See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/326460294

Atomic Structure & Basic Concepts of Chemistry

Chapter · April 2018

CITATIONS READS
0 19,354

1 author:

Ramesh Duraisamy
Arba Minch University
20 PUBLICATIONS   121 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Phytochemical Screening, Toxicological Profile and In-Vivo Anti-Arthritic Activity of “Cymbopogon citratus” Leave Extracts in Lab Animals. View project

Fish Leather processing and sugar technolgy researches View project

All content following this page was uploaded by Ramesh Duraisamy on 18 July 2018.

The user has requested enhancement of the downloaded file.

E – MATERIAL for CHEMISTRY GRADUATES

Atomic Structure & Basic Concepts of Chemistry

Prepared By

Dr. RAMESH DURAISAMY

Assistant Professor
Department of Chemistry
Arba Minch University
Arba Minch (Ethiopia)
 Table of Contents
Chapter. I Introduction to Chemistry ..............4
1.1 Suggestions for Studying General Chemistry,
practicing with the new fact or skill. ...................4
1.1.1 Take responsibility for your own learning
.......................................................................4
1.1.2 Studying .................................................4
1.1.3 Develop an effective set of study skills ...4
1.1.4 Develop your problem-solving skills ......4
1.2 The Scientific Methods .................................5
1.2.1 Law and Hypothesis ...............................5
1.2.2 Theory....................................................5
1.3 Measurement and units in chemistry .............5
1.3.1 SI units ...................................................5
1.3.1.2 Density and Specific gravity ................6
1.3.1.4 Mole concept...........................................7
1.4 The Classification of Matter ..........................7
1.4.1 Three states of matter .............................7
1.5 Some Basic Definitions. ................................8
1.5.1 Physical and Chemical properties ...........8
1.5.2 Atoms and Molecules .............................8
1.5.3 Substances and Mixtures ........................9
1.5.4 Elements and Compounds ......................9
1.5.5 Molecules and Ions............................... 10
1.5.5.1 Molecules.............................................. 10
1.6 Significant Figures ...................................... 10
1.6.1 Guidelines for using Significant figures 10
Chapter-II Atomic Structure....................... 12
2.1 Atomic theory & fundamental particles ....... 12
Atomic Theory.................................................. 12
2.2 The structure of the Atom ........................... 12
2.2.1 The Electron ......................................... 12
2.2.2 The proton and Nucleus........................ 13
2.2.3 The Neutron ......................................... 14
2.3 Atomic number, Mass number and Isotopes 14
2.4 Nature of light and Electromagnetic radiation
......................................................................... 14
2.4.1 Corpuscular Theory .............................. 14
2.4.2 Characteristic of electromagnetic
radiation ....................................................... 15
2.4.3 Properties of Waves and Electromagnetic
radiation ....................................................... 15
2.4.4 Characteristics of wave motion............. 15
2.5 Electromagnetic Radiation .......................... 16
2.6 Quantum effects and photons ...................... 16
2.6.1 Planck’s Quantization Energy .............. 17
2.6.2 Photoelectric effect .............................. 17
2.7 Spectrum .................................................... 17
2.7.1 Atomic Spectra .................................... 17
2.7.2 Emission Spectra.................................. 17
2.7.3 Absorption Spectra............................... 18
2.8 Bohr model of the atom .............................. 19
2.8.1 Limitations of Bohr’s Theory: .............. 20
2.9 Dual Nature of the Electron ........................ 20
2.10 Quantum mechanics .................................. 20
2.10.1 Heisenberg Uncertainty Principle ....... 20
2.10.2 Schrodinger wave mechanics ............. 21
2.11 The Quantum mechanical Description of the
hydrogen atom .................................................. 21
2.12 Quantum Numbers .................................... 21
2.12.1 Principal quantum number (n) ............ 22
2.12.3 Magnetic quantum number ................. 22
2.12.4 Spin quantum number ........................ 23
2.13 Atomic Orbitals ........................................ 23
2.13.1 The energies of Orbitals ..................... 23
2.13.2 Electron Configuration ....................... 24
2.13.3 General Rules for Assigning Electrons
to Atomic Orbitals ........................................ 24
2.13.4 Method of writing electronic
configuration: ............................................... 24
nlx method and Box method .......................... 24
2.14 Pauli Exclusion Principle .......................... 25
2.15 Hund’s Rule .............................................. 25
2.15.1 Paramagnetism and Diamagnatism ..... 25
2.15.2 The shielding effect in Many-Electron
Atoms ........................................................... 25
2.16 The Building-Up Principle ........................ 26
Chapter-III Periodic Properties ............. 28 5.7 Precipitation Reactions ............................... 53
3.1 Need to classify elements ............................ 28 5.7.1 Solubility ............................................. 53
3.2 Brief history of modern periodic law and 5.8 Molecular equations and Ionic equations..... 55
modern periodic table.................................. 28 5.9 Acid-base neutralization.............................. 57
3.2.1 Modern periodic Law ........................... 28 5.10 Oxidation-Reduction Reactions ................. 57
3.2.2 Modern periodic table ( Long form of... 28 5.10.1 Oxidation Number.............................. 58
periodic table) ............................................... 28 5.10.2 Types of redox reactions .................... 60
3.3 Class of periodic elements : Based on 5.10.3 Balancing of Redox reactions ............. 62
electronic configuration .................................... 29
3.3.1 s - block elements ................................. 30
3.4 Chemical Properties of s-block elements ..... 32
3.4.1 IA Group elements (Alkali metals) ....... 32
3.5 p-block elements ......................................... 33
3.5.1 Introduction.......................................... 33
3.5.2 General aspects and trends in the p-block
elements........................................................ 33
3.6 Groups in p-block elements ......................... 34
3.6.1 Boron Family ....................................... 35
3.6.2 Elements of group IV A (Carbon family)
..................................................................... 36
3.6.3 Elements of VA (15th) group (Nitrogen
family) .......................................................... 37
3.6.4 Oxygen family (Elements of group VIA)
..................................................................... 38
3.7 IIA Group elements (Alkaline earth metals)
......................................................................... 39

Chapter - IV Molecular Geometry ........ 40

4.1 Molecular Geometry ................................... 40
4.2 Dipole moments .......................................... 42
4.3 Valence Bond Theory ................................. 43

Chapter. V Chemical Reactions .................. 44

5.1 Chemical Equations .................................... 44
5.1.1 Writing chemical equations .................. 44
5.2 The mole concept ........................................ 44
5.3 Balancing of the chemical equations ........... 46
5.4 Amount of reactants and products ............... 47
5.5 Limiting Reagents ....................................... 50
5.6 Reaction Yield ............................................ 51

Atomic Structure & Basics of Chemistry Page 3

Chapter. I Introduction to Chemistry
1.1 Suggestions for Studying General Chemistry
One of the most common challenges that General
Chemistry students have is that they don't realize the
importance of being actively involved in their own
learning. Many seem to think that coming to class
and passively listening to the instructor's pearls of
wisdom is all that is needed. Generally, everyone is
a little different; everyone has at least slightly
different intellectual equipment and a different set of
life and school experiences, which they bring to the
learning situation. Therefore, the learning
experience is a little different for each person, even
those in same classroom. The person who wishes to
become a learner must be actively involved in
constructing his or her own set of ideas. This
process will be different in its details for each
person, but each must go through a similar process
of hearing (or seeing or reading) the new item,
comparing it with what is already in his or her mind,
and integrating the new information into the
memory bank. This is not a simple process--it
requires work! The work may take the form of
reading and re-reading, thinking about the new
information and how it fits in, practicing with the
new fact or skill.
1.1.1 Take responsibility for your own learning
 Put in the required effort
 Read the assignments carefully before
coming to class, and then again after class.
 Do the assigned problems and may be
extras for good measures.
 Come to class prepared and on time. Class
attendance is important even if your
instructor doesn't specifically require it.
 Take complete notes in class
 Pay attention in class. Listen to your
instructor, not to the student next to you.
 If you miss class, make sure that you get all
the necessary information from the
instructor or another responsible student.
 Try to capture the ideas & concepts of lecture
Atomic Structure & Basics of Chemistry
 Take notes and review them immediately
after class.
 Use the five R's of note taking
1. Record: The meaningful ideas and
concepts
2. Reduce: After class, summarize the main
ideas and concepts
3. Recite: Say out loud in your own words
the main ideas of the class.
4. Reflect: Take a few minutes to ponder
over the main ideas of the class.
5. Review: Once a week, review the ideas of
all lectures.
1.1.2 Studying
 Study before each class. The material will be
fresh in your mind.
 Allow time for sleep.
 Set realistic goals for yourself. You can reward
yourself for being successful. If you waste all
afternoon and then set a goal of studying
chemistry from 6:00 p.m. to midnight, you may
not be realistic.
1.1.3 Develop an effective set of study skills
 Pace your studying throughout the week and
throughout the semester
 Get enough rest and otherwise take care of your
health.
 Find a place in which you can study effectively
 Form a study group with classmates and discuss
words, concepts, problem-solving strategies, etc.
to the benefit of all the members of the group.
1.1.4 Develop your problem-solving skills
 Sharpen your basic mathematical skills
 Learn how to use your calculator effectively.
 Learn & practice using units for physical
quantities.
 If you need a piece of information, look it up
using the index of your text or other suitable
source. Don't be afraid to be wrong, as Sir Isaac
Newton said many years ago, "Truth comes more
easily out of error than out of confusion."
Page 4
1.2 The Scientific Methods be determined directly. Microscopic properties, on
The study of chemistry concerned with the the atomic or molecular scale, must be determined
observations, theories and laws that give this science by an indirect method. A measured quantity is
its foundation and that form a framework into which usually written as a number with an appropriate unit.
information fits to make an integrated area of The same is true in chemistry; units are essential to
knowledge. This framework develops from the stating measurements correctly.
persuit of answers to many questions, each of which
can be subjected to experimental investigation by an 1.3.1 SI units
approach often called the scientific method. Many years’ scientists recorded measurements in
1.2.1 Law and Hypothesis metric units, which are related decimally (i.e. by
Scientists identify problems or questions through powers of 10). On 1960‘s the general conference of
their own observations and experiments and get the weights and measures notified, the international
conclusions, compare with earlier observations of system of units (SI). The SI system consists of the
the same. The first step of the scientific method, to a following seven units, from which other units of
problem involves carefully planning the experiments weight and measure can be derived. Measurements
to gather the information about all phases of the that we will utilize frequently in our study of
problem. The results are examined for general chemistry include time, mass, volume, density and
relationships that will unify the observations. temperature.
Sometimes a wide variety of observations can be
summarized in a general verbal statement or SI base units:
mathematical equation known as a law. ---------------------------------------------------------------
One example is the law of conservation of mass, Physical property Name of unit Symbol
which summarizes the results of thousands of ---------------------------------------------------------------
experimental observations. More often, is suggested Length meter m
Mass kilogram kg
a tentative explanation. Such a proposal is called a
Time second s
hypothesis.
Electric current Ampere A
1.2.2 Theory
Temperature Kelvin K
A hypothesis is tested by further experiments, and, if Luminous intensity Candela cd
it is capable of explaining the large body of Amount of substance mole mol
experimental data, it is dignified by the name of ---------------------------------------------------------------
theory. The data obtained in a research study may be the powers to which 10 is raised as, common
both quantitative, consisting of general observations prefixes used in the metric system
about the system, and qualitative, comprising ---------------------------------------------------------------
numbers obtained by various measurements and Prefix Symbol Factor Example
observations. ---------------------------------------------------------------
1.3 Measurement and units in chemistry pico p 10-12 1 picoeter (pm)
-9
nano n 10 1nano gram (ng)
The measurements chemists make are often used in
micro  10-6 1microliter (L)
calculations to obtain other related quantities.
milli m 10-3 2milliseconds(ms)
Different instruments enable us to measure a centi c 10 -2
5centimeters(cm)
substance’s properties. The meter stick measures deci d 10-1 1 deciliter (dL)
length or scale; the buret, the pipette, the graduated 3
kilo k 10 1kilometer(km)
cylinder and volumetric flask measure volume; the mega M 106 3 mega grams (Mg)
9
balance measures mass; the thermometer measures giga G 10 5 giga meters (Gm)
temperature. These instruments provide tera T 1012 1 tera litre (TL)
measurements of microscopic properties, which can ---------------------------------------------------------------

Atomic Structure & Basics of Chemistry Page 5

Chemists are interested primarily in mass, which can 1 g/cm3 = 1g/mL = 1000 kg/m3
be determined readily with a balance; the process of 1g/L = 0.001g/mL
measuring mass is called weighing. The SI base unit The term specific gravity denotes the ratio of the
of mass is the kilogram (kg), but in chemistry the density of a substance to the density of a reference
smaller gram (g) is more convenient; substance. Usually, the reference substance for
1 kg = 1000g = 1x103g solids and liquids is water.
1.3.1.1 Mass and Weight Density of substance
Mass is a measure of the amount of matter in an Specific gravity = -----------------------------------------
object, it is an invariable quantity. On the other Density of reference substance
hand, the weight of a body is the force that gravity Specific gravity, being the ratio of two densities, has
exerts on the body; it is variable, since the attraction no units. Usually the specific gravity of any
depends on the distance from planet’s center. substances is numerical.
Scientists measure quantities of matter in terms of Workout.1 Calculate the density and specific
mass rather than weight because the mass of a body
gravity of a body that has a mass of 321g and a
remains constant, whereas its weight is an accident
volume of that 45 cm3 at 250C.
of its environment. However, that the term weight is
often used loosely for the mass of a substance.
Mass 321g
The mass of an object is found by comparing it to Density = --------------- = ------------ = 7.13 g/cm3
other objects of known mass. The instrument used to Volume 45 cm3
make this comparison is called a balance. The
standard object to which all SI and other metric units Density of sample
Specific gravity = --------------------------
of mass are referred a cylinder of platinum-iridium
Density of water
alloy. The unit of mass, the kilogram (kg), is defined The density of water at 250C is 0.99 g/cm3, specific
as the mass of this cylinder; some times kilogram gravity of sample is 7.13.
expressed in pounds (1 kilogram is about 2.2
pounds). The gram (g) is equal to exactly 0.001 Workout.2 What is the mass in kg of 10.5g (39.7L)
times mass of the std kilogram (1x10-3 kg) and is of gasoline with a specific gravity of
nearly equal to the weight of 1cm3 of water. 0.82?
1.3.1.2 Density and Specific gravity Because gasoline has a specific gravity of 0.82 the
One of the physical properties of a solid, liquid or a density of 1mL of gasoline is 0.82 times that of
gas is its density. Density is defined as mass per unit 1mL of water.
volume. This is mathematically expressed as, Density = Specific gravity x density of water
Mass M = 0.82 x 0.997 g/cm3
Density = ------------- (or) D -------
Volume V = 0.82 g/cm3 (or 0.82 g/mL)
Conversion of 39.7 L to mL followed by
Substances usually have different densities, multiplication by the mass of 1mL of gasoline gives
Substances Density (at 250C and 1atm.) the total mass.
Air 1.29 g/L
He 0.179 g/L
H2O 0.997 g/cm3 1000 mL
Glycerin 1.26 g/cm3 Volume = 39.7L x ------------- = 39700 mL
Hg 13.6 g/cm3 1L
Salt 2.17 g/cm3
Iron 7.86 g/cm3 Mass = Density x Volume
Silver 10.5 g/cm3 = 0.82 g/mL x 39700 mL
= 33,000 g
Here, density for all cases expressed as, g/cm3 Mass = 33kg

