical fertilizers like urea, ammonium sulphate, calcium nitrate etc., for
the better production of crops.
Insecticides such as DDT, BHC, chlorinated hydrocarbons, aldrin, malathion,
dieldrin, furodan etc., for the protection of crops from insects and to help in
the safe storage of foodgrains.

Preservatives like sodium benzoate, sodium metabisulphite and salicylic

acid for better preservation of food to and check its wastage.

Chemistry in life styles

In every walk of life, chemistry has been the pioneer contributor towards
enabling the comfort, convenience and pleasures of man. Chemistry has
helped us in getting a number of amenities. Some examples are:

Domestic requirements such as better fabrics, soaps, shampoos, cosmetics,

dyes, oils, flavouring essences, paper etc.

Air conditioning, refrigeration and domestic gadgets: To keep the

environment cool and food fresh in all seasons, we make use of air
conditioning. Chemical substances like liquid ammonia, liquid sulphur dioxide,
CFC etc., are used in these machines. All consumer electronic gadgets based
on Printed Circuit Board technology (PCB'S) use specialized chemical coatings
for their functioning.

Chemistry and energy resources

The energy resources of the world are mainly petroleum, coal, wood, nuclear
fuels. To conserve the fast depleting reserves of coal and petroleum,
attempts are being made by chemists to utilize alternate energy fuels as
nuclear energy, solar energy, ocean energy (hydrogen from seawater). These
may provide inexhaustible sources and are being studied under chemistry for
future energy needs.

Particulate Nature of Matter

The entire universe is made of two basic things, matter and energy; and that
matter is defined as the entity, which has mass and occupies space. Today's
scientific concept of matter has resulted from a process of continual
modification of historical episodes.

Scientists have generally agreed, since the times of the ancient Greeks, that
everything that takes up space, or matter, is made up of tiny bits of material,
which have come to be known as elementary particles. At Around 440 B.C.,
the Greek philosopher Democritus, believed that between separate bits of
matter there were spaces, which contain no matter i.e., all matter was
particulate in nature. He conceived that atoms - (derived from the Greek
word 'atomos' for indivisible) were the smallest constituents of matter. In
science this is called the 'atomic nature of matter.'

The atomic theory of Democritus fell by the wayside for many years, as the
great philosopher Aristotle, a hundred years later, preferred to think of the
nature of matter in more concrete terms, as the four elements: air, fire,
wind, and water. Aristotle's theories about the nature of matter, turned out
to be wrong. However, it was only at the start of the nineteenth century that
the atomic theory view returned to the forefront of science.

In the early days of quantitative science, several important events solidified

the concept of particulate matter. French chemist Antoine Lavoisier
discovered in the late 1700s, that the total original 'mass' of different
components in a chemical reaction remained the same, in spite of radical
change in terms of appearance and form. The next step came when, Joseph
Proust, another French chemist demonstrated conclusively that every pure
chemical compound maintains the same constant proportions in weight of the
elements that make it up. It appeared that some basic part of the
components did not change, although it could not be seen.

In about 1800, scientists began wondering whether the behavior of matter

could be ruled by something that even their microscopes could not perceive.
Soon afterward, in 1808, John Dalton proposed a scenario in which every
element was composed of a huge number of identical atoms that caused
chemical compounds to come about through the combination of a smaller
number of atoms from different elements. In 1811, Italian chemist and
physicist Amadeo Avogadro later clarified that the basic components of a
pure element were not necessarily individual atoms, but rather molecules
existing as compound atoms (e.g., HCl or H2).

A scientific conference, in 1860, officially adopted the atomic-molecular

theory of Dalton and Avogadro; soon afterwards chemists began creating an
accurate compilation of relative atomic masses. Yet all this developed without
any real, direct proof of the particulate nature of matter.

The first hard evidence of the existence of fundamental particles came in

1897, when English physicist Joseph Thomson discovered 'electrons' within
an atomic 'nucleus'. This was the end of the belief that the atom is the
smallest particle that makes up matter. British physicist Ernest Rutherford
advanced Thomson's findings in the early 1900s, by showing that every atom
consisted of a positively charged nucleus in the center, surrounded by what
they termed a "cloud" of negatively charged electrons. The atomic nucleus
itself (except for hydrogen) consisted of positive protons and electrically
neutral neutrons. Collectively, these components are known as 'subatomic
particles'.
Scientific advances since then, have shown us that atoms of matter contain
even smaller particles than electrons, protons, and neutrons, and that there
are at least several smaller kinds of particles that make up each atom. These
discoveries only strengthen the fundamental truth of the particulate nature of
matter. Nevertheless, the atom remains the most stable and convenient way
to understand and discuss the nature of matter - especially since it is the
smallest particle that can enter into chemical combination.

Matter can be classified in different ways, as different kinds of substances are

made up of different kinds of matter.

All around us are substances made up of matter. Matter has mass and
occupies some space. Different kinds of substances are made up of different
matter. Matter can be thus classified in many ways. Two basic classifications
of matter are based on its physical and chemical properties. The physical
classification of matter shows its physical appearance it describe the shape,
hardness, softness, melting and boiling points. The chemical classification of
matter shows the ability of matter to change its composition to form new
substances.

Physical classification of matter

Based on its physical characteristics, matter is divided into solids, liquids and
gases.

Solids

In solids the particles are closely packed and bound by strong inter-particle
attraction, which makes them rigid and geometrical. This gives solids definite
shape and definite volume. Examples: rock, wood, steel girders etc.

Liquids

Liquids arise when the particles are loosely packed and are bound to each
other with forces weaker than those of solids. This gives them definite
volume but not definite shape. Thus liquids are mobile and take the shape of
the container in which they are placed.