Atomic Structure & Basics of Chemistry Page 6

Workout.3 A piece of gold in got with a mass of
301g has a volume of 15.6 cm3. Calculate
the density of gold.
D = M/V = 301g / 15.6 cm3
D = 19.3 g/cm3
1.3.1.3 Volume
The SI unit of length is the meter (m) and the SI
derived unit for volume is the cubic meter (m3).
Generally, chemists work with smaller volumes,
such as cubic centimeter (cm3) and the cubic
decimeter (dm3).
1cm3 = (1x10-2m)3 = 1x10-6m3
1dm3 = (1x10-1m)3 = 1x10-3m3
Another common unit of volume is the liter (L). A
liter is the volume occupied by one cubic decimeter.
One liter volume is equal to 1000 mL or 1000 cm3.
1L = 1000 mL
= 1000 cm3 (1mL = 1cm3)
= 1 dm3
1.3.1.4 Mole concept
Usually, number of atoms is measured in the units of
6.023x1023. This unit called one mole of atoms
(1mol). The number of atoms in one mole of any
element (1 mol. of atom has 6.023 x 1023 atoms) is
also called Avogadro’s number. For example, let us
consider a sample of carbon tetra chloride by
combining 1 mole of carbon atoms with 4 moles of
Cl atoms. This would be a produce 6.023 x 1023
molecule of CCl4.
Workout.4 How many CCl4 molecules can be made
by the combination of 0.050 mol of
carbon atoms with Cl atom?
The formula of CCl4 tells us that one CCl4 molecule
contains one carbon atom (1 molecule CCl4/ 1 atom
of C). If we can determine number of carbon atoms
present, we can determine the number of CCl4
molecules that can be made. One mole of C atoms,
contains 6.023x1023 C atoms; 0.050 mole of C
atoms contains,
0.050 mol C atoms x 6.023 x 1023 mol of C atoms
-----------------------------------------------------------------
1 mol of C atoms
= 3x1022 C atoms
A single CCl4 molecule contains 1 atom of carbon.
Therefore, we can make 1 molecule of CCl4 for each
Atomic Structure & Basics of Chemistry
carbon atom. Because we have 3x1022 atoms of
carbon we can make,
1 CCl4 molecule
22
3 x 10 C atoms x -------------------------
1 C atom
22
= 3x10 CCl4 molecules
Problem.5 How many moles of chlorine atom are
required to react with 0.050 mol of
carbon atoms to convert all of the carbon atoms to
CCl4.
The formula CCl4 indicates that there are 4 Cl atoms
for each C atom in a molecule, thus we must take
four times as many Cl atoms as C atoms,
6.023x1023 C atoms
0.050 mol C atoms x -------------------------------
1 mol C atoms
22
= 3x10 C atom
4 Cl atoms
3x10 C atoms x ---------------- = 1.2x1023 Cl atoms
22
1 C atoms
calculate the number of moles of Cl atoms from the
definition of a mole, 1 mole of Cl atoms contains
6.023x1023 Cl atoms [1 mol Cl atom / 6.023x1023 Cl
atoms)
1 mol Cl atom
23
1.2x10 Cl atoms x -----------------------------
6.023x1023 Cl atoms
= 0.20 mol of Cl atom
1.4 The Classification of Matter
The chemistry deals the study of matter and the
changes it undergoes. Matter is anything that
occupies space and has mass. Thus, everything in
the universe has a “chemical” connection. Chemical
distinguish among several subcategories of matter
based on composition and properties. The
classification of matter includes substances,
mixtures, elements and compounds, as well as atoms
and molecules.
1.4.1 Three states of matter
All substances, at least in principle, can exist in
three states: solid, liquid, and gas. The gases differ
from liquids and solids in the distances between the
molecules. In a solid, molecules are held close
Page 7
together in an orderly fashion with little freedom of
motion. Molecules in a liquid are close together but
are not held so rigidly in position and can move past
one another. In a gas, distances that are large
compared with the size of the molecules separate the
molecules.
The three states of matter can be interconverted
without changing the composition of the substance.
Upon heating, a solid (ice) will melt to form a liquid
(water) the temperature at which this transition
occurs is called the melting point. Further heating
will convert the liquid into a gas, this conversion
take place at the boiling point of the liquid. On the
other hand, cooling a gas will cause it to condense
into a liquid. When the liquid is cooled further, it
will freeze into the solid form.
1.5 Some Basic Definitions: Mass and Weight,
Physical and Chemical properties, Atoms and
molecules, Substances and Mixtures, Elements
and Compounds.
1.5.1 Physical and Chemical properties
Substances are identified by their properties as well
as composition. Color, melting point, and boiling
point are physical properties. A physical property
can be measured and observed without changing the
composition or identity of a substance. For
example, we can measure the melting point of ice by
heating a block of ice and recording the temperature
at which the ice is converted to water. Water differs
from ice only in appearance, not in composition, so
this is a physical change; we can freeze the water to
recover the original ice. Therefore, the melting point
of a substance is a physical property. Similarly,
when we say that helium gas is lighter than air, we
are referring to a physical property.
On the other hand the statement. “Hydrogen gas
burns in oxygen gas to form water”, describes a
chemical property of hydrogen, because in order to
observe this property we must carry out a chemical
change, in this case burning. After the change, the
original chemical substance, the hydrogen gas, will
have vanished, and all that will be left is a different
chemical substance. In the case, of water we cannot
recover the hydrogen from the water by means of a
physical change, such as boiling or freezing.
Atomic Structure & Basics of Chemistry
All measurable properties of matter fall into one of
two additional categories: extensive properties and
intensive properties. The measured value of an
extensive property depends on how much matter is
being considered. Mass, which is the quantity of
matter in a given sample of a substance, is an
extensive property. More matter means more mass.
Values of the same extensive property can be added
together. For example, two copper pennies will have
a combined mass that is the sum of the masses of
each penny, and the length of two tennis courts is
the sum of the lengths of each tennis court. Volume,
defined, as length of cubed, is another extensive
property. The value of an extensive quantity
depends on the amount of matter.
The measured value of an intensive property does
not depend on how much matter is being considered.
Density, defined as the mass of an object divided by
its volume, is an intensive property. We consider the
temperature. Suppose that we have two beakers of
water at the same temperature. If we combine them
to make a single quantity of water in a larger beaker,
the temperature of the larger quantity of water will
be the same as it was in two separate beakers.
Unlike mass, length, and volume, temperature and
other intensive properties are not in additive.
1.5.2 Atoms and Molecules
An atom is the smallest particle of an element that
can enter into a chemical combination. The word
atom comes from the Greek word atomos, which
means indivisible. John Dalton, an English chemist
and physicist, presented an atomic theory and
supported with quantitative measurements, found it.
A molecule is the smallest particle of an element or
compound that can have a stable, independent
existence. A molecule may consist of a single atom,
as in helium, of two or more identical atoms, as in
nitrogen and sulfur, or of two or more different
atoms, as in water. Water has a definite composition
and a set of chemical properties that enable us to
recognize it as a distinct substance. Each water
molecule is a unit that contains two hydrogen atoms
and one oxygen atom. Subdivision of a water
molecule results in the formation of the gases
hydrogen and oxygen, each of which has properties
Page 8
quite different from those of water and those of each For convenience, chemists use symbols of one or
other. two letters to represent the elements. The first letter
1.5.3 Substances and Mixtures of a symbol is always capitalized, but any following
A substance is a form of matter that has a definite letters are not. For example, Co is the symbol for the
(constant) composition and distinct properties. element cobalt, whereas CO is the formula for the
Examples are water, ammonia, sucrose, gold and carbon monoxide molecule. Names and symbols of
oxygen. Substances differ from one another in some of the more common elements are presented
composition and can be identified by their as,
appearance, smell, taste, and other properties. -----------------------------------------------------------------
A mixture is a combination of two or more Name Symbol Name Symbol
substances in which the substances retain their -----------------------------------------------------------------
distinct identities. Some familiar examples are air, Aluminum Al Fluorine F
soft drinks, milk, and cement. Mixtures do not have Oxygen O Arsenic As
constant composition. Gold Au Phosphorus P
Mixtures are either homogeneous or heterogeneous. Barium Ba Hydrogen H
When a spoonful of sugar dissolves in water we Platinum Pt Bismuth Bi
obtain a homogeneous mixture in which the Iodine I Potassium K
composition of the mixture is the same throughout. Bromine Br Iron Fe
If sand is mixed with iron filings, however, the sand Silicon Si Calcium Ca
grains and the iron filings remain separate. This type Lead Pb Silver Ag
of mixture is called a heterogeneous mixture Carbon C Magnesium Mg
because the composition is not uniform. Sodium Na Chlorine Cl
Any mixture, whether homogeneous or Manganese Mn Sulfur S
heterogeneous, can be created and then separated by Chromium Cr Mercury Hg
physical means into pure components without
Tin Sn Cobalt Co
changing the identities of the components. Thus,
Nickel Ni Tungsten W
sugar can be recovered from a water solution by
Copper Cu Nitrogen N
heating the solution and evaporating it to dryness.
Zinc Zn
Condensing the vapor will give us back the water
---------------------------------------------------------------
component.
The symbols of some elements are derived from
1.5.4 Elements and Compounds
An element is a substance that cannot be separated their Latin names-for example, Au from aurum
into simpler substances by chemical means. To date, (gold), Fe from ferrum (iron), and Na from natrium
115 elements have been positively identified. (sodium), while most of them come from English
Eighty-three of them occur naturally on Earth. names.
Scientists via nuclear processes have created the Atoms of most elements can interact with one
others. another to form compounds. For example, hydrogen
Only a few elements, such as the gases helium, gas burns in oxygen gas to form water, which has
neon, and argon, consist of a collection of individual properties that are distinctly different from those of
atoms that move about independently of one the starting materials. Water is made up of two parts
another. Other elements, such as the gases nitrogen, hydrogen and one part oxygen. Thus, water is a
oxygen and chlorine, consist of pairs of atoms, each compound, a substance composed of atoms of two
pair moving as a single unit. The element or more elements chemically united in fixed
phosphorous consists of units composed of four proportions.
phosphorus atoms; sulfur, of units composed of
eight sulfur atoms.
Atomic Structure & Basics of Chemistry Page 9
1.5.5 Molecules and Ions
Out of all the elements, only the six noble gases (He,
Ne, Ar, Kr,Xe, and Rn) exist in nature as single
atoms. For this reason, they are called monatomic
(mean a single atom) gases. Most matter is
composed of molecules or ions formed by atoms.
1.5.5.1 Molecules
A molecule is formed from least two atoms in a
definite arrangement held together by chemical
forces (called chemical bonds). A molecule may
contain atoms of the same element or atoms of two
or more different elements joined in a fixed ratio.
Thus, a molecule is not necessarily a compound,
which is made up of two or more elements. For
example hydrogen gas is a pure element, but it
consists of molecules made up of by two H atoms.
On the other hand, water is a molecular compound
that contains hydrogen and oxygen in a ratio of two
H atoms and one O atom. Like atoms, molecules are
electrically neutral.
The hydrogen molecule, H2, is called a diatomic
molecule because it contains only two atoms of the
same element. Other elements that normally exist as
diatomic molecule are nitrogen (N2) and oxygen
(O2) as well as F2, Cl2 and I2. A diatomic molecule
can also contain atoms of different elements. For
example are hydrogen chloride (HCl) and CO.
The vast majority of molecules contain more than
two atoms. They can be atoms of the same element,
as in ozone (O3), which is made up of three atoms of
oxygen, or they can be combinations of two or more
different elements. Molecules containing more than
two atoms are called polyatomic molecules. Like
ozone, water (H2O) and ammonia (NH3) are
polyatomic molecules.
1.5.5.2 Ions
An ion is an atom or a group of atoms that has a net
positive or negative charge. The loss of one or more
electrons from a neutral atom results a cation
(positive charge). For example, a sodium atom (Na)
can readily lose an electron to become sodium
cation, which is represented by Na+:
Na atom: 11 protons and 11 electrons
Na+ ion : 11 protons and 10 electrons
An anion is an ion whose net charge is negative due
to an increase in the number of electrons. A chlorine
Atomic Structure & Basics of Chemistry
atom (Cl) can gain an electron to become the
chloride ion Cl-
Cl atom: 17 protons and 17 electrons
Cl- ion : 17 protons and 18 electrons
Sodium chloride (NaCl), table salt, is an ionic
compound because it is formed from cations and
anions. An atom can lose or gain more than one
electron. The ions Na+ and Cl- are called monatomic
ions because they contain only one atom. In
addition, two or more atoms can combine to form an
ion that has a net positive or net negative charge.
Examples of ions formed by the loss or gain more
than one electron are Mg2+,Fe3+,S2- and N3-.
Polyatomic ions such as OH- (hydroxide ion), CN-
(cyanide ion) and NH4+ (ammonium ion) ions are
containing more than one atom.
1.6 Significant Figures
Except when all the numbers involved are integers,
it is often impossible to obtain the exact value of the
quantity under investigation. For this reason, it is
important to indicate the margin of error in a
measurement by clearly indicating the number of
significant figures, which are the meaningful digits
in a measured or calculated quantity. When
significant figures are used, the last digit is
understood to be uncertain.
1.6.1 Guidelines for using Significant figures
We must always be careful in scientific work to
write the proper number of significant figures. In
general, it is fairly easy to determine how many
significant figures a number has by following these
rules:
 Any digit that is not zero is significant. Thus 815
cm has three significant figures, 1.374 kg has
four significant figures, and so on.
 Zeros between nonzero digits are significant.
Thus 608 m contains three significant figures,
30,403 kg contains five significant figures, and so
on.
 Zeros to the left of the first nonzero digit are not
significant. Their purpose is to indicate the
placement of the decimal point. For example,
0.08 L contains one significant figure; 0.000756 g
contains three significant figures, and so on.
Page 10
 If a number is greater than 1, then all the zeros
written to the right of the decimal point count as
significant figures. Thus 2.0mg has two
significant figures, 40.062 mL has five significant
figures, and 3.040 dm has four significant figures.
If a number is less than 1, then only the zeros that
are at the end of the number and the zeros that are
between nonzero digits are are significant. This
means that 0.090 kg has two significant figures,
0.3005 L has four significant figures, 0.00420
min. has three significant figures, and so on.
 For numbers that do not contain decimal points,
the trailing zeros may or may not be significant.
Thus 400 cm may have one significant figure (the
digit 4), two significant figures (40), or three
significant figures (400). We cannot know which
is correct without ambiguity. In this particular
case, we can express the number 400 as 4x102 for
one significant figure, 4.0x102 for two significant
figures, or 4.00x102 for three significant figures.
The following example shows the determination
of significant figures.
Example.1 Determine the number of significant
figures in the following measurements: (a) 468 cm
(b) 5.03 g (c) 0.798 m (d) 0.046 kg (e)
23
1.340x10 atoms (f) 6000ml
Solution: We follow the rules for determining
significant figures. (a) Three (b) Three (c)
Three (d) Two (e) Four (f) This is an
ambiguous case. The number of significant figures
may be four (7.000x103), three (7.00x103), two
(7.0x103), or one (7x103).
A second set of rules specifies how to handle
significant figures in calculations.
 In addition and subtraction, the answer cannot
have more digits to the right of the decimal point
than either of the original numbers. Consider
these examples.
89.332 + 1.1 = 90.432 -------- round off to 90.4
2.097 – 0.12 = 1.977 --------- round off to 1.98
The rounding off procedure is as follows, to
round off a number at a certain point we simply
drop the digits that follow if the first of them is
less than 5. Thus, 8.723 rounds of 8.72 if we want
Atomic Structure & Basics of Chemistry
only two digits after the decimal point. If the first
digit following the point of rounding off is equal
to or greater than 5, we add 1 to the proceeding
digit. Thus 8.727 rounds off to 8.73 and 0.425
rounds of to 0.43.
 In multiplication and division, the original
number that has the smallest number of
significant figures determines the number of
significant figures in the final product or quotient.
The following examples illustrate this rule:
2.8 x 4.5039 = 12.61092 --- round off to 13
6.85/112.04 = 0.0611388789 round off to 0.0611
 Keep in mind that exact numbers obtained from
definitions or by counting numbers of objects can
be considered to have an infinite number of
significant figures. If an object has a mass of
0.2786g, then the mass of eight such object is,
0.2786 g x 8 = 2.229 g
We do not round off this product to one significant
figure, because the number 8 is 8.00000 …… by
definition.
Similarly, to take the average of the two measured
lengths 6.64 cm and 6.68 cm, we write
6.64 cm + 6.68 cm
----------------------- = 6.66 cm
2
Because the number 2 is 2.00000 …….. by
definition.
Page 11
Chapter-II Atomic Structure
2.1 Atomic theory & fundamental particles
Atomic Theory
In fifth century, the Greek philosopher Democritus
expressed that all matter consists of very small,
indivisible particles, named as ‘atomos’ (means
uncuttable or indivisible), but his idea was not
accepted. Experimental evidence from early
scientific investigations provides support for the
‘atomism’ and gradually gave the modern
definitions of elements and compounds. It was in
1808, English scientist John Dalton, formulated a
precise definition of the indivisible building blocks
of matter that we call atoms. According to this
Daltons’s summarized the atomic theory as,
1. Elements are composed of extremely small
particles called atoms. All atoms of a given
element are identical, having the same size, mass
and chemical properties. The atoms of one
element are different from the atoms of all other
elements.
2. Compounds are composed of atoms of more than
one element. In any compound, the ratio of the
number of atoms of any two elements present is
either an integer or a simple fraction.
3. A chemical reaction involves only the separation,
combination or rearrangement.
Dalton’s concept of an atom was far more detailed
and specific than Democritus and Dalton’s proposed
the three hypotheses are as follows,
First hypothesis
It states that atoms of one element are
different from atoms of all other elements. Dalton
made no attempt to describe the structure or
composition of atoms, he had no idea about, what an
atom is really like. But he did realize that the
different properties shown by different elements
such as hydrogen and oxygen can be explained by
assuming that hydrogen atoms are not the same as
oxygen atoms.
Second hypothesis