Examples: Water, oil, milk etc.

Gases

In gases the particles are separated by much greater distances, almost 10 to

100 times the size of the constituting particles. The operating forces of
attraction are virtually non-existent in gases, resulting in loosely packed
particles, which are free to move in any direction. Thus gases possess neither
definite volume nor shape and occupy the whole volume of the vessel in
which they are placed. Examples: air in balloons, oxygen in cylinders.

The three states of matter are inter-convertible. This is achieved by heating

and cooling, which affect the kinetic energy of the particles. Heating
increases the kinetic energy of matter and as a result, solids when heated
become liquids and liquids become gas when heated.

Comparison of the properties of solids, liquids and gases

Chemical classification of matter

Based on its broad chemical composition, matter is classified as elements,

compounds and mixtures.

Elements

An element is the simplest form of matter that cannot be split into simpler
substances or built from simpler substances by any ordinary chemical or
physical method. There are 110 elements known to us, out of which 92 are
naturally occurring while the rest have been prepared artificially. Elements
are further classified into metals, non-metals and metalloids.

Metals:

All elements (except hydrogen) which form positive ions by losing electrons
during chemical reactions are called metals. Thus metals are electropositive
elements. They are characterized by bright lustre, hardness, ability to
resonate sound and are excellent conductors of heat and electricity. Metals
are solids under normal conditions except mercury. They are ductile (can be
drawn into wire) and malleable (can be beaten into very thin sheets).

Non-metals:

Elements that tend to gain electrons to form anions during chemical reactions
are called non-metals. These are electronegative elements. They are non-
lustrous, brittle and poor conductors of heat and electricity (except graphite).
Non-metals can be gaseous, liquids or solids.

Metalloids:

Elements that behave like both metals and non-metals are called metalloids.

Common metal, non-metals and metalloids

Compounds

Characteristics of compound

Compounds always contain a definite proportion of the same elements by

mass. For example, water as a compound, always contains hydrogen and
oxygen in the ratio 1:8 by mass.

The properties of compounds are totally different from the elements from
which they are formed. For example, while water is normally used for
extinguishing fire, its elements are not. Hydrogen is combustible and oxygen
is a supporter of combustion.

Compounds are homogeneous substances

During the formation of a compound, energy in the form of heat, light or

electricity is either evolved or absorbed. Coal when burnt, gives heat and
light energy.

Compounds are broadly classified into inorganic and organic compounds.

Inorganic compounds are those, which are obtained from non-living sources
such as minerals. For example, common salt, marble and limestone. Organic
compounds are those, which occur in living sources such as plants and
animals. They all contain carbon. Common organic compounds are oils, wax,
fats etc.
Mixtures

A mixture is a combination of two or more elements or compounds in any

proportion, so that the components do not lose their identity. Air is an
example of a mixture (several gases mix to form air).

Mixtures are of two types, homogeneous and heterogeneous.

Homogeneous mixtures have the same composition throughout the sample.

The components of such mixtures cannot be seen under a powerful
microscope. They are also called solutions. Examples of homogeneous
mixtures are air, sea-water, gasoline, brass etc.

Heterogeneous mixtures consist of two or more parts (phases), which have

different compositions. These mixtures have visible boundaries of separation
between the different constituents and can be seen with the naked eye e.g.,
sand and salt, chalk powder in water etc.

Classification of matter can be summarized as follows:

Separation of mixtures

The separation of mixtures into its constituents in a pure state is an

important process in chemistry. The constituents of any mixture can be
separated on the basis of differences in their physical and chemical
properties e.g., particle size, solubility, effect of heat, acidity or basicity etc.

Some of the methods for separation of mixtures are:

Sedimentation or decantation

Principle
The coarse particles of the solid being heavier than the liquid (usually water),
settle down due to gravity. The clear upper layer of the liquid is then gently
poured out into another container. Settling down of the coarse particles due
to the effect of gravity is called sedimentation. The mechanical transfer of
the clear upper liquid without disturbing the settled solid particles is called
decantation.

Process

The mixture is taken in a container and allowed to stand for sometime. The
solid particles settle down with time. Settling down of the particles leaves the
upper layers of the liquid clearer. Bigger particles settle down faster than the
finer particles. Sometimes the sedimentation process is hastened by adding a
small quantity of alum. Al3+ ions in alum cause the coagulation of the fine
particles by undergoing hydrolysis to Al(OH)3 that has a strong tendency for
adsorption.

Separation of the coarse particles of a solid from a liquid by sedimentation and

decantation
Filtration

Aim

To separate the insoluble solid component of a mixture from a liquid

completely i.e., separating the precipitate (solid phase) from a solution.

Experiment

Principle

The solvent molecules and the molecules/ions present in the solution can
pass through the porous membranes while the suspended particles cannot
and are retained on the porous membrane.

Process

The solution containing the suspended impurities is made to pass through a

porous membrane such as filter paper, filter cloth etc. Only solvent or
solution containing dissolved substances pass through the porous membrane.
This is called filtrate. The insoluble solid suspended particles remain on the
porous membrane. It is termed residue. When the suspended impurities are
very fine, a small amount of alum is added to the suspension makes. It
filtration faster.

Separation by filtration
Evaporation

Aim

To separate a non-volatile soluble salt from a liquid or recover the soluble

solid solute from the solution. The solvent is lost into the surroundings.
Experiment

Principle

Liquids evaporate at all temperatures. Evaporation becomes faster at higher

temperatures.

Process

The solution containing the mixture is taken in a china dish and heated
gently. Gradually the solvent evaporates and the solution containing the
dissolved solute becomes thicker. The semi-solid mass left on the china dish
is slowly heated to dryness.

Evaporation of a solution

Crystallization

This method is used to separate a solid compound in pure and geometrical

form. A nearly saturated solution of an impure substance is prepared in a hot
solvent. The prepared solution is quickly filtered and the filtrate is then
allowed to cool slowly in a china dish. The resulting pure crystals that form
are removed with the help of a spatula. They are dried by pressing them
between the folds of filter papers and finally put into a dessicator.
Sublimation

This method is used to separate volatile solids, from a non-volatile solid. The
mixture is taken in a china dish covered with a perforated filter paper on
which an inverted glass funnel is placed to collect the vapours. Upon heating,
the volatile substance vapourizes and gets deposited on the walls of the
funnel. The non-volatile solid is left in the dish.

Distillation

Distillation is the process for separating the constituents of a liquid mixture,

which differ in their boiling points. Depending upon the difference in the
boiling points of the constituents, different types of distillation like fractional
distillation, steam distillation etc. are employed.

Magnetic separation method

Aim

To separate a magnetic component from a mixture containing non-magnetic

components

Experiment

Principle

The magnetic component of the mixture is separated with the help of the
magnetic attraction of a magnet.

Process

A magnet is moved over the mixture containing the magnetic substance e.g.,
iron filings. These get attracted to the magnet. The process is repeated until
the magnetic material is completely separated from the mixture.
Separation of a magnetic substance by a magnet

Gravity method

Aim

To separate mixtures in which components have different densities.

Principle

Particles with higher density settle to the bottom while lighter particles are
separated through various processes such as winnowing (grain separation)
and washing (panning of gold in the river bed).

Process

Riverbed sand containing fine particles of gold is repeatedly washed in a pan

with flowing water. Gold particles settle to the bottom of the pan because of
higher density while lighter sand particles are washed over the edge of the
pan.

Solvent extraction method

Organic compounds, which are easily soluble in organic solvents but insoluble
or immiscible with water, form two separate layers. These two layers can be
easily separated. The aqueous solution of the mixture is mixed with a small
quantity of organic solvent in a separating funnel. The separating funnel is
stoppered and shaken strongly. It is allowed to stand for some time. The
organic liquid and water form two separate layers. The bottom aqueous layer
is collected separately by opening the stop-cock. The aqueous layer is again
transferred to the separating funnel. The process is repeated with more
organic solvent.

Chromatography

This technique is based on the differential adsorption of various components

of a substance which is a mixture, on a suitable adsorbent called the
stationary phase. The liquid in which the substance is dissolved is called the
mobile or moving phase. Depending on the nature of the two phases there
are various types of chromatography. In column chromatography, the
adsorbent-alumina is packed in a column. This acts as a stationary phase.
The mixture is dissolved in a suitable solvent and this solution is poured on
top of this column. The mixture moves down and the different components of
the mixture get adsorbed in different strengths on the alumina surface. The
adsorbed components are then eluted out by the mobile phase (solvent).

Laws of Chemical Combination

The study of reactions is one of the important areas of Chemistry. There are
many aspects of a reaction like the rate of reaction, energy absorbed or
evolved, mechanism of a reaction etc. that can be evaluated only with weight
and volume relationships. A study of reactions is possible by understanding
the definite laws and patterns regulating them.

Law of Conservation of Mass

This law was put forth by a French chemist A. Lavoisier in 1774. It states
that in 'any chemical reaction, the total mass of the system before and after
the reaction is the same although its matter can undergo a physical change'.

If 'a' grams of A and 'b' grams of B react to give 'c' grams of C and 'd' grams
of D, then,
Total mass of the reactants = Total mass of the products

(a + b) grams = (c + d) grams

Therefore, matter is neither created nor destroyed as a result of any

chemical or physical change. This law can be verified by a simple experiment.

A solution of sodium chloride and silver nitrate are taken separately in the
two limbs of an 'H' shaped tube. The tube is sealed and weighed precisely.
The two reactants are made to react by inverting the tube. The following
reaction takes place.

The whole tube is kept undisturbed for sometime so that the reaction is
complete. When the tube is weighed again it is observed that:

Weight before the reaction = Weight after the reaction

This verifies the law of conservation of mass.

Law of Definite Proportions or Law of Constant Composition

This law was proposed by Louis Proust in 1799, which states that:

'A chemical compound always consists of the same elements combined

together in the same ratio, irrespective of the method of preparation or the
source from where it is taken'.

For example, water is always found to contain only two elements hydrogen
and oxygen combined in a fixed ratio by mass (1:8) irrespective of its
source. Similarly carbon dioxide is always found to contain carbon and
oxygen in the mass ratio of 3:8. This law can be verified by studying the
electrolysis of water into hydrogen and oxygen of different samples. It is
found that the ratio of hydrogen and oxygen is 2:1 (by volume) and 1:8 (by
mass) always.
However, this law does not hold good when the compound is obtained by
using different isotopes of the combining elements and when the compounds
are non-stoichiometric.

Law of Multiple Proportions

Proposed by Dalton in 1803, this law states that:

'When two elements combine to form two or more compounds, then the
different masses of one element, which combine with a fixed mass of the
other, bear a simple ratio to one another'.

This law is evident when one element combines with another to give more
than one compound of different stoichiometry e.g., nitrogen reacts with
oxygen to form nitrous oxide (N2O) and nitric oxide (NO). The Law of Multiple
Proportions does not hold good when different isotopes are used to obtain
different compounds.