The 2nd hypothesis suggests that, in order to
form a certain compound, we need not only atoms of
Atomic Structure & Basics of Chemistry
the right kinds of elements, but specific numbers of
these atoms as well. This idea is an extension of law
published by Joseph Proust (in 1799), a French
chemist. Proust’s law of definite proportions states
that different samples of the same compound always
contain its constituent elements in the same
proportion by mass.
Dalton’s 2nd hypothesis supports another important
law, the law of multiple proportions. According to
this law, if two elements can combine to form more
than one compound, the masses of one element that
combine with a fixed mass of the other element are
in ratios of small whole numbers. Dalton’s theory
explains the laws of multiple proportions, different
compounds made up of the same elements differ in
the number of atoms of each kind that combine. For
example, carbon forms two stable compounds with
oxygen, namely carbon monoxide and carbon
dioxide.
Third hypothesis
It is another way of stating the law of
conservation of mass, which is that matter can be
neither created nor destroyed. Since matter is made
of atoms that are unchanged in a chemical reaction,
it follows that mass must be conserved as well.
2.2 The structure of the Atom
On the basis of Dalton’s atomic theory, we
can define an atom as the basic unit of an element
that can enter into chemical combination. Dalton
imagined an atom that was both extremely small and
indivisible. However, a series of investigations,
clearly demonstrated that, atoms actually posses
internal structures; that is, they are made up of even
smaller particles, which are called subatomic
particles. This research discovered the three such
particles, named as electrons, protons and neutrons.
2.2.1 The Electron
One device used to investigate the atomic structure
was a cathode ray tube; it is a glass tube from which
most of the air has been evacuated. When the two
metal plates are connected to a high-voltage source,
the negatively charged plate, called the cathode,
emits a ray. The cathode ray is drawn to the
positively charged plate, called anode, where it
Page 12
passes through a hole and continues traveling to the
other end of the tube. When the ray strikes the
specially coated surface, it produces a strong
fluorescence, or bright light.
In some experiments two electrically charged plates
and a magnet were added to the outside of the
cathode ray tube. When the magnetic field is on and
the electric field is off, the cathode ray strikes point
A. When only the electric field is on, the ray strikes
point C. When both magnetic and the electric fields
are off or when they are both on but balanced so that
they cancel each other’s influence, the ray strikes
point B. According to electromagnetic theory, a
moving charged body behaves like a magnet and can
interact with electric and magnetic fields through
which it passes. Since the cathode ray is attracted by
the plate bearing positive charges and repelled by
the plate bearing negative charges, it must consist of
negatively charged particles. We know these
negatively charged particles as electrons.
An English physics, J.J.Thomson, used a cathode
ray tube and his knowledge of electromagnetic
theory to determine the ratio of electric charge to the
mass of an individual electron. The number he came
up, -1.76x108 C/g, where C stands for coulomb,
which is the unit of electric charge. Thereafter, in a
series of experiments carried out, R.A.Millikan
succeeded in measuring the charge of the electron
with great precision. His work proved that
the charge on each electron was exactly the same.
In his experiment, he suspended the charged drops
in air by applying an electric field and followed their
motions through a microscope. Using his knowledge
of electrostatics, Millikan found the charge of an
electron to be –1.6022x10-19 C. From these data he
calculated the mass of an electron.
Charge
mass of an electron = -------------------
Charge/mass
-1.6022x10-19C
= --------------------- = 9.10 x 10-28 g
- 1.76 x 108 C/g
Radioactivity
The German physicist Wilhelm Rontgen noticed (in
1895), that cathode rays caused glass and metals to
Atomic Structure & Basics of Chemistry
emit very unusual rays. This highly energetic
radiation penetrated matter, darkened covered
photographic plates, and caused a variety of
substances to fluoresce. Since a magnet could not
deflect these rays, they could not contain charged
particles as cathode rays. Rontgen called them X
rays because their nature was not known.
After Rontgen’s discovery, Antoine Becquerel,
began to study the fluorescent properties of
substances, he found that exposing thickly wrapped
photographic plates to a certain uranium compound
caused them to darken, even without the stimulation
of cathode rays. Like X rays, the rays from the
uranium compound were highly energetic and could
not be deflected by a magnet, but they differ from X
rays because they arose spontaneously. One of
Becquerel’s students, Marie Curie, suggested the
name radioactivity to describe this spontaneous
emission of particles and/or radiation.
Since then, any element emits the radiation as
spontaneously is said to be radioactive.
Three types of rays are produced by the decay, or
breakdown, of radioactive substances such as
uranium. Two of the three are deflected by
oppositely charged metal plates (shown in figure).
Alpha () rays consist of positively charged
particles, called  particles, and therefore are
deflected by the positively charged plate. Beta ()
rays, or  particles, are electrons and are deflected
by the negatively charged plate. The third type of
radioactive radiation consists of high-energy rays
called gamma () rays. Like X rays,  rays have no
charge and are not affected by an external field.
2.2.2 The proton and Nucleus
By the early 1900s, two features of atoms had
become clear: they contain electrons, and they are
electrically neutral. To maintain electric neutrality,
an atom must contain an equal number of positive
and negative charges. Therefore, Thomson proposed
that an atom could be thought of as a uniform,
positive sphere of matter in atoms.
The New Zealand physicist Ernest Rutherford,
studied with Thomson at Cambridge University,
decided to use  particles to probe the structure of
atoms. Rutherford carried out a series of
Page 13
experiments using very thin foils of gold and other
metals as targets for  particles from a radioactive
source.
He was observed that the majority of particles
penetrated the foil either un-deflected or with only a
slight deflection. But, a  particle was scattered at a
large angle. Rutherford, explained the results of the
-scattering experiment in terms of a new model for
the atom. According to Rutherford concept, most of
the atom must be an empty space. This explains why
the majority of  particles passed through the gold
foil with little or no deflection. The atoms have
positive charges, which is in central core of the
atom, called nucleus. The positively charged
particles in the nucleus are called protons. In
separate experiments, it was found that each proton
carries the same quantity of charge as an electron
and has a mass of 1.6262 x 10-24 g about 1840 times
the mass of the oppositely charged electron.
2.2.3 The Neutron
Rutherford’s model of atomic structure left one
major problem unsolved. It was known that
hydrogen, the simplest atom, contains only one
proton and that the helium atom contains two
protons. Therefore, the ratio of the mass of a helium
atom to that of a hydrogen atom should be 2:1. In
reality, however, the ratio is 4:1. Rutherford and
others postulated that there must be another type of
subatomic particle in the atomic nucleus; another
English physicist, James Chadwick, provided the
proof. When Chadwick bombarded a thin sheet of
beryllium with  particles, a very high-energetic
radiation similar to  rays was emitted by the metal.
Later experiments showed that the rays actually
consisted of a third type of subatomic particles,
which Chadwick named neutrons, because they
proved to be electrically neutral particles having a
mass (1.67493 x 10-24), slightly greater than that of
protons.
2.3 Atomic number, Mass number and Isotopes N
Atomic number
The number of protons and neutrons they contain
can identify all atoms. The atomic number (Z) is the
number of protons in the nucleus of each atom of an
element. In a neutral atom the number of protons is
Atomic Structure & Basics of Chemistry
equal to the number of electrons, so the atomic
number also indicates the number of electrons
present in the atom. For example, the atomic number
of nitrogen is 7. This means that each neutral
nitrogen atom has 7 protons and 7 electrons.
Mass number
The mass number (A) is the total number of protons
and neutrons present in the nucleus of an atom of an
element. Except for the most common form of
hydrogen, which has one proton and no neutron, all
atomic nuclei contain both protons and neutrons. In
general the mass number is given by,
Mass number = No. of protons + No. of neutrons
= Atomic number + No. of neutrons
The number of neutrons in an atom is equal to the
difference between the mass number and the atomic
number, (A-Z). For example, the mass number of
fluorine is 19 and the atomic number is 9 (indicate 9
protons in the nucleus). Thus the number of neutrons
in an atom of fluorine is 19-9=10. The atomic
number, number of neutrons and mass number all
must be positive integer (whole numbers).
The accepted way to denote the atomic number and
mass number of an atom of an element is
represented as ZXA, A is mass number and Z is an
atomic number.
Isotopes
Most of the elements have two or more isotopes;
atoms that have the same atomic number but
different mass numbers. For example, there are three
isotopes of hydrogen. One, simply known as
hydrogen, has one proton and no neutrons. The
deuterium isotope contains one proton and one
neutron, and tritium has one proton and two
neutrons. Thus, for the isotope of hydrogen, we
write 1H1 (hydrogen), 1H2 (deuterium) and 1H3
(tritium). As another example, consider two
common isotopes of uranium with mass numbers of
235 and 238, respectively: 92U235, 92U238.
2.4 Nature of light and Electromagnetic radiation
2.4.1 Corpuscular Theory
Earliest view of light due to Newton regarded light
as made up of particles (corpuscles). This is due to
Page 14
some facts such as reflection and refraction. But it is
failed to explain interference and diffraction.
Hygens proposed wave like character of light
explains the phenomenon of interference and
diffraction. In 1856 James Clark Maxwell proposed
that light in the form of waves. These waves have
electric and magnetic field associated with them,
therefore electromagnetic radiations or
electromagnetic waves.
2.4.2 Characteristic of electromagnetic radiation
1. These consist of electric and magnetic fields that
oscillate in the directions perpendicular to each
other.
2. All electromagnetic waves travel with same
velocity. The velocity equal to that of light,
3x108 m/sec.
3. These electromagnetic radiations donot require
any medium for propagation. E.g. light reaches
us from the Sun through an empty space
2.4.3 Properties of Waves and Electromagnetic
radiation
According to Rutherford’s model, an atom consists
of a nucleus is many times smaller than the atom
itself, with electrons occupying the remaining space.
Each element has a characteristic line spectrum
because of the emission of light from atom in the hot
gas. The spectra can be used to identify elements.
This spectrum of each element was characterized
through the waves (i.e. electromagnetic radiation).
Wave motion
A familiar example of a electromagnetic waves like
waves in the surface of water. The waves originate
from the centre of disturbance and propagate in the
form of up and down movements.
That is, if we drop a stone into one end of quiet
pond, the impact of the stone with water starts an
up-and-down motion of the water surface. This up-
and-down motion travels outward from where the
stone hit.
A wave is a continuously repeating change or
oscillation in matter at regular intervals. Light is also
a wave; it consists of oscillations in electric and
magnetic fields that can travel through space.
Visible light, X rays and radio waves all are the
Atomic Structure & Basics of Chemistry
forms of electromagnetic radiation. The point of
maximum upward displacement is called crest, and
maximum downward displacement is called trough.
Thus, waves may be considered as a continuous
sequence of alternating crest and troughs.
2.4.4 Characteristics of wave motion
A wave was characterized by its wavelength and
frequency.
1. Wave length ()
The wavelength denoted by  (lambda) is defined as
the distance between any two adjacent peaks (crests)
or troughs on successive waves.
Unit – A0 (Angstron) 1A0 = 10-8 cm = 10-10 m
SI unit:  (micrometer), m (milli micron) ,
nm (nanometer), pm (picometer).
1A0 = 10-10m; 1 = 10-6m; 1m = 10-9m
1nm = 10-9m; 1pm=10-12m
2. Frequency ()
The frequency,  (nu) is the number of waves or
cycles per second pass through a given point.
In following figure shows the frequency corresponds
to the number of times per second that moves
through a complete cycle of upward and downward
motion. The frequency is expressed in the unit of
cycles per second (s-1) or Hertz (Hz).
1 Hz = 1 cycles per second  = C/
3. Amplitude: It is the vertical distance from the
midline of a wave to the peak or trough. Height of
crest or depth of trough i.e. intensity or brightness.
4. Velocity (C): Distance travelled by a light in one
second. The unit of velocity is ms-1 or cms-1
5. Wave number (): The number of waves per unit
length. Unit: cm-1 or m-1,  = 1/
Relationship: C =  x  ;  = C/
1/  =  ;  = C 
Exercise.1 Calculate the speed of a wave whose
wavelength and frequency are 17.4cm and 87.4 Hz,
respectively.
This is directly solved by the application of c= 
c= 17.4 cm x 87.4 Hz ; c = 17.4cm x 87.4/s
= 1.52 x 103 cm/s
Page 15
2.5 Electromagnetic Radiation
There are many kinds of waves, such as
water waves, sound waves, and light waves. In
1873 James Clerk Maxwell proposed that light
consists of electromagnetic waves. According to
Maxwell’s theory, an electromagnetic wave has an
electric field component and a magnetic field
component. These two components have the same
wavelength and frequency, and hence the same
speed, but they travel in mutually perpendicular
10-12 10-11 10-10 10-8 10-7
Wavelength
(nm)  rays X rays Far Near Vis Near Far IR Microwave Radio
UV UV
Frequency (Hz) 1020 1018 1016
Fig.1a Types of electromagnetic radiation
Violet
400 nm 500nm
Fig.1b Visible light ranges from 400nm (violet) to 700nm (red)
The fig.1a shows various types of electromagnetic
radiation, which differ from one another in
wavelength and frequency. The range of
frequencies or wavelengths of electromagnetic
radiation is called the electromagnetic spectrum.
The motions of electrons within atoms and
molecules produce the shorter, visible light waves.
The shortest waves, which also have the highest
frequency, are associated with  rays, which result
from changes within the nucleus of the atom.
In fig.1b visible light extends from the violet end
of the spectrum, which has a wavelength of about
400nm, to the red end, with a wavelength of less
than 800 nm. Beyond these extremes,
electromagnetic radiation is not visible to the
human eye. IR radiation has wavelengths greater
Atomic Structure & Basics of Chemistry
planes, and his model describes how energy in the
form of radiation can be propagated through space
as vibrating electric and magnetic fields.
Electromagnetic radiation is the emission and
transmission of energy in the form of
electromagnetic waves.
10-6 10-4 10-3 10-1
IR Radar TV, FM
1015 1014 1012 1010
Red
600nm 700nm
than 800nm and ultraviolet radiation has wavelengths
less than 400nm.
2.6 Quantum effects and photons
Issac Newton, who studied the properties of light in
the 17th century, believed that light consisted of a
beam of particles. In 1801, British physicist Thomas
Young showed that light like waves could be
diffracted.
By the early part of the twentieth century, the wave
theory of light appeared to be well entrenched. But in
1905, the German physicist Albert Einstein
discovered that he could explain a phenomenon
known as the photoelectric effect by postulating that
light had both wave and particle properties. Einstein
based this idea on the work of the German physicist
Max Planck.
Page 16
2.6.1 Planck’s Quantization Energy
Max Planck found a theoretical formula that
exactly describes the intensity of light of various
frequencies emitted by a hot solid at different
temperatures.
According to Planck, the atoms of the solid
oscillate, or vibrate with a definite frequency,,
depending on the solid and he found it necessary
strong idea.
1. Radiant energy is not emitted or absorbed
continuously but discontinuously in the form of
small pockets of energy called quanta. Each
such quanta is associated with a definite
amount of energy.
In the case of light, the quanta of energy are
often called photon.
2. The amount of energy associated with a
quantum of radiation is proportional to the
frequency of light.
E  or E = h  and
Where, h is a Planck’s constant with the value
6.63 x 10-34 J.s.
This relation found to be valid for all type of
electromagnetic radiation.
3. The total amount of energy emitted or absorbed
by a body (matter) will be some whole number
multiple of quantum.
E= nh ----------- (1) n=1,2,3,…………
This means that a body can emit or absorb
energy equal to h, 2h, 3h, ………. Or any
other integral multiple of h. But cannot emit or
absorb fractional value of h.
We know that, C =  ;  = C/
E= h C/ ---------- (2)
Equations (1) and (2) give the relation between
energy of radiation and its frequency or
wavelength.
A radiation which has higher the frequency or
lowers the wavelength has more energy. For
example, violet light is larger frequency has more
energy than red light which is having lower
frequency.
Atomic Structure & Basics of Chemistry
2.6.2 Photoelectric effect
Einstein used this photon concept to explain the
photoelectric effect.
The photoelectric effect is the ejection of electrons
from the surface of a metal or from another material
when light shines on it. Electrons are ejected, only
when the frequency of light exceeds at a certain
threshold value of the particular metal.
For example, violet light will cause potassium metal
to eject electrons; not in red light (which has lower
frequency).
When the photon hits the metal, its energy h is takes
up by the electron. The photon cease to exist as a
particle; it is said to be absorbed and emits the
electron as radiations (light).
The wave and particle pictures of light should be
regarded as complementary views, called wave-
particle duality of light. The equation E = h 
displays this duality.
i.e., E is the energy of a light particles or photon and
 is the frequency of the associated wave.
2.7 Spectrum
When white light from Sun is passed through a prism,
it split into a series of color band known as rainbow
colors (VIBGYOR). This means that Sunlight is
composed of collection of electromagnetic waves
having different wave length. The splitting of light
into seven colors is known as dispersion and the
series of color bands is called a spectrum. In this
spectrum, there is continuity of colors such a
spectrum is known as continuous spectrum.
2.7.1 Atomic Spectra
Unlike the spectrum obtained by analyzing the
sunlight, the spectra of atoms of elements can be
made to emit energy by subjecting them to electric
discharge or by heating are not continuous
(discontinuous).
The spectrum of atoms consists of sharp well-defined
lines or bands corresponding to definite frequencies.
There are two types of atomic spectra. (i) Emission
spectra (ii) Absorption spectra.
2.7.2 Emission Spectra
Emission spectra are obtained when the radiations
emitted from substances are analyzed with the help of
spectroscope.
Page 17
When the gases or vapor of chemical substances
are analyzed with heated by electric spark, light is
emitted. The color of light depends upon the
substance under investigation. Example, sodium
gives a yellow light and potassium produces violet
color.
This type of spectrum consists of sharp well-