This law can be verified by heating 1.00 g each of the oxide of copper CuO
and Cu2O in a current of hydrogen. Both the oxides react with hydrogen
producing metallic copper. From the weight of the copper obtained, the
respective weights of oxygen in the two compounds are determined. From
this, the different weights of oxygen, which combine with the same weight of
copper in the two compounds are calculated. Since these weights are found
to bear a simple whole number ratio, the law is verified.

Law of Reciprocal Proportions or Law of Equivalent Proportions

This law was proposed by Ritcher in 1792. It states that 'when two different
elements combine separately with the same weight of a third element, the
ratio of the masses in which they do so will be the same or some simple
multiple of the mass ratio in which they combine with each other'.

For example, oxygen and sulphur react with copper to give copper oxide and
copper sulphide respectively. Suphur and oxygen also react with each other
to give SO2. Then,

In CuS, Cu:S = 63.5:32

In CuO, Cu:O = 63.5:16

S:O = 32:16
S:O = 2:1

Now in SO2

S:O = 32:32

S:O = 1:1

Thus the ratio between the two ratios is

Gay Lussac's Law of Gaseous Volumes

This law, put forward by Gay Lussac states that 'whenever gases react
together under constant conditions of temperature and pressure, the
volumes of the reacting gases as well as products (gases) bear a simple
whole number ratio between themselves'.

For example, in the reaction,

The ratio of volumes of hydrogen, chlorine, and hydrogen chloride is 1:1:2 (a

simple ratio).

Dalton's Atomic Theory

John Dalton provided a simple theory of matter to provide theoretical

justification to the laws of chemical combinations in 1805. The basic
postulates of the theory are:

All substances are made up of tiny, indivisible particles called atoms.

Atoms of the same element are identical in shape, size, mass and other
properties.

Each element is composed of its own kind of atoms. Atoms of different

elements are different in all respects.

Atom is the smallest unit that takes part in chemical combinations.

Atoms combine with each other in simple whole number ratios to form
compound atoms called molecules.
Atoms cannot be created, divided or destroyed during any chemical or
physical change.

The main achievement of Dalton's theory was the derivation of the laws of
chemical combination. But later discoveries found that it could not explain:

The law of gaseous volumes

Why atoms of different elements have different masses, sizes, valencies etc.

Why atoms of different elements combine with each other to form molecules.

The nature of forces that bind together atoms in a molecule

The fundamental particles that make the element or the compound

Modern Atomic Theory

In view of new discoveries about atoms, Dalton's atomic theory was modified
as given below:

Atom is no longer indivisible as it has a complex structure of sub atomic

particles (electrons, protons and neutrons).

Atoms of the same element may posses different relative masses (isotopes).

Certain atoms of different elements have same relative masses but their
chemical properties are entirely different (isobars).

Although the atom is composed of sub-atomic particles, it still is the smallest

unit that takes part in a chemical reaction.

The ratio in which the different atoms combine may be fixed and integral but
may not always be simple.

Atom of one element may be changed into atoms of another element

(transmutation).

The mass of an atom can be changed into energy (E = mc2). This shows that
atom is no longer indestructible.
Avogadro's Hypothesis

In trying to correlate Dalton's atomic theory with Gay Lussac's law of

gaseous volume, Berzelius put forward the hypothesis that equal volumes of
all gases contain equal number of atoms under similar conditions of
temperature and pressure. However, it was found that even a fraction of an
atom could be involved in certain chemical reactions. This went against
Dalton's atomic theory. Therefore, Avogadro postulated the existence of
molecules along with atoms as two kinds of ultimate particles. According to
Avogadro's postulates,

The smallest particle of an element, which may or may not have independent
existence and takes part in a chemical reaction is an atom.

The smallest particle of a substance (element or compound) capable of

independent existence is called molecule.

Avogadro's Law

Avogadro's law states that 'under similar conditions of temperature and

pressure, equal volumes of all gases contain equal number of molecules'.

For example, if equal volumes of different gases like hydrogen, oxygen and
chlorine are held in separate containers under similar conditions of
temperature and pressure, then each container will contain the same number
of molecules. The total mass and size of each gas in the container may differ
from each other.

Different gases under same conditions of pressure and temperature

Experimental evidences show that one mole of all gases under similar
conditions of temperature and pressure occupy the same volume. This
volume is called molar volume (Vm). Molar volume of all gases under normal
pressures (1 atm) and normal temperature (273K) have a value of 22.4 litre
and contains 6.023 x 1023 molecules. This number is called the Avogadro's
number or Avogadro's constant and is denoted by NA.
Avogadro's law is very useful in chemistry and has some important
applications like in the deduction of the atomicity of elementary gases, the
derivation of relationship between molar mass and vapour density, and
determination of the molecular formula of a gaseous compound.

Problems

1. 1.375 g of cupric oxide on reduction in hydrogen gas gives 1.098 g of

copper. In another experiment, 1.179 g of metallic copper produced 1.476 g
of copper oxide. Show that these results illustrate the law of constant
proportions.

Solution

Mass of copper oxide taken in experiment 1 = 1.375 g

Mass of copper obtained = 1.098 g

Mass of copper oxide produced in experiment 2 = 1.476 g

Mass of copper used = 1.179 g

Since the percentage of copper in the two samples of copper oxide is the
same, the law of definite proportion is verified.

2. Carbon and oxygen are known to form two compounds. The carbon
content in one of these is 42.9% while in the other it is 27.3%. Show that
this data is in agreement with the law of multiple proportions.

Solution

For the first compound, mass % of C = 42.9

Mass % of O = 57.1

Thus, 42.9 g of C reacts with 57.1 g of oxygen

=1.33 g of oxygen

For the second compound, mass % of C = 27.3

Mass % of O = 72.7

Thus, 27.3 g of C reacts with 72.7 g of oxygen

= 2.66 g of oxygen

The ratio of oxygen masses, which combine with 1 g of C is 1.33:2.66 or 1:2

This is a simple ratio and supports law of multiple proportions.

3. Hydrogen sulphide contains 94.11% sulphur. Sulphur dioxide contains

50% oxygen. Water contains 11.11% hydrogen. Show that the results are in
agreement with the law of reciprocal proportions.

Solution

In H2S, 100 - 94.11 = 5.89 g of hydrogen combines with 94.11 g of sulphur.

So, 1 g of hydrogen combines with of sulphur

In H2O, 100 - 11.11 = 88.89 g of oxygen combines with 11.11 g of

hydrogen.

So, 1g of hydrogen combines with

Ratio of the masses of sulphur (H2S) and oxygen (H2O)

Ratio of the masses of sulphur and oxygen (SO2)

The first ratio is double of the second, which is a simple ratio. This illustrates
the law of reciprocal proportions.

Atoms and Molecules

Matter occurs in the form of various substances. Elements are the simplest
form of substances. Elements may or may not have independent existence,
but they cannot be separated into simpler substances. The atom is the
smallest particle of an element. Each element has its own type of properties
and the atom of an element will always have the properties of that element.

Atoms are the basic building blocks of matter that make up everyday objects.
A desk, the air, even you are made up of atoms! There are 90 naturally
occurring kinds of atoms and Scientists in labs have been able to make about
25 more. They are also the smallest particles of matter that enter into
chemical combinations.

A molecule is formed when two or more atoms join together chemically. A

molecule is the smallest particle of a substance that can have an independent
existence.

When two or more elements join together chemically, they form a substance
called a compound. A compound is a molecule that contains the atoms of
least two different elements. Water (H2O), carbon dioxide (CO2) and methane
(CH4) are compounds because each is made from more than one element.
These are known as heteroatomic molecules.

But not all molecules are compounds. Molecular Hydrogen (H2), molecular
oxygen (O2) and molecular nitrogen (N2) are substances composed of a
single element and are not compounds. They are known as Homoatomic
molecules. The smallest bit of each of these substances would be referred to
as a molecule. For example, a single molecule of molecular hydrogen is made
from two atoms of hydrogen.

Atomic mass unit

Dalton's atomic theory proposed that atoms possess mass. But, an atom is a
very minute particle and so the actual mass of an atom is extremely small. It
is physically not possible to measure such small masses easily. In 1811,
Avogadro suggested that atomic and molecular masses can be expressed on
an atomic mass scale relative to that of a standard reference atom. The
standard reference atom chosen by IUPAC in 1961 is carbon-12 isotope
designated as 12C6 or simply as12C. The 12C isotope has been assigned an
atomic mass of 12.000 atomic mass unit. Hence, one atomic mass unit
(amu) may be defined as follows: The mass equal to 1/12th of the mass of a
12
C atom. It is abbreviated as amu or mau

12
Absolute mass of C atom is 1.9924 x 10-23g

Atomic and Molecular Masses

Atomic mass

It is known that the atomic mass of an element/compound is not the mass of

one atom or molecule of the said element/compound because they occur as a
mixture of isotopes. As the atomic and molecular masses are expressed on a
relative scale based on a mass of 12C atom, all atomic and molecular masses
are in fact the weighted average of the mass of these isotopes. Thus, atomic
mass of an element is defined as the average relative mass of an atom of an
element as compared to the mass of an atom of carbon (12C ) taken as 12.

For example, chlorine occurs in nature in the form of two isotopes with
atomic mass 35 and 37 in the ratio of 3:1. Therefore,

Thus, an atom of chlorine is 35.5 times heavier that 1/12th of the mass of a
12
C atom.

Gram atomic mass

The quantity of an element whose mass in grams is numerically equal to its

atomic mass. In simple terms, atomic mass of an element expressed in
grams is the gram atomic mass or gram atom.

For example, the atomic mass of oxygen = 16 amu

Therefore gram atomic mass of oxygen = 16 g

The gram atom should not be confused with the mass of one atom of the
element in grams, which is the actual mass of the atom.
Molecular mass

Molecular mass of a substance is defined as the average relative mass of its

molecule as compared to the mass of an atom of 12C taken as 12. It
expresses as to how many times the molecule of a substance is heavier than
1/12th the mass of an atom of carbon.

For example, a molecule of carbon dioxide is 44 times heavier than 1/12th

the mass of an atom of carbon. Therefore the molecular mass of CO2 is 44
amu.

Gram molecular mass

A quantity of substance whose mass in grams is numerically equal to its

molecular mass is called gram molecular mass. In simple terms, molecular
mass of a substance expressed in grams is called gram molecular mass.

For example the molecular mass of oxygen = 32 amu

Therefore, gram molecular mass of oxygen = 32 g

The gram molecular mass should not be confused with the mass of one
molecule of the substance in grams, which is the actual mass of the
molecule.

Mole Concept

In chemistry, the term mole represents a definite or mass of atoms,

molecules, ions or electrons. Just as common man measures quantity in
terms of kilograms or dozens, a chemical scientist deals with a 'mole' of
atoms, molecules, ions or electrons.

Mole is defined as the amount of a substance, which contains the same

number of chemical units (atoms, molecules, ions or electrons) as there are
atoms in exactly 12 grams of pure carbon-12. A mole represents a collection
of 6.023 x 1023 ( Avogadro's number) chemical units. Thus a mole represents
the quantity of material, which contains one Avogadro's number of chemical
units of any substance. The unit of mole is denoted as 'mol'.