defined line each corresponding to a definite
frequency (or wavelength). Such spectrum is
called line spectrum of discontinuous spectrum.
The line spectrum also known as atomic spectrum
because, it is obtained from atoms by the
application of heat or other energy (electric).
Each element gives a unique spectrum irrespective
of even the form in which it present. Example,
Sodium always gives lines at 589nm and 589.6nm
(yellow). From this reason line spectra are also
called as finger prints of atoms.
2.7.3 Absorption Spectra
When a continuous electromagnetic radiation
(white light) is allowed to pass through a gas or a
solution of some salt and the transmitted light is
analyzed. We obtain a spectrum in which dark
lines are observed. These dark lines indicate that
the radiations of corresponding wavelength have
been absorbed by the substances from the white
light.
Such a spectrum containing few dark lines due to
absorption of light is known as absorption
spectrum. The dark lines of wavelengths are also
character of a substance. Example, absorption of
Na consists of lines at 589nm and 589.6nm same
as that of emission spectrum.
2.7.4 Emission Spectrum of hydrogen atom
The spectrum of hydrogen atom has played a very
important role in the development of atomic
structure. The spectrum of hydrogen atom can be
obtained by passing an electric discharge current
through the hydrogen gas taken in the discharge
tube under low pressure.
The emitted light (radiation) is analyzed by
spectroscope. The spectrum consists of large
number of lines appearing in different wavelengths
(visible, UV, IR regions).
Atomic Structure & Basics of Chemistry
In 1885, J.J.Balmer developed a relationship among
the different wavelengths,  in the visible region in
hydrogen spectrum, could be reproduced by simple
formula:
i.e., 1/ = (cm-1) = 109678 (1/22 – 1/ni2)
or (cm-1) = 1.097 x 107(1/22 – 1/ni2)
ni is an integer but greater than 2, ni = 3,4,5,…..
These series of lines which appear in visible region
are named as Balmer series.
Afterwards, a series of spectral lines of H2 atom in
different regions were discovered. These series of
lines named after the name of its discoverers. These
are Lyman, Balmer, Paschen, Brackett and Pfund
series.
Lyman – UV region ; Balmer – Visible
Paschen, Brackett and Pfund – IR region
As the other series of hydrogen spectral lines were
discovered, a more general expression was found by
Rydberg, and is known as Rydberg equation derived
as,
E = - RH / n2 ------------ (1) n = 1,2,3,.., 
(for hydrogen atom)
Where, RH is Rydberg constant has the value
2.18x10-18J
n is principal quantum number
negative sign indicates arbitrary convention.
The energy levels of the electron in the hydrogen
atom do undergo a transition of electron between
energy levels; electron loses energy, which is emitted
as photon. The difference between the energies of the
initial and final state is:
E = Ef – Ei or Ei - Ef
From equation (1), Ef = - RH(1/nf2) and
Ei = - RH (1/ni2)
Therefore, E = - RH / nf2 – (- RH/ni2)
= RH/ni2 – RH/nf2
E = RH [1/ni2 – 1/nf2] --------- (2)
Because this transition results in the emission of a
photon of frequency,  and energy h, we can write:
E = h = RH [1/ni2 – 1/nf2]
and, we have  = c/, we can write this
hC/ = RH [1/ni2 – 1/nf2]
1/ =  = RH/hC [1/ni2 – 1/nf2] ------- (3)
Page 18
When a photon is emitted, ni > nf. Consequently
the term is negative and E is positive.
If when energy is absorbed, ni < nf and the term is
positive, so E is positive.
The brightness of a spectral line depends on how
many photons of the same wavelength are emitted.
In equation (3) by substituting RH=2.18x10-18J,
h=6.623x10-34 J.sec. and C=3x108m/sec, we found
that RH/hC is 1.097x107 m, which is the constant
given in the Balmer equation.
The emission spectrum of hydrogen includes a
wide range of wavelengths from the IR to UV, and
lists the series of transitions in the hydrogen
spectrum; they are named as,
Series nf ni Spectral region
Lyman 1 2,3,4,…… Ultraviolet
Balmer 2 3,4,5,…… Visible and UV
Paschen 3 4,5,6,……. IR
Brackett 4 5,6,7,……. IR
Pfund 5 6,7,8,……. IR
The above equation (3), and lines only applicable
for hydrogen atom. But other atoms lines are
complicated and equation is also not obeyed. The
energy levels of hydrogen atom with series of
emission spectral transition are labeled with their
principal quantum numbers.
The spectrum of hydrogen atom holds the key to
the inner structure of atom. Bohr proposed the
theory of atom based on Planck’s quantum theory
and spectra of hydrogen atom.
2.8 Bohr model of the atom
1. Maxwell’s law is not applicable to electron in
an atom.
2. An atom consists of a massive positively
charged nucleus. The electrons revolving
around the nucleus in a certain circular orbits
without radiation energy. These non-radiating
orbits are known as stationary states.
3. Each orbit is at different distance from the
nucleus and they are associated with definite
Atomic Structure & Basics of Chemistry
amount of energy. Hence, stationary states also
called as energy levels.
The energy associated with different energy levels
increases with increase in distance from the nucleus.
The letters of orbit (shell) : K,L,M,N,……
The numbers of orbit (shell) : 1,2,3,4,………
are used to designate the energy levels.
4. Energy associated with an energy level is given by
the relation:
- 2π2k2Z2me4
En = -------------------------
n2h2
Where, Z – atomic number
m – mass of electron
h – Planck’s constant
e –charge of electron
n – orbit number, and k = 9 x 109 Nm2c-2
k = 1/ 4 π0 ;
0 being permittivity of empty space
For hydrogen atom, Z = 1;
- 2π2k2me4
En = -------------------------
n2h2
substituting the value of m, e, π, k and h:
EH = - 1312 / n2 kJ/mol
For He+, Z = 2  EHe+ = 4 EH
For Li2+, Z = 3  ELi+ = 9 EH
1. Different energy levels are not equally spaced. i.e.,
the energy difference between two successive
energy levels is not same. It goes on decreasing
with increasing the value of n.
2. Angular momentum of an electron is a whole
number multiple of h/2π.
i.e. mvr = nh / 2π
h - Planck’s constant; m- mass of electron
v - tangential velocity;
r - radius of the orbit and, r = nh/2πmv
The velocity of electron in nth orbit of an atom is
given by vn = 2πe2Z / nh, and
r = n2h2 / 4π2mZe2
substituting the value of h, π, m, Z and e for
hydrogen, Z=1 comes to be 0.53A0
Page 19
3. Because of electron transition between two
stationary states of E1 and E2, then the energy is
emitted or absorbed in the form of quanta.
The frequency,  of the emitted or absorbed
radiation is given by, h = E2 – E1
4. Since energy cannot be lost continuously, and
an electron continuously to move in a particular
energy level without losing energy. Such a state
of the atom is known as ground state.
On gaining energy from an external source
electron jumps from a lower energy level to a
higher energy level is known as excited state.
However the excited state is unstable, and
excited electron jumps down from higher to
lower energy level (either directly or in steps)
by losing energy in the form of electromagnetic
radiation. This accounts for the spectral lines in
the hydrogen spectrum.
2.8.1 Limitations of Bohr’s Theory:
1. It is applicable only to hydrogen atom or
hydrogen like ions which contain only one
electron.
2. The spectra of multi electron system cannot be
explained by Bohr’s theory.
3. The experimental value of ionization energy
and the value calculated from Bohr’s theory
does not agree.
4. Bohr Theory cannot explain the mode of
formation of bonds between atoms.
5. It gives the flat model of the orbit.
6. By using spectroscope of high resolving power,
it is observed that each line in the ordinary
spectrum is split into a number of component
lines, differing slight in their frequencies, this is
called fine structure of spectral lines. Bohr’s
theory fails to explain the fine spectrum.
7. Bohr’s theory predicts definite orbits for
electrons. This goes against the modern ideas of
wave nature of electron.
2.9 Dual Nature of the Electron
De Broglie stated that if light waves can behave
like a stream of particles (photons), then particles
such as electrons could possess wave properties.
He argued that if an electron does behave like a
standing wave in the hydrogen atom, the
Atomic Structure & Basics of Chemistry
wavelength of the wave must fit exactly with
circumferences of the orbit.
The relation between the circumference of an allowed
orbit (2r) and the wavelength () of the electron is
given by,
2r = n ---------------- (1)
Where, r is the radius of the orbit,  is the wavelength
of the electron wave and n=1,2,3, ….. So, energy of
electron depends on size of the orbit, its value must
be quantized.
Thus, the waves can behave like particles and
particles can exhibit wavelike properties. So, De
Broglie deduced that the particle and wave properties
are related by the expression,
 = h/mu ----------------- (2)
Where, m and u are the wave length associated with
a moving particle. Note that the left side of equation
(2) involves the wavelike property of wavelength,
whereas the right side makes references to mass, a
distinct property of particle.
Workout:
1. Calculate the de-Broglie wavelength of a ball of
mass 0.1kg moving with a velocity 100ms-
(Ans: 6.626x10-35m).
2. The mass of an electron is 9.1x10-31kg. The
velocity is 800 ms-1. Calculate its wavelength.
2.10 Quantum mechanics
Bohr’s approach did not account for the emission
spectra of atoms containing more than one electron,
such as atoms of He and Li. He did not explain why
extra lines appear in the hydrogen emission spectrum
when a magnetic field is applied and could not define
the precise location of a wave.
Describe the problem of trying to locate a subatomic
particle that behaves like a wave, Heisenberg
formulated the uncertainty principle.
2.10.1 Heisenberg Uncertainty Principle
It stated that it is impossible to know simultaneously
both the momentum (p) and the position (x) of a
particle with certainty. It is stated mathematically,
x p  h/4 ---------------------- (3)
Where x and p are the uncertainties in measuring
the position and momentum.
Page 20
Applying Heisenberg uncertainty principle to the
H atom, we see that in reality the electron does not
in orbit the nucleus in a well-defined path, as Bohr
thought.
If it did, we could determine precisely the position
of the electron and its momentum at the same
time, a violation of the uncertainty principle.
Significance:
1. The principle is no significance for macro
objects. Because x p for ion ball having
mass 100. Example, x v= h/4m
= 6.623x10-27 erg.sec / 4x3.142x100
= 0.526x10-29 cm2sec-1
2. The principle cannot be neglected for
microscopic particle like electron. Example,
x v for electron having mass(m) is
9.1x10-28g
x v = h/4m = 6.62x10-27 erg.sec
-------------------------------
4x3.142x9.1x10-28 kg
It is applicable and cannot be ignored.
Uncertainty principle and idea of probability
picture of an atom.
According to bohr’s model, electrons revolved in
well defined circular orbits. But uncertainty
principle is not possible to know the exact position
and path of electron. This new approach called
wave mechanics.
2.10.2 Schrodinger wave mechanics
In 1927 Erwin Schrodinger (Austrian physicist)
used a complicated mathematical technique
formulated an equation that describes the behavior
and energies of submicroscopic particles.
In general the Schrodinger equation requires
advanced calculus to solve and it is important to
know that the equation incorporates both particles
behavior in terms of mass, m and wave behavior in
terms of wave function  (psi), which depends on
the location in space of the system.
According to wave theory, the intensity of light is
proportional to the square of the amplitude of the
wave or 2. The most likely to find a photon is
where the intensity is greatest, that is, where the
value of 2 is greatest. Schrodinger wave equation
Atomic Structure & Basics of Chemistry
(E=H) began a new area in physics and chemistry
called the quantum mechanics (wave mechanics).
2.11 The Quantum mechanical Description of the
hydrogen atom
The Schrodinger equation specifies the possible
energy states of the electron can occupy in a
hydrogen atom and identifies the corresponding wave
functions (). These energy states and wave
functions are characterized by a set of quantum
numbers, with which we can construct a model of the
hydrogen atom.
In quantum mechanics, concept of electron density
gives the probability that an electron will be found in
a particular region describes the atom.
The square of the wave functions, 2, defines the
distribution of electron density in three-dimensional
space around the nucleus.
According to quantum mechanics, an atomic orbital
can be thought as the wave function of an electron in
an atom. When we say that an electron is in a certain
orbital, it means that the distribution of the electron
density or the probability of finding the electron in
space is described by the square of the wave function
(2) associated with an orbital. Therefore, an atomic
orbital has a characteristic energy, as well as a
characteristic distribution of electron density. “An
orbital is defined as a region in space around the
nucleus where the probability of finding the electron
is maximum”.
The Schrodinger equation is applicable nicely for the
simple hydrogen atom with its one proton and one
electron, but it turns out that it cannot be solved
exactly for many-electron atoms. So, chemists and
physicist have learned to get the solution for this kind
by applying approximation methods. So, they
concluded that the behavior of electrons in many-
electron atoms is not the same as in the hydrogen
atom.
2.12 Quantum Numbers
In quantum mechanics, three quantum numbers are
required to describe the distribution of electrons in
atoms. These numbers are derived from the
mathematical solution of the Schrodinger equation
for the hydrogen atom. They are called the principal
Page 21
quantum number (n), the angular momentum
quantum number (l) and the magnetic quantum
number (ml).
These quantum numbers will be used to describe
atomic orbitals and label the electrons. A fourth
quantum number, spin quantum number describes
the behavior of specific electron.
2.12.1 Principal quantum number (n)
The principal quantum number (n) can have
integer values 1,2,3,……… The value of n
determines the energy of an orbital. In the case of
hydrogen atom or single electron atomic ions, such
as Li2+ and Be3+, the energy of these determined
by their principal quantum number. For other
atoms, the energy also depends on the angular
momentum quantum number (l).
The size of an atom also depends on the value of
n. The orbitals of the same quantum state “n” are
said to belong to the same shell. Shells are
designates by the following letters,
Letter K L M N O P 2 0, 1
n 1 2 3 4 5 6 3 0, 1, 2 3s, 3p, 3d
2.12.2 Angular momentum or Azimuthal quantum
number
This quantum number distinguishes the orbitals of
a given “n” having different shapes. The values
of l depends on the value of principal quantum
number, it can have any integer value from 0 to n-
1. With each shell of quantum number, n, there are
n different kinds of orbitals, each with a different
shape denoted by an “l” quantum number. For
example,
If, n = 1 has only one l i.e., l=0
n = 2 has two l values i.e., l=0,1
n = 3 has three l values i.e., l=0,1,2
n = 4 has four l values i.e., l=0,1,2,3
An electron has a n value is 3, the possible value
for l are 0,1 and 2. Thus, with in the M shell (n=3),
there are three kinds of orbitals, each having
different shape.
The energy also depends on the “l” quantum
number, orbitals of the same ‘n’ but different, ‘l’
values are said to belong different sub-shells of a
given shell, usually denoted by letters as,
Atomic Structure & Basics of Chemistry
Letter s p d f g h
l 0 1 2 3 4 5
n = 2, l = 0,1 has two sub shells (i.e. s, p)
n = 3, l = 0,1,2 has 3 sub shells (i.e. s, p, d)
n = 4, l = 0,1,2,3 has four sub shells (i.e. s, p, d, f)
Thus, if l=0, we have an s orbital; if l=1, we have a s
and p orbital and so on.
We denote a sub-shell with a particular shell, we
write the value of n quantum number for the shell,
followed by the letter designation for the sub-shell.
Thus, n=1, l=0 has one sub shell ---- s
and, maximum number of electrons in each sub-shell:
s - 2; p - 6 ; d-10 and f - 14.
For example, 2p denotes a sub-shell with quantum
numbers n = 2 and l = 1.
Correlation between n and l:
--------------------------------------------------------------
n l sub-shell no.of sub-shell no.of eles.
--------------------------------------------------------------
1 0 1s one 2
2s, 2p two 8
three 18
4 0, 1, 2, 3 4s, 4p, 4d, 4f four 32
--------------------------------------------------------------
2.12.3 Magnetic quantum number
The magnetic quantum number (ml) describes the
orientation of the orbital in space. Within a sub-shell,
the value of ml depends on the value of the angular
momentum quantum number, l. The allowed values
are the integers as follows:
-l,….. ,0,……+l (or) –l,(-l+1),…,0,---. (+l-1),+l
For l=0 (s subshell), the allowed ml quantum number
is 0 only; ther is only one orbital in the s sub-shell.
For l=1 (p subshell), ml=-1,0 and +1; there are 3
different orbitals in the p sub-shell. The orbitals have
the same sub-shell, but it has different orientation in
space (as in px, py and pz).
if, n=2, ml = -2,-1,0,+1,+2 has five orientation: dxy,
dyz, dxz, dx2 - y2, dz2.
if, n=3, ml=-3,-2,-1,0,+1,+2,+3 has seven orbital
orientations. But the orientation of ‘f’ orbital is
difficult to suggest.
In addition each orbital of a given sub-shell has the
same energy, note there are (2l+1) orbitals in each
sub-shell of quantum number.
Page 22
2.12.4 Spin quantum number
According to electromagnetic theory, a spinning
charge generates a magnetic field, and it is this
motion that causes an electron to behave like a
magnet.
The following figure shows the two possible
spinning motions of an electron, one clockwise
and the other counter clockwise. It is necessary to
introduce a fourth quantum number, called the
electron spin quantum number (ms), which has a Figure.1 Orbital energy levels in H2 atom
value of +1/2 or –1/2.
2.13 Atomic Orbitals The hydrogen’s electron has the same energy whether
The following table shows the relation between it is in the 2s orbital or a 2p orbital. The 1s orbital in a
permissible quantum numbers and atomic hydrogen atom corresponds to the most stable
orbital’s. We see that when l=0, (2l+1) = 1 and condition, the ground state. An electron residing in
there is only one value of ml, thus we have an s this orbital is most strongly held by the nucleus
orbital. When l=1, (2l+1) = 3, so there are three because it is closest to the nucleus. An electron in the
values of ml or three p orbital’s, labeled px, py and 2s,2p or higher orbital’s in a hydrogen atom is in an
pz. When l=2, (2l+1)=5 and there are five values of excited state.
ml, and the corresponding five d orbital’s are
labeled with more elaborate subscripts.
Table: Relation between quantum numbers and
atomic orbitals
-------------------------------------------------------------
n l m Number of orbital
Atomic orbital Designations
-------------------------------------------------------------
1 0 0 1 1s
Figure.2 Orbital energy levels for many e- atom
2 0 0 1 2s
The energy picture is more complex for many-
1 -1, 0, 1 3 2px, 2py, 2pz
electron atoms than for hydrogen. The energy of an
3 0 0 1 3s
electron in such an atom depends on its angular
1 -1, 0, 1 3 3px, 3py, 3pz
momentum quantum number as well as on its
2 -2,-1, 0, 1, 2 5 3dxy, 3dyz, 3dxz
principal quantum number (shown in figure.2). For
3dx2- y2, 3dz2
many electron atoms, the 3d energy level is very
--------------------------------------------------------------
close to the 4s energy level. Due to the repulsion
2.13.1 The energies of Orbitals
between the electrons, it turns out that the total
We know that, En=-RH (1/n2), from this
energy of an atom is lower when the 4s subshell is
equation the energy of an electron in a hydrogen
filled before a 3d subshell. Figure.3 depicts the order
atom is determined by its principal quantum
in which atomic orbital’s are filled in a many-electron
number. Thus the energies of hydrogen orbital
atom.
increase as follows,
1s  2s = 2p 3s=3p=3d  4s=4p=4d=4f  ……..