For example

One mole of hydrogen atoms = 6.023 x 1023 atoms of hydrogen

One mole of hydrogen molecules = 6.023 x 1023 molecules of hydrogen

One mole of electrons = 6.023 x 1023 electrons

One mole of sodium ions (Na+) = 6.023 x 1023 Na+ ions

It can be thus concluded that,

One mole of atoms = 6.023 x 1023 atoms = Gram atomic mass of the
element.

One mole of molecules = 6.023 x 1023 molecules = Gram molecular mass.

Molar volume

The volume occupied by one mole of any substance is called its molar
volume. It is denoted by Vm. Molar volume of the substance depends on
temperature and pressure. One mole of all gaseous substances at 273 K and
1 atm pressure occupies a volume equal to 22.4 litres or 22,400 mL. The unit
of molar volume is litre per mol or millilitre per mol.

The various relationships of mole can be summarized as follows:

Mole relationships

Problems

4. Calculate the average atomic weight of silicon having 92.2% of Si-28

isotope of relative mass 27.98 amu, 4.7% of Si-29 isotope of relative mass
28.98 amu and 3.1% of Si-30 isotope of relative mass 29.97 amu.
Solution

Data given: 92.20% of silicon of mass 27.98 amu

4.7% of silicon of mass 28.98 amu

3.1 % of silicon of mass 29.97 amu

Average atomic weight

= 25.80 + 1.36 + 0.93

= 28.09 amu.

Average atomic weight of silicon is 28.09 amu.

5. One million silver atoms weigh 1.79 x 10-16 g. Calculate the gram atomic
mass of silver.

Solution

Number of silver atoms = 1 million = 1 x 10-16

Mass of one million Ag atoms = 1.79 x 10-16 g

Gram atomic mass of silver is equal to the mass of 6.023 x 1023 atoms of
silver.

Mass of 6.023 x 1023 atoms of silver

= = 107.8 g

So, the gram atomic mass of silver is 107.8 g

6. Chlorophyll, the green colouring matter of plants responsible for

photosynthesis, contains 2.68% of magnesium by weight. Calculate the
number of Mg atoms in 2.00 g of chlorophyll.

Solution
100 g of chlorophyll contains 2.68 g of Mg

1 mole of Mg = 24 g of Mg = 6.023 x 1023 atom of Mg

24 g of Mg contains, 6.023 x 1023 atom of Mg

=1.34 x 1021 Mg atoms

7. A sample of gaseous substance weighing 0.5 g occupies a volume of 1.12

litre under NTP conditions. Calculate the molar mass of the substance.

Solution

1 mole of any gaseous substance at NTP occupies 22.4 L.

1.12 L of gaseous substance = 0.5 g

The molar mass of the substance therefore is 10 g/mol.

Chemical Formulae

Every chemical substance is known by a specific name. But many a times

these names are cumbersome, confusing, and do not provide information
about its chemical composition. To overcome this, each chemical compound
is represented by a chemical formula that gives its composition (constituent
elements present) and the number of elements of each type present. There
are two types of chemical formula. They are:

Molecular formula
The formula that gives the symbolic representation of the actual number of
atoms of various elements present in one molecule of the compound is called
the molecular formula. Discrete molecules can be described by this formula.
As the molecular formula represents one molecule of the substance, giving
the names and number of atoms of the various elements present, it denotes
the molecular mass of the substance.

For example, the molecular formula of water is H2O, which means that one
molecule of water contains two atoms of hydrogen and one atom of oxygen.
This also represents the molar mass, which is the sum of the gram atomic
mass of all the atoms.

Gram atomic mass of 2 hydrogen atoms = 2 x 1.008 g

Gram atomic mass of oxygen atom = 16 g

Total molecular mass = 18 g

Empirical formula

Empirical formula is defined as the simplest formula of the substance, which

gives the relative number of atoms of each element present in the molecule
of that substance. Substances which have no discrete molecules such as ionic
and network covalent compounds are described by this empirical formula.
This is also called as stoichiometric formula. It gives the simplest whole
number ratio between the number of atoms of all the elements present in the
compound.

For example, in the compound benzene, C6H6 there are six carbon atoms and
six hydrogen atoms. The lowest whole number ratio between them is 1:1
(6:6 can be simplified to 1:1). Therefore, the empirical formula of benzene
having molecular formula of C6H6 is CH.

Empirical formula mass or formula mass is equal to the sum of atomic

masses of all the atoms present in the empirical formula. The empirical
formula of benzene is CH. So,

The formula mass of CH is (12+1) = 13 amu or 13 g/mol.

Relationship between empirical and molecular formulae

The two formulas, empirical and molecular are related as follows:

Molecular formula = n x empirical formula

where 'n' has whole number values of 1,2,3.... The value of 'n' can be
obtained by the following relationship

For example, the molecular mass of benzene is 78 and its empirical formula
is CH and therefore, its empirical formula mass is 13.

Therefore, the molecular formula of benzene is 6 x (CH) = C6H6.

Steps for writing the empirical formula of a compound

The empirical formula of a compound is determined from the percentage

composition of different elements and atomic masses of the elements. The
various steps involved in determining the empirical formula are:

The percentage of each element is divided by its atomic mass. This gives the
relative number of atoms of various elements in the molecule of the
compound.

The result obtained in the above step is divided by the smallest value to get
the simplest ratio of various elements.

The values obtained are made to the nearest whole number ratio (multiplied
if necessary by a suitable integer to make the values whole numbers).

The symbols of various elements are written side by side and the above
obtained numerical value is inserted at the right hand lower corner of each
symbol as subscripts..

Steps for writing the molecular formula of a compound

The empirical formula of the compound is written.