Atomic Structure & Basics of Chemistry Page 23


Figure.3 The order in which atomic sub shells
are filled in a many electron atom
The increasing order of the orbital as follows,
1s  2s  2p  3s  3p  4s  3d  4p  5s  4d 
5p  6s  4f  5d  6p  7s  5f  6d  7p  6f 
7d  7f  ………
2.13.2 Electron Configuration
By using the four quantum numbers n, l,ml and ms,
label completely an electron in any atom. For
example the four quantum numbers for a 2s orbital
electron are n = 2, l = 0, ml = 0 and ms= +1/2 and
ms = -1/2. It is convenient to write out all the
individual quantum numbers, and so we use the
simplified notation (n, l, ml, ms).
For example, above, their quantum numbers are
either (2, 0, 0, +1/2) or (2, 0, 0, -1/2). The value of
ms has no effect on the energy, size, shape or
orientation of an orbital.
In the case of hydrogen atom, contains only one
electron. The electron may be in the 1s orbital
(ground state) or it may be found in some higher-
energy orbital (an excited state). For many
electron atoms, we must know the electron
configuration of the atom is how the electrons
distributed among the various atomic orbitals.
2.13.3 General Rules for Assigning Electrons to
Atomic Orbitals
We can formulate some general rules for
determining the maximum number of electrons
that can be assigned the various subshells and
orbital’s for a given value of n.
 Each shell or principal level of quantum
number n contains n subshells. For example, if
n=2, then there are two subshells (two values
Atomic Structure & Basics of Chemistry
of l) of angular momentum quantum numbers 0 and
1.
 Each subshell of quantum number l contains 2l+1
orbital’s. For example, if l=1, then there are three
p orbital’s.
 No more than two electrons can be placed in each
orbital. Therefore, the maximum number of
electrons is simply twice the number of orbitals
that are employed.
 A quick way to determine the maximum number
of electrons that an atom can have in a principal
level ‘n’ is to use the formula 2n2.
2s  2p  3s  3p  4s  3d  4p  5s  4d  5p  6s 
5d  6p  7s  5f  6d  7p  6f  7d  7f  ………
The following example illustrates the procedure to
calculating the number of electrons in orbital and
labeling electrons with the four quantum numbers.
i.e. What is the maximum number of electrons that
can be present in the principal level for which n=3?
When n=3, then l=0, 1 and 2. The number of orbitals
for each value of l is given by
Value of l Number of orbital’s (2l+1)
0 1
1 3
2 5
The total number of orbital’s is nine. Since each
orbital can accommodate two electrons, the
maximum number of electrons that can reside in the
orbital’s is 2x9 or 18 or using the formula 2n2, we
have n=3 and so 2(3)2 = 18.
2.13.4 Method of writing electronic configuration:
nlx method and Box method
Electronic configuration is expressed by indicating
the principal quantum number and its representative
sub-shell along with number of electrons present in it.
For example, in ground state hydrogen atom must be
in the 1s orbital, so its electron configuration is 1s1.
Page 24
A box for an orbital (square or circular) an arrow 1s2 2s2 2px2 2py2 2pz1
for an electron, the direction of arrow giving F atom
orientation of spin. Example, electron 1s2 2s2 2px2 2py2 2pz2
configuration of carbon is: Ne atom
1s2 2s2 2px1 2py1 2pz

Based on the above rules the electronic configuration

In the ground state electronic configuration of an
atom, the electrons are filled or distributed in
various orbitals in order of their increasing
energies. Thus, an orbital with lowest energy will
be filled first.
The electrons occupy the various orbital’s can be
easily remembered with the help of Moeller’s
diagram, and increasing order of atomic orbitals:
2.14 Pauli Exclusion Principle
In the case of many electron systems we can use
the Pauli Exclusion Principle to determine electron
configurations. It states that no electrons in an
atom can have the same set of four quantum
numbers. If two electrons may occupy in the same
atomic orbital, and these electrons must have
opposite spins. For example we consider the
helium atom, which has two electrons are in
opposite spin written as,
He
2.15 Hund’s Rule
The Hund’s rule states that the most stable
arrangement of electrons in subshell is the one
with the greatest number of parallel spins. For
example, the electron configuration of carbon
(Z=6) is 1s2 2s2 2p2. The orbital diagram
representation of this is:
1s2 2s2 2px1 2py1 2pz
C atom
The fact that carbon atoms are paramagnetic, each
containing two unpaired electrons, is in accord
with Hund’s rule. Similarly the electronic
configuration of nitrogen, oxygen, fluorine and
neon are:
1s2 2s2 2px1 2py1 2pz1
N atom
1s2 2s2 2px2 2py1 2pz1
O atom
of atoms having atomic number up to 30:
Name Symbol Atomic Ele.configuration
Number
Hydrogen H 1 1s1
Helium He 2 1s2
Lithium Li 3 1s22s1
Beryllium Be 4 1s22s2
Boron B 5 1s22s22p1
Carbon C 6 1s22s22p2
Nitrogen N 7 1s22s22p3
and soon……..
2.15.1 Paramagnetism and Diamagnatism
If the two electrons in the 1s orbital of a helium atom
had the same, or parallel spins their net magnetic
fields would reinforce each other. Such an
arrangement would make the helium atom is
paramagnetic one. Paramagnetic substances are those
that are attracted by a magnet.
On the other hand, if the electron spins are paired or
antiparallel to each other, the magnetic effects cancel
out and the atom is diamagnetic. Diamagnetic
substances are slightly repelled by a magnet. Also by
experimentally we confirmed that the helium atom is
diamagnetic in the ground state.
Thus, an odd number of electrons must be
paramagnetic and atoms containing an even number
of electrons may be either diamagnetic or
paramagnetic. If, consider the lithium atom (Z=3)
which has three electrons, third electron has the
parallel spin (unpaired electron) compare with first
electron of this atom and is therefore paramagnetic.
2.15.2 The shielding effect in Many-Electron Atoms
Experimentally we find that the 2s orbital lies at a
lower energy level than the 2p orbital in many-
electron atom. Why? The 2s and 2p orbitals are larger
than the 1s orbital; an electron in either of these

Atomic Structure & Basics of Chemistry Page 25

orbital’s will spend more time away from the
nucleus than an electron in the 1s orbital. Thus, we
can speak a 2s or 2p electron being partly shielded
from the attractive force of the nucleus by the 1s
electrons. The important consequences of the
shielding effect are that it reduces the electrostatic
attraction between protons and the electron in the
2s or 2p orbital.
The manner in which the electron density varies as
we move from the nucleus outward depends on the
type of orbital. The density near the nucleus is
greater for the 2s electron than for the 2p electron.
In other words, a 2s electron spends more time
near the nucleus than a 2p electron. For this
reason, the 2s orbital is said to be penetrating than
the 2p orbital, and it is less shielded by the 1s
electrons.
In fact, for the same principal quantum number n,
the penetrating power decreases as the angular
momentum quantum number l increases as,
s  p  d  f  ………
Since the stability of an electron is determined by
the strength of its attraction to the nucleus, it
follows that a 2s electron will be lower in energy
than a 2p electron. Thus, less energy is required to
remove a 2p electron than a 2s electron because a
2p electron is not held quit as strongly by the
nucleus.
The hydrogen atom has only one electron and
therefore is not in such shielding effect. On the
other hand, the atoms having more than one
electron they can cause the shielding effect by
lower orbital electrons.The beryllium atom has
diamagnetic in nature; because it has four
electrons are arranged as paired configuration (1s2
2s2) with unparallel spins. But in boron atoms has
paramagnetic one, due to boron has five electrons
are arranged as 1s2 2s2 2p1 with unpaired p
electron is represented as:
1s2 2s2 2px1
B atom
Atomic Structure & Basics of Chemistry
2.16 The Building-Up Principle
This process is based on the Aufbau principle (The
German word “Aufbau” means “building up”).
The Aufbau principle states that as protons are added
one to the nucleus to build up the elements, electrons
are similarly added to the atomic orbitals. Through
this process we gain a detailed knowledge of the
ground state electron configuration of the elements.
The electron configuration helps us to understand and
predict the properties of the elements; it also explains
why the periodic table works so well.
The following table gives the ground-state electron
configuration of elements from H (Z=1) through Mt
(Z=109). The electron configurations of all elements
except hydrogen and helium are represented by a
noble gas core, which shows in brackets the noble gas
element that most nearly precedes the element being
considered, followed
by the symbol for the highest filled subshells in the
outermost shells for the elements sodium (Z=11)
through argon (Z=18) follow a pattern similar to
those of lithium (Z=3) through neon (Z=10).
As mentioned already, the 4s subshell is filled before
the 3d subshell in a many electron atom. Thus the
electron configuration of potassium (Z=19) is 1s2 2s2
2p6 3s2 3p6 4s1. We can simplify the electron
configuration of potassium include with argon, [Ar]
4s1. Similarly we can write the electron configuration
of calcium (Z=20) as [Ar] 4s2.
The elements from scantium (Z=21) to copper (Z=29)
are transition metals. Transition metals either have
incompletely filled d subshells or readily give rise to
cations that have incompletely filled d subshells.
Consider the first transition metal series, from
scandium through copper. In this series additional
electrons are placed in the 3d orbitals, according to
Hund’s rule. However, there are two irregularities.
The electron configuration of chromium (Z=24) is
[Ar] 4s13d5 and not [Ar] 4s23d4. Similarly in copper,
whose electron configuration is [Ar] 4s13d10 and not
[Ar] 4s2 3d9. The reason for these irregularities is that
a slightly greater stability is associated with the half-
filled (3d5) and completely filled (3d10) subshells.
Electrons in the same subshell have equal energy but
different spatial distributions. Consequently, their
Page 26
shielding of one another is relatively small, and the
electrons are more strongly attracted by the nucleus
when they have the 3d5 configuration. According to
Hund’s rule, the orbital diagram for Cr is,
3d5 4s1
Cr [Ar]
Thus, Cr has a totally six unpaired electrons.
The orbital diagram for copper is,
3d10 4s1
Cu [Ar]
Again, extra stability is gained in this case by having
the 3d subshell completely filled.
For elements Zn (Z=30) through Kr (Z=36), the 4s
and 4p subshells fill in a straightforward Figure: Classification of groups of element in the
periodic table according to the type of outermost
manner. With rubidium (Z=37), electron begin to subshell being filled with electrons
enter the n=5 energy level.
Exercise.1 An oxygen atom has a total of eight
The sixth period of the periodic table begins with Cs
electrons. Write the four quantum numbers for each
(Z=55) and barium (Z=56), whose electron
of the eight electrons in the ground state.
configuration are [Xe] 6s1 and [Xe] 6s2 respectively.
1s2 2s2 2px2 2py1 2pz1
Next we come to lanthanum (Z=57), in this case
O atom
after filling the 6s orbital we would place
additional electrons in 4f orbitals. In reality, the
Solution:
energies of the 5d and 4f orbitals are very close; in
We start with n=1, so l=0, a subshell corresponding
fact, for lanthanum 4f is slightly higher in energy
to the 1s orbital. This orbital can accommodate a total
than 5d. Thus lanthanum’s electron configuration
of two electrons. Next, n=2 and l =0,1. The l=0
is [Xe] 6s2 5d1 and not [Xe] 6s24f1.Following
subshell contains one 2s orbital, which can
lanthanum are the 14 elements known as the
accomo=modate two electrons. The remaining four
lanthanides or rare earth series [ce(Z=58) to
electrons are placed in the l=1 subshell, which
lutetium (Z=71)]. The rare earth metals have
contain three 2p orbitals. The orbital diagram is,
incompletely filled 4f subshells or readily give rise
The results are summarized in the following table,
to cations that have incompletely filled 4f
----------------------------------------------------------------
subshells. Note that the electron configuration of
Electron n l ml ms Orbital
gadolinium gains extra stability by having a half-
----------------------------------------------------------------
filled subshell (4f7).
1 1 0 0 +1/2 1s
The last row of elements is the actinide series,
2 1 0 0 -1/2 1s
which starts at thorium (Z=90). Most of these
3 2 0 0 +1/2 2s
elements are not found in nature but have been
4 2 0 0 -1/2 2s
synthesized. The following figure (skeleton of
5 2 1 -1 +1/2 2px
periodic table) shows the groups the elements
6 2 1 0 +1/2 2py
according to the type of subshell in which the
7 2 1 1 +1/2 2pz
outermost electrons are placed.
8 2 1 -1 -1/2 2px
----------------------------------------------------------------