The empirical formula mass is calculated by adding the atomic masses of all
atoms present in the empirical formula.

The molecular mass or molar mass is obtained from experiment or from the
vapour density relationship:
molecular mass = 2 x vapour density

The value of 'n' is obtained through the relation

The molecular formula is obtained from the relation:

Molecular formula = n x empirical formula

Percentage composition of a compound

The mass percentage of each constituent element present in any compound

is called its percentage composition. This may be obtained from the
molecular formula of the compound by using the relationship:

This can also be determined by a suitable chemical method of chemical

analysis of the compound by using the same relationship.

Problems

8. Determine the percentage composition of potassium nitrate, (KNO3)

(Atomic masses in amu are, K = 39, N= 14, O=16)

Solution

Formula mass of KNO3 = (39 amu + 14 amu + 3 x 16 amu) = 101 amu

Then,
The percentage composition of KNO3 is K=38.6%, N=13.9%, O=47.5%.

9. A compound contains 75% carbon and 25% hydrogen. Determine its

empirical formula. The molecular mass of this compound is 16 amu.
Determine its molecular formula also. The atomic masses are: C = 12 amu,
H = 1 amu.

Solution

The above results are written as follows:

So,

The empirical formulae of the compound = C1H4 or CH4

The empirical formula mass = (1 x 12) + (4 x 1) = 12 + 4 = 16 amu

Molecular mass (given) = 16 amu

Therefore, Molecular formula = 1 x Empirical formula = 1 x CH4 = CH4.

Stoichiometry of Chemical Reactions

A chemical reaction can be represented by a chemical equation, which may

be defined as a chemical change in terms of symbols and formulae of the
substances involved in the reaction. The substances that react among
themselves to bring about the chemical changes are known as reactants,
where as the substances that are produced as a result of the chemical
change, are known as products.

Essentials of a chemical equation

A chemical equation should satisfy the following conditions:

It should represent a true chemical reaction.

It should be molecular in nature. Ionic reactions must be represented by

ionic equations.

It should be a balanced equation i.e. the number of atoms of each elements

on both sides should be equal.

Writing of a chemical equation

Steps for writing a chemical equation are:

The reactants and products of the reaction are identified and written down.

The formulae or symbols of the reactants are written on the left hand side
with a '+' sign in between them.

The formulae or symbols of the products are written on the right hand side
with a '+' sign in between them.

The two sides (reactants and products) are separated either by a sign of
equality (=) or that of an arrow ( ) pointing towards the products.

For a reversible reaction a sign ( ) is used in place of an arrow.

The number of atoms of each element are counted on both the sides. If they
are equal, then it is termed as balanced chemical equation. If they are not
equal, the balancing of the equation is done by adjusting the coefficients
before the symbols and formulae of the reactants and products.

In qualitative terms, a chemical equation conveys:

The names of various reactants and the products

In quantitative terms it represents:

The relative number of atoms and molecules (reactant and product species)
taking part in the reaction

The relative number of moles of the reactants and products

The relative masses of the reactants and products

The relative volumes of gaseous reactants and products

Thus the chemical equation gives us the quantitative relationship between
the reactants and products or the stoichiometry of the reaction.

Making a chemical equation more informative

The physical states of the reactants and products are specified. We use 's' for
solids, 'l' for liquids and 'g' for gases. Sometimes 'aq' is used for aqueous - to
represent that the given substance has been dissolved in excess of water.

The strength of acid or base used in the reaction is prefixed by the words
'conc'. for concentrated and 'dil'. for diluted.

The conditions of the reaction such as catalyst, temperature, pressure etc.

are written on the arrow between the reactants and products.

The above equation indicates that the reaction has been carried out in the
presence of a catalyst Fe/Mo at 723 K at 600 atm pressure.

Heat changes (absorption and evolution) in the reaction may be expressed in

the equation as

The distinction between slow and fast reactions can be made by writing the
words slow and fast on the arrow head.

The evolution of a gas in the reaction can be indicated by an arrow pointing

upward ( ) while the formation of a precipitate can be indicated by an arrow
pointing downwards ( ) or by writing the word 'ppt'.

The reversible nature of the reaction is indicated by a double headed arrow,

indicating that the reaction occurs in the forward as well as backward
direction.

Balancing of Chemical Equation

A chemical equation should be balanced so as to satisfy the requirements of

the law of conservation of mass, as no matter is destroyed or created during
a chemical reaction.

The two popular methods of balancing are the hit and trial method and
partial equation method.

Hit and trial method or inspection method

The symbols and formulae of the reactant and products are written as a
skeletal equation.

Any elementary gas (O2, H2, N2 etc.) appearing on either side of the skeletal
equation, is written in the atomic state.

The formula containing the maximum number of atoms is selected to begin

the process of balancing. If this method is not convenient, then balancing
begins with atoms, which appear minimum number of times.

Atoms of elementary gases are balanced at the last.

When the balancing is complete, the equation is converted to the molecular

form.

Problem

10. Balance the chemical equation,

By hit and trial method.

Solution

(i) Skeletal equation

(ii) Elementary gas in atomic form

(iii) Starting with KMnO4: K and Mn are balanced

(iv) Balancing O atoms

(v) Balancing H atoms

(vi) Balancing Cl atoms

The equation is now balanced in the atomic form.

(vii) To make it molecular multiply the equation by the original number of

gaseous atom (Cl2 i.e., 2)

So the balanced molecular equation is

Partial equation method

When equations contain many reactants and products they cannot be

balanced by the hit and trial method. They are then balanced by the partial
equation method. In this method the overall reaction is assumed to take
place through two or more simpler reactions, which can be represented by
partial equations. The steps involved are:
The given chemical equation is split into two or more partial equations.