Atomic Structure & Basics of Chemistry Page 27

Chapter-III Periodic Properties
The periodic table is the most important concept in
chemistry, both in principle and practice.
3.1 Need to classify elements
At present 118 elements were known. Out of them,
the recently discovered elements are man-made.
With such a large number of elements it is very
difficult to study individually the chemistry of all
these elements and their compounds individually.
To ease out this problem, Scientists searched for a
systematic way to organize their knowledge by
classify the elements.
3.2 Brief history of modern periodic law and
modern periodic table
The periodic law, as we know it today owes, it
development to the Russian chemist, Dmitri
Mendeleev and the German chemist, Lother
Meyer. Working independently, both the chemists
in 1969 proposed that on arranging elements in the
increasing order of their atomic weights.
Similarities appear in physical and chemical
properties at regular intervals.
Lother meyer plotted the physical properties such
as atomic volume, melting point and boiling point
against atomic weight and obtained periodically
repeated pattern, he observed a change in length of
that repeating pattern.
Mendeleev published the periodic law for the first
time, stated as; the properties of the elements are a
periodic function of their atomic weights.
Mendeleev arranged elements in horizontal rows
and vertical columns of a table in order of their
increasing atomic weights in such a way that the
elements with similar properties occupied the
same vertical column or group. Mendeleev’s
system of classifying elements was more elaborate
than that of Lothar Meyer’s. He fully recognized
the significance of periodicity and used broader
range of physical and chemical properties to
classify the elements. In particular, Mendeleev
relied on the similarities in the empirical formulas
and properties of the compounds formed by the
Atomic Structure & Basics of Chemistry
elements. He realized that some of the elements did
not fit in with his scheme of classification if the order
of atomic weight was strictly followed. He ignored
the order of atomic weights, thinking that the atomic
measurements might be incorrect, and placed the
elements with similar properties together. For
example, iodine with lower atomic weight than that
of tellurium (Group VI) was placed in Group VII
along with fluorine, chlorine, bromine because of
similarities in properties (Fig. 3.1). At the same time,
keeping his primary aim of arranging the elements of
similar properties in the same group, he proposed that
some of the elements were still undiscovered and,
therefore, left several gaps in the table. For example,
both gallium and germanium were unknown at the
time
Mendeleev published his Periodic Table. He left the
gap under aluminium and a gap under silicon, and
called these elements Eka-Aluminium and Eka-
Silicon. Mendeleev predicted not only the existence
of gallium and germanium, but also described some
of their general physical properties.
3.2.1 Modern periodic Law
According to Henry’s Mosely, Mendeleev’s periodic
law was modified. This is known as the modern
periodic law and can be stated as: The physical and
chemical properties of the elements are periodic
functions of their atomic numbers.
3.2.2 Modern periodic table ( Long form of
periodic table)
Many different forms of a periodic classification of
the elements have appeared since the 1871 periodic
table by Mendeleev. Some forms emphasize chemical
reactions and valence, whereas others stress the
electronic configuration of elements. A modern
version, the so-called “Long form” of the periodic
table (shown in fig.1), is the most convenient and
widely used.
The horizontal rows (series)of periodic table are
called periods and the vertical columns called groups.
Elements having similar chemical properties, and are
arranged in 1-18 horizontal rows referred to as groups
or families.
Page 28
The inert gases are placed at the extreme right of
the table, reflecting the completion of the s and
p sub-shells of their outer or valence shell.
There are seven horizontal rows, called periods.
The period number corresponds to the highest
principal quantum number (n) of the elements in
the period. The first period contains 2 elements,
the second and third containing 8 elements, the
fourth and fifth periods containing 18 elements,
and the sixth and seventh periods containing
32 elements. This gives a total of 118 elements.
In this form of the periodic table, 14 elements of
both sixth and seventh periods (lanthanides and
actinides, respectively) are placed at the main
body of the periodic table.
Each set of elements appearing in the vertical
column of a periodic table is called a Group and
represents a family of elements that have similar
physical and chemical properties. Group IA is the
alkali family; Group IIA is the alkaline earth
family; Group VIA is the Oxygen family; Group
VIIA is the halogen family. On the left side of the
table ware Group IA elements (except hydrogen),
which are soft metals that undergo similar
chemical reactions. The elements in Group IIA
form similar compounds and are much harder than
their neighbors in Group IA.
The most accurate observations, that all elements
within a particular group have similar physical and
chemical properties. This observation is most
accurate at the extreme sides of the table. All
elements in Group VIIIA are unreactive gases, and
all elements in Group VIIA have similar chemical
properties, although there is a gradual change in
physical properties. For example, fluorine (F) is a
gas while iodine (I) is a solid at room temperature.
Groups with a B designation (IB through VIIB)
and Group VIII are called transition groups. In this
region of the table, exceptions begin to appear
within any group in this region, all the elements
are metals, but their chemical properties may
differ. In some cases, an element may be more
similar to neighbors within its period than it is to
elements in its group. For example, iron (Fe) is
more similar to cobalt (Co) and nickel (Ni) than it
Atomic Structure & Basics of Chemistry
is to ruthenium (Ru) and osmium (Os). Most of these
elements have several charges, and their ions in
solution are colored (ions of all other elements are
colorless).
In this region of the table, the rule of group
similarities loses much of its usefulness. In Group
IVA, for example, carbon (C) is a nonmetal; silicon
(Si) and germanium (Ge) are semi-metals; and tin
(Sn) and lead (Pb) are metals.
The first element in the periodic table, hydrogen,
does not have properties that satisfactorily place it in
any group. Hydrogen has two unique features: (a) the
highest energy shell of a hydrogen atom can hold
only two electrons, in contrast to all others (except
helium) that can hold eight or more; and (b) when
hydrogen loses its electron, the ion formed, H+, is a
bare nucleus. The hydrogen ion is very small in
comparison with a positive ion of any other element,
which must still have some electrons surrounding the
nucleus. Hydrogen can either gain or lose an electron.
It has some properties similar to Group IA elements,
and some similar to Group VIIA elements.
3.3 Class of periodic elements : Based on
electronic configuration
s – Block elements
Group 1 (IA) and group 2 (IIA) which have ns1 and
ns2 outermost electronic configuration belongs to the
s-block elements. They are all reactive metals with
low ionization energies, readily forms +1 and +2 ion
respectively. Because of high reactivity they are
never found pure form in nature.
p - block elements
The p-block elements comprise those belonging to
group 13-18 and these together with the s-block
elements (except noble gases) are called
representative or main group elements . The outer
most electronic configuration varies from ns1 np1 to
ns2 np6 in each period. At the end of each period
placed a noble gas element.
Proceeding the noble gas family are two chemically
important groups of non-metals. They are the
halogens group 17) and the chalcogens (group 16).
The non-metallic character increases as we move
from left to right across a period and metallic
character increases as we go down the group.
Page 29
d – block elements
These are the elements of group 3 - 12 in the
centre of the periodic table. These elements have
the general outer electronic configuration (n-1)d1
to 10
ns0 to 2. They are all metals. Transition metals
form a bridge between the chemically active
metals of s-block elements and the less active
elements of groups 13 - 14.
f - block elements
The two rows of elements at the bottom of the
periodic table, called lanthanides (58Ce – 71Lu) and
actinides (90Th – 103Lr) are characterized by the
outer electronic configuration (n-2)f1 to 14 (n-
0 – 1 2
1) d ns . The last electron added to each
element is filled in f – orbital.
These two series of elements are hence called the
inner transition elements (f-block elements).They
are also metals.
Actinide elements are radioactive. Many of the
actinide elements have been made only in
nanogram or even less by nuclear reactions and
their chemistry is not fully explored. The elements
after uranium are called trans-uranium elements,
3.3.1 s - block elements
The elements in the first two groups of the
periodic table are characterized as “s-block”
elements because of their outer shell having one or
two electrons in an s-orbital.
The elements in group IA (alkali metal) and group
IIA (alkaline earth metals) of the periodic table
have the valence shell configuration of ns1 and ns2
respectively. These group elements are readily
forms +1 and +2 ions respectively. All naturally
occurring compounds of these elements containing
the atoms in those forms (i.e., ionic form) due to
these elements are very reactive, hence they are
not found in natural as elemental state.
A large number of compounds of the group IA and
IIA metals occur naturally (salt, soda, limestone,
etc.). These compounds have been important for
thousands of years and they are useful still.
Moreover lime is still produced enormous quantity
of heat upon heating the limestone.
Atomic Structure & Basics of Chemistry
3.3.1.1 Chemistry of IA group elements (Alkali
metals)
The alkali metals such as Lithium (Li), Sodium (Na),
potassium (K), Rubidium Rb), Caesium (Cs) and
Francium (Fr) are members of group 1 ((IA) of the
periodic table, and each has a ground state valence
electronic configuration as ns1.
Electronic configuration
All the alkali metals have one valence electron, ns1
outside the noble gas core. The loosely hold s-
electron in the valence shell of these elements makes
them the more electropositive metals, M+ ions. Hence
they are never found as free elemental state in nature.
Lithium (3Li) [He] 2s1
Sodium (11Na) [Ne] 3s1
Potassium (19K) [Ar] 4s1
Rubidium (37Rb) [Kr] 5s1
Caesium (55Cs) [Xe] 6s1
Francium (87Fr) [Rn] 7s1
Atomic and ionic Radii
The alkali metal atoms have the largest size than their
corresponding monovalent ions (M+) i.e., Na > Na+;
K > K+.
By increase in atomic number, the atom of IA group
elements becomes larger. Hence the atomic and ionic
radii of alkali metals increase on moving down the
group i.e., they increase in size while going from Li
to Cs.
Ionization energy (ionization potential)
The ionization energy of the alkali metals are
considerably low and decreases down the group from
Li to Cs. This is because the effective nuclear charge
and the outermost electron are very well screened
from the nuclear charge.
As a result of the decrease in ionization energy, the
reactivity of the metals in group IA increase in
progressing down in the group.
The electronegativities of alkali metals range from
0.8 to 1.0, so all are very strong reducing agents that
form binary compounds with most non metallic
elements and even some other metals that have higher
electronegativity.
Because, the IA group metals are such a strong
reducing agents and so reactive, and they are
generally prepared by electrolysis reactions. Na is
Page 30
produced by the electrolysis of molten mixture
that contains NaCl and CaCl2. Li is produced by
the electrolysis of a mixture of LiCl and KCl. The
production of K is carried out by using Na as
reducing agent at 850C under equilibrium
condition. Na(s) + K+  Na+ + K(g)
Negative ions
In most instances, the IA group metals
form +1 ions, but this is not always the case.
Because the low ionization potential of Na, an
unusual situation exists with regard to forming Na+
and Na- ions pair as:
Na(g) + Na(g)  Na+(g) + Na-(g)
We find that it requires 496 KJ/mol to remove an
electron from a sodium atom (the I.P). Adding the
electron to another Na atom, Na(g) + e- Na-(g)
Hydration energy
The hydration energy of alkali metal ions
decreases with increase in ionic sizes.
Li+ > Na+ > K+ > Rb+ > Cs+
Li+ has maximum degree of hydration and for this
reason Lithium salts are mostly hydrates.
e.g. LiCl . 2H2O
Physical properties
 All the alkali metals are silvery white, soft
and light metals.
 Because of the larger size, these elements
have low density which increases down the
group. However K is lighter than Na.
 The melting and boiling points of the alkali
metals are low indicating weak metallic
bonding due to the presence of single
valence electron.
 The alkali metals and their salts impart
characteristic color to an oxidizing flame.
These elements gives a characteristic color
under in flame as,
Li – Crimson red Rb – Red violet
Na – Yellow Cs - Blue
K – Violet
3.3.1.2 Chemistry of IIA group elements
Elements: 4Be, 12Mg, 20Ca, 38Sr, 56Ba & 88Ra
These elements follow alkali metals are known as
alkaline earth metals. The first element Be differs
Atomic Structure & Basics of Chemistry
from the others and shows a diagonal relationship to
Al.
Electronic Configuration
These elements have two electrons in the s -orbital of
the valence shell. Their general electronic
configuration may be represented as [noble gas] ns2.
Like alkali metals, the compounds of these elements
are also predominantly ionic as M2+.
Beryllium - 4Be [He] 2s2
Magnesium - 12Mg [Ne] 3s2
Calcium - 20Ca [Ar] 4s2
Strontium - 38Sr [Kr] 5s2
Barium - 56Ba [Xe] 6s2
Radium - 88Ra [Rn]7s2
Atomic and Ionic Radii
The atomic and ionic radii of the alkaline earth metals
are smaller than those of the corresponding alkali
metals in the same periods. This is due to the
increased nuclear charge in these elements. Within
the group, the atomic and ionic radii increase with
increase in atomic number.
Ionization Energy
The alkaline earth metals have low ionization
energies due to fairly large size of the atoms. Since
the atomic size increases down the group, their
ionization enthalpy decreases. The first
ionization energy of the alkaline earth metals are
higher than those of the corresponding Group 1
metals, e.g., Mg+ > Na+. This is due to their small
size as compared to the corresponding alkali metals.
It is interesting to note that the second ionization
energies of the alkaline earth metals (like Mg2+) are
smaller than those of the corresponding alkali metals.
Hydration Energy
Like alkali metal ions, the hydration energies of
alkaline earth metal ions decrease with increase in
ionic size down the group.
Be2+ > Mg2+ > Ca2+ > Sr2+ > Ba2+
The hydration energies of alkaline earth metal ions
are larger than those of alkali metal ions. Thus,
compounds of alkaline earth metals are more
extensively hydrated than those of alkali metals, e.g.,
MgCl2 and CaCl2 exist as MgCl2.6H2O and CaCl2·
6H2O while NaCl and KCl does not form such
hydrates.
Page 31
Physical Properties
 The alkaline earth metals, in general, are silvery
white, lustrous and relatively soft but harder
than the alkali metals.
 Beryllium and magnesium appear to be
somewhat grayish.
 The melting and boiling points of these metals
are higher than the corresponding alkali metals
due to smaller sizes. The trend is, however, not
systematic. Because of the low ionization
enthalpies, they are strongly electropositive in
nature. The electropositive character increases
down the group from Be to Ba.
 Calcium (Ca), Strontium (Sr) and Barium (Ba)
impart characteristic brick red, crimson and
apple green colors to the flame.
 The electrons in Be and Mg are too strongly
bound to get excited by flame. Hence these
elements do not impart any color to the flame.
 The flame test for Ca, Sr and Ba is helpful their
detection in qualitative analysis ans estimation
by flame photometry.
 The alkaline earth metals like those alkali
metals have high electrical and thermal
conductivities which are typical characteristic
of metals.
3.4 Chemical Properties of s-block elements
3.4.1 IA Group elements (Alkali metals)
Oxides, peroxides, superoxides, suboxides
and ozonides
When the group 1 metals are heated in an excess
of air or in O2, the principal products obtained
depend on the metal:
lithium oxide, Li2O (1),
sodium peroxide, Na2O2 (2), and the
superoxides KO2, RbO2 and CsO2 (3).
4Li + O2  2Li2O oxide formation
2Na + O2  Na2O2 peroxide formation
K + O2  KO2 superoxide formation
The oxides Na2O, K2O, Rb2O and Cs2O can be
obtained impure by using a limited air supply, but
are better prepared by thermal decomposition of
the peroxides or superoxides.
Atomic Structure & Basics of Chemistry
The colors of the oxides vary from white to orange;
Li2O and Na2O form white crystals while K2O is pale
yellow, Rb2O yellow and Cs2O orange.
All the oxides are strong bases, the basicity
increasing from Li2O to Cs2O. Peroxide of lithium
can be obtained by the action of H2O2 on an ethanolic
solution of LiOH, but it decomposes on heating.
Sodium peroxide (widely used as an oxidizing agent)
is manufactured by heating Na metal on Al trays in
air; when pure, Na2O2 is colorless and the faint
yellow color usually observed is due to the presence
of small amounts of NaO2. The superoxides and
peroxides contain the paramagnetic [O2]- and
diamagnetic [O2]2- ions respectively.
Partial oxidation of Rb and Cs at low temperatures
yields suboxides such as Rb6O, Rb9O2, Cs7O and
Cs11O3. The formulae of the suboxides are misleading
in terms of the oxidation states. Each contains M+ and
O2-ions, and, for example, the formula of Rb6O is
better written as (Rb+)6(O2-).4e- indicating the
presence of free electrons.
The alkali metals oxides, peroxides and superoxides
react with water, strongly basic solution are produced
according to equations 4-6. One use of KO2 is in
breathing masks where it absorbs H2O producing O2
for respiration and KOH, which absorbs exhaled CO2
(reaction.7)
M2O + H2O  2MOH (4)
M2O2 + 2H2O  2MOH + H2O2 (5)
2MO2 + 2 H2O  2MOH+ H2O2 + O2 (6)
KOH + CO2  KHCO3 (7)
Sodium peroxide reacts with CO2 to give Na2CO3,
rendering it suitable for use in air purification in
confined spaces (e.g. in submarines); KO2 acts
similarly but more effectively. Although all the group
1 peroxides decompose on heating according to
equation 8, their thermal stabilities depend on cation
size; Li2O2 is the least stable peroxide, while Cs2O2 is
the most stable. The stabilities of the superoxides
(with respect to decomposition to M2O2 and O2)
follow a similar trend.
M2O2(s)  M2O (s) + ½ O2(g) (8)
Ozonides, MO3, containing the paramagnetic, bent
[O3]- ion, are known for all the alkali metals.
Page 32
 The salts KO3, RbO3 and CsO3 can be prepared
from the peroxides or superoxides by reaction with
ozone, but this method fails, or gives low yields,
for LiO3 and NaO3. These ozonides have recently
been prepared in liquid ammonia by the
interaction of CsO3 with an ion-exchange resin
loaded with either Li+ or Na+ ions. The ozonides
are violently explosive.
Hydroxides
When the oxygen compounds of group IA
and IIA metals react with water, strongly basic
solutions are produced regardless of whether an
oxide, peroxide, or superoxide is involved.
Li2O + H2O  2LiOH (9)
Na2O2 + 2H2O  2NaOH + H2O2 (10)
2KO2 + 2 H2O  2KOH+ H2O2 + O2 (11)
Sodium hydroxide, sometimes referred to as
caustic soda or simply caustic, is produced in
enormous quantities by the electrolysis of an
aqueous solution of sodium chloride.
2 NaCl + 2 H2O + 2NaOH + Cl2 + H2
The fact that this is also the reaction used to
prepare chlorine makes it especially important.
However, sodium hydroxide will react with
chlorine as shown in the equation
2OH- + Cl2  OCl- + Cl- + H2O
Halides
Sodium chloride is found in salt beds, salt
brines, and sea water throughout the world, and it
is also mined is some locations. Consequently,
sodium chloride is the source of numerous other
sodium compounds. A large portion of the sodium
chloride utilized is consumed in the production of
sodium hydroxide. The production of sodium
metal involves the electrolysis of the molten
chloride, usually in the form of a eutectic mixture
with calcium chloride. Sodium carbonate is an
important material that is used in many ways such
as making glass. It was formerly produced from
NaCl by means of the Solvay process, in which the
overall reaction is
NaCl(aq)+CO2(g)+H2O(l)+NH3(aq)NaHCO3(s)+NH4Cl(aq)
The solid compound decomposes when heatedas
follows: NaHCO3(s)  Na2CO3(s) + H2O(g)
Atomic Structure & Basics of Chemistry
3.5 p-block elements
3.5.1 Introduction
p-block elements are placed in groups 13 to 18 of the
periodic table. Their valence shell electronic
configuration is ns2np1–6
The properties of p-block elements are greatly
influenced by atomic sizes, ionization energy,
electron affinity and electronegativity.
Groups IIIA to 0 constitute the p-block in the
Periodic Table. The atoms of all the elements in these
groups have, besides two electrons in the s-orbitals,
one or more valence electrons in the p-orbitals.
Unlike the s-block elements, which show similar
chemistry and regular variations in properties,
elements of p-block, except the halogens, show more
dissimilarities in their properties. In general, p-block
elements are mainly non-metals. Their first ionization
energies are high because their atoms have large
effective nuclear charge. Therefore, they have little
tendency to form positive ions and are more
electronegative than s-block elements. When forming
compounds with metals, p-block elements tend to
form negative ions by gaining electrons to attain the
octet configuration. However, they tend to form
covalent bonds by sharing electrons when combining
with non-metals.
3.5.2 General aspects and trends in the p-block
elements
 Most p-block elements can adopt more than one
oxidation state, they normally vary in units of 2.
 Group 13 compounds act as Lewis acids, as can
compounds of Group 14 and 15 if they contain
elements of the third period or lower.
 Group 15, 16, and 17 compounds have lone pairs,
so they can act as Lewis bases, but the strength of
the base depends on the type of orbital the electron
pair is in.
Trends across the periods on p-block
 The atomic radius decreases, this is because of the
addition of electrons takes place in the same
valence shell and are subjected to an increased pull
of the nuclear charge at each step.
The valence electrons are pulled closer to the
nucleus. This result in decreasing the atomic size
Page 33
 from as we move left to the right in periodic
elements.
 Atomic size decreases and nuclear charge
increases, both the factors lead to an increase
in the force of attraction between the nucleus
and the valence shell electrons. Thus
ionization energy increases as we move from
left to right in period of elements. It reaches
maximum value at neon which has ns2np6
electronic configuration (i.e stable octet) and
that is why noble gases have highest ionization
energies.
 The electronegativity increases across a period.
As the effective nuclear charge increases along
a period the pull of the nucleus of an electron
of the other atom increases strongly.
 The metallic character of an element decreases
from left to right across a period of the p block
due to increasing ionization enthalpies.
 The maximum oxidation state increases across
a period, though expansion of the octet is not
possible for the second period elements.
 The ionic character of the oxides and halides
decreases across each period.
 The acidic character of the oxides increases
across each period.
Trends down the groups on p block
 The atomic size increases, this is due to new
electronic shell which is added when we move
from one element to the next in group.
 The additional increase in the energy level
more than compensates for the added nuclear
charge.
 The ionization energy decreases due to
increasing size of the atom down the group of
elements therefore, the force of attraction for
the nucleus and outermost valence shell
electron decreases. Thus ionization energy is
lowered.
 Electronegativity decreases down a group. As
the atomic size increases, the bond electrons
are further from the nucleus and thus the force
of attraction between the nucleus of an atom and the
bond electrons decreases.
Atomic Structure & Basics of Chemistry
 The metallic character of an element decreases
down each group of the Periodic Table due to
decreasing ionization enthalpies.
 The oxidation state increases in importance down
Groups 13–15. This is known as the inert pair
effect.
Inert pair effect: The tendency of ns2 electron
pair to participate in bond formation decreases
with the increase in atomic size. Within a group
the higher oxidation state becomes less stable with
respect to the lower oxidation state as the atomic
number increases. This trend is called ‘inert pair
effect’. In other words, the energy required to
unpair the electrons is more than energy released
in the formation of two additional bonds.
 Bond energies generally decrease down each
group, but when the atoms have lone pairs the
bond enthalpy is low for the second period
element due to high electron–electron repulsion.
 The ionic character of the oxides and halides
increases down the groups and the oxides become
more basic.
 pi bonding becomes less important going down
each group.
3.6 Groups in p-block elements
1. Boron family: Elements of group 13 – boron (B),
aluminium (Al), gallium (Ga), indium (In) and
thallium (Tl) belong to configuration is ns2np1.
2. Carbon family: Elements of group 14 – carbon
(C), silicon (Si), germanium (Ge), tin (Sn) and
lead (Pb) belong to configuration is ns2np2.
3. Nitrogen family: The elements of group 15 –
nitrogen (N), phosphorus (P), arsenic (As),
antimony (Sb) and bismuth (Bi) belong to
configuration is ns2 np3.
4. Oxygen family: Group 16 consists of five
elements – oxygen (O), sulphur (S), selenium (Se),
tellurium (Te) and polonium (Po). Their general
electronic configuration is ns2np4.
5. Halogen family: Group 17 elements, fluorine (F),
chlorine (Cl), bromine (Br), iodine (I) and astatine
(At), belong to halogen family. Their general
electronic configuration is ns2 np5.
6. Group 18 elements: Helium (He), neon (Ne),
argon (Ar), krypton (Kr), xenon (Xe), and radon
Page 34
(Rn) are Group 18 elements. They are also called
noble gases. Their general electronic configuration
is ns2 np6. Except helium which has electronic
configuration 1s2 other elements are called noble
gases because they show very low chemical
reactivity.
3.6.1 Boron Family
Boron is a non-metal, whereas the other Group 13
elements are metals. The most common oxidation
state for Group 13 is +3, but the +1 oxidation state
becomes increasingly important going down the
group.
1. Electronic Configuration
The valence shell electronic configuration of
these elements is ns2np1. Boron and aluminium
have noble gas core, gallium and indium have
noble gas plus 10 d-electrons, and thallium has
noble gas 14 f-electrons plus 10 d-electrons cores,
Thus the electronic structures of these elements
are more complex than for the IA and IIA group
elements. This difference in electronic structure
affects the other properties and consequently the
chemistry of all the elements of this group.
2. Atomic radii
On moving down the group, for each successive
member one extra shell of electrons is added and,
therefore, atomic radius is expected to increase.
However, a deviation can be seen. Atomic radius
of Ge is less than that of Al. This can be
understand by the presence of additional 10 d-
electrons offer poor screening (shielding) effect
for the valence electrons from the increased
nuclear charge in gallium. Consequently, the
atomic radius of gallium (135 pm) is less than that
of aluminium (143 pm). i.e., Al > Ga ; Ga > In; In
> Tl.
3. Ionization Energy
The ionization energy values as expected from the
general trends do not decrease smoothly down the
group. The decrease from B to Al is associated
with increase in size. The observed discontinuity
in the ionization energy values between Al and
Ga, and between In and Aluminium and gallium
are
Atomic Structure & Basics of Chemistry
amphoteric, but indium and thallium show more
metallic character and do not dissolve in alkalis. This
group of elements shows a wide variation in
properties. Boron is typical non-metal, aluminium is a
metal but shows many chemical similarities of boron,
and gallium, Tl are due to inability of d- and f-
electrons, which have low screening effect, causes
higher nuclear charge.
4. Electronegativity
Down the group, electronegativity first decreases
from B to Al and then increases marginally. This is
because of the discrepancies in atomic size of the
elements.
5. Chemical properties
Due to smaller size of boron, ionization energies is
very high and this prevents it to form +3 ions and
forces it to form only covalent compounds.
Ionization energies of Al considerably lower, and is
there a form able Al3+ ion. In fact, Al is a highly
electropositive metal.
The relative stability of +1 oxidation state increases
for heavier elements: Al < Ga < In < Tl.
Like BF3 molecule called electron deficient molecule
sharing their electrons with others achieve stable
electronic configuration and thus, behave as Lewis
acids.
BCl3 easily accept lone pair of electrons from NH3, to
fom BCl3’NH3.
AlCl3 achieves stability by forming a dimer.
6. Diagonal relationship of boron with silicon
1. Both are non-metals, bad conductor of electricity,
have high melting points and low densities.
2. They exist in two allotropic forms viz. amorphous
and crystalline. Their crystalline forms are harder
than amorphous forms.
3. They do not form such an oxy-salt in which boron
and silicon may present in cationic form.
4. Their oxides (B2O3 and SiO2) are acidic in nature,
dissolve in alkalis to form borate and silicate.
B2O3 + 6 NaOH  2Na3BiO3 + 3H2O
SiO2 + 2 NaOH  Na2SiO3 + H2O
They can reduce by Mg to B and Si.
Page 35
 B2O3 + 3 Mg  2B + 3MgO
SiO2 + 2Mg  Si + 2MgO
5. Both form a number of covalent hydrides which
have similar properties e.g.
Boron: Diborane (B2H6), Tetraborane (B4H10)
etc.
Silicon: Silane (SiH4), Disilane (Si2H6) etc.
6. Both burn in halogens to form halides which
are co-valent in nature. Fluorides of both are
hydrolysed by water forming acids.
4BF3 + 2H2O  HBO2 + 3HB4
Meta boric Hydrofluo
acid boric acid
3SiF4 + 3H2O  H2SiO3 + 2H2SiF6
Silicic acid Hydrofluo
silicic acid
The chlorides of both (BCl3 and SiCl4) are liquids,
fume in moist air and are hydrolyzed by water.
BCl3 + 3H2O  H3BO3 + 3HCl
SiCl4 + 4H2O  H4SiO4 + 4HCl
7. The carbides of both the elements (B4C and
SiC) are very hard substances and used as
abrasive.
8. Both dissolve in alkalis forming borate and
silicate.
2B + 6NaOH  2Na3BO3 + 3H2
Si + 2NaOH + H2O  Na2SiO3 + 2H2
9. Both form complexes e.g. hydrofluoboric acid,
HBF4 and hydrofluosilicic acid, H2SiF6
Anomalous Behavior of Boron
Boron and its compounds differ from other family
members in the following properties.
1. Boron is non-metallic in nature while other
members are either metalloids or metals.
2. Melting point of boron (23000C) is highest in
comparison with the melting point of other
family members.
3. It has lowest value for atomic radius and
highest value of ionization potential.
Atomic Structure & Basics of Chemistry
4. Boron forms covalent compounds only, while
other family members form electrovalent
compound also.
5. Boron does not form hydrated ions of the type
[M(H2O)6]+.
6. Oxides and hydroxides of boron are acidic, those
those aluminimum and gallium are amphoteric
while those of indium and thallium are basic.
7. Boron forms electron deficient compounds in
which it acts as electron acceptors (Lewis acid)
while the other of family members do not show
this property.
3.6.2 Elements of group IV A (Carbon family)
The IVA sub group of the periodic table contains five
elements viz. Carbon (C), Silicon (Si), Germanium
(Ge), Tin (Sn) and Lead (Pb). They are p-block
elements and also known as Carbon family.
3.6.2.1 Similarities and gradation in physical
properties
1. Electronic configuration
The electronic configurations of these elements are
as follows:
2 2
6C = [He] 2s 2p
2 2
14Si = [Ne] 3s 3p
10 2 2
32Ge = [Ar] 3d 4s 4p
10 2 2
50Sn = [Kr] 4d 5s 5p
14 10 2 2
82Pb = [Xe] 4f 5d 6s 6p
It appears that these elements have ns2np2
electrons in their valence shell.
2. Metallic character: The metallic character
increases as we move down the group e.g. carbon
and silicon are non-metals, germanium is a
metalloid while tin and lead is metals.
3. Atomic radius: Increases gradually from carbon
to lead, even for poor ability to screening the
nucleus from the valence electrons due to metallic
nature increases down the group.
4. Ionization Energy: The value of ionization
energy decreases gradually on moving from C to
Sn. The I.E for Pb is slightly greater due to poor
screening (shielding) effect of f-orbitals of
metallic lead.
Page 36
5. Conductivity:Carbon (diamond) bad conductor, silicon and germanium are semi-conductors
while tin and lead are good conductors.
6. Oxidation states: Carbon and silicon have +4
oxidation state, while the remaining elements of this group show +2 and +4 oxidation states.
The stability of +4 oxidation state decreases while that of +2 oxidation state increases.
7. Allotropy: All these elements (except Pb) show allotropy. Carbon exists in two important
crystalline forms – diamond and graphite.
Silicon exists in crystalline and amorphous
forms while germanium exists in two crystalline forms. Tin exists in three solid forms:
Grey (α) tin  white () tin  brittle tin
8. Diagonal relationship between carbon (C) and phosphorous (P)
Carbon (IVA) is diagonally related to phosphorous (VA) in the following respect:
1. Both are reactive non-metallic elements.
2. Both the elements show allotropy
3. Carbon and phosphorous form covalent
compounds.
4. Oxides of both are acidic in nature.
5. Oxy-acids and their salts of both the
elements are stable.
6. Hydrides, nitrides and carbides are covalent.
7. Both have tendency of catenation.

3.6.3 Elements of VA (15th) group (Nitrogen family)

The VA sub group of the periodic table contains five elements viz. nitrogen (N), phosphorous
(P), arsenic (As), antimony (Sb) and bismuth (Bi). They are also known as nitrogen family.
3.6.3.1 Similarities & gradation in physical properties
1. Electronic configuration (valence
electrons ns2np3)
2 3
7N = [He] 2s 2p
2 3
15P = [Ne] 3s 3p
10 2 3
33As= [Ar] 3d 4s 4p
10 2 3
51Sb= [Kr] 4d 5s 5p
14 10 2 3
83Bi = [Xe] 4f 5d 6s 6p

 The first two elements of this group, nitrogen and phosphorous are non-metals, the next two,
arsenic and antimony are metalloids whereas the last element, bismuth is a metal.
 All the elements of this group have five electrons in their valence shells as ns2np3.
 Atomic radii is expected