Each partial equation is separately balanced by the hit and trial method.

These balanced partial equations are multiplied with suitable coefficients in

order to exactly cancel out those common substances which do not appear in
the overall chemical equations.

The balanced partial equations so obtained, are added to arrive at the

balanced chemical equation.

Problem

13. Balance the equation, by partial equation method.

Solution

The given skeleton equation can be split into two partial equations.

Partial eq.1

Partial eq.2

The two partial equations are balanced by hit and trial method.

Balanced partial eq.1

Balanced partial eq.2

NaClO does not appear in the overall equation and so to cancel it, the partial
balanced equation 1 is multiplied by 3 and the two equations are added to
get the overall balanced equation.
Limiting reagent

In a desired chemical reaction some reactants may be present in lesser or

greater proportions than the stoichiometry as indicated by the balanced
chemical equation. The reactant, which is completely used up first as per the
stoichiometry, limits the amount of product that can be formed and does not
allow the reaction to go further. This is the limiting reagent. The excess
reactants are left behind as unconsumed reagents, being limited by the
limiting reagent. In such cases the desired reaction does not go to 100%
completion.

Stoichiometric Calculations Involving Reactions/Solutions

Most chemical reactions are carried out in solutions. It is therefore important

to know how to express the concentration of a substance in its solution. The
most common ways of expressing concentration of any solute in a solution
are:

Mass percent: It is the mass of the solute in grams per 100 grams of the
solution.

A 5 % solution of sodium chloride means that 5 g of NaCl is present in 100g

of the solution.

Volume percent: It is the number of units of volume of the solute per 100
units of the volume of solution.

A 5 % (v/v) solution of ethyl alcohol contains 5 cm3 of alcohol in 100 cm3 of

the solution.

Molarity and molarity equation

Molarity of the solution is defined as the number of moles of solute
dissolved per litre (dm3) of the solution. It is denoted by the symbol M.
Measurements in Molarity can change with the change in temperature
because solutions expand or contract accordingly.

The Molarity of the solution can also be expressed in terms of mass and
molar mass

In terms of weight, molarity of the substance can be expressed as:

The units of molarity are moles per liter (mol L-1).

Molarity equation

To calculate the volume of a definite solution required to prepare another

solution of different molarity, the following equation is used:

M1V1 = M2V2,

where M1= initial molarity,

M2= molarity of the new solution,

V1= initial volume and

V2= volume of the new solution.

The molarity equation is commonly used to calculate the molarity of solutions

after dilution.
Normality

Normality: It is defined as the number of gram equivalents of solute present

per litre (dm3) of the solution at any given temperature. It is expressed as N.

The normality of the solution can also be expressed in terms of mass and
equivalent mass

In terms of weight, normality of the substance can be expressed as:

Measurements in normality can change with the change in temperature

because solutions expand or contract accordingly.

Normality equation

To calculate the volume of a definite solution required to prepare solutions of

different normality, the following equation is used:

N1V1 = N2V2,

where N1=initial normality

N2=normality of the new solution,

V1= initial volume and

V2= volume of the new solution.

The normality equation is commonly used to calculate the normality of

solutions after dilution. The above equation is also called as dilution formula
because it helps in calculating the volume of the solvent required in diluting a
concentrated solution. The same equation holds good for calculations
involving molarity (M).
Relationship Between Normality and Molarity of Solutions

Normality and Molarity are related as:

For acids

Normality = Molarity x Basicity

where basicity is the number of H+ ions a molecule of an acid can give.

For bases

Normality = Molarity x Acidity

where acidity is the number of OH- ions a molecule of a base can give.

Problems

11. Commercially available concentrated hydrochloric acid contains 38% HCl

by mass.

(a) What is the molarity of this solution? The density is 1.19 g/mL.

(b) What volume of concentrated HCl is required to make 1.00 L of 0.10 M

HCl?

Solution

(a) 38% solution, means 38 g of HCl in 100 g of solution.

Then, Mass of the solution= 100 g

Molar mass of HCl = 36.5 g mol-1

(b) The molarity of conc. HCl sample = 12.38 mol/L

Molarity of HCl solution to be prepared = 0.10 mol/L

Volume of HCl solution to be prepared =1.00 L= 1000mL

Then, using molarity equation, M1V1 = M2V2

Thus, to obtain 1.0 L of 0.10 M HCl, one should dissolve 8.08 mL of

concentrated HCl in a volume of 1.0 L of matter.

12. Concentrated nitric acid used as a laboratory reagent is usually 69% by

mass of nitric acid. Calculate the volume of the solution which contained 23 g
HNO3. Density of the concentrated HNO3 solution is 1.41 g cm-3.

Solution

Let, mass of conc. HNO3 sample = 100 g

Mass of HNO3 in 100 g of sample = 69 g

Mass of water in 100 g of sample = 31 g

Density of conc. HNO3 sample = 1.41 g cm-3

Thus, 69 g of HNO3 is contained in 70.92 cm3 of conc. HNO3

1g of HNO3 is contained in of conc. HNO3

23 g of HNO3 is contained in of conc. HNO3 = 23.6 cm3

Thus 23.6 cm3 concentrated HNO3 sample contained 23 g of HNO3.

Other Methods of Expressing Concentration of Solution

Molality: It is defined as the number of moles of solute dissolved per 1000 g

(1 kg) of solvent. Molality is expressed as 'm'.

Mole fraction is the ratio of number of moles of one component to the total
number of moles (solute and solvents) present in the solution. It is
expressed as 'x'.

Mole fraction of the solute + Mole fraction of solvent = 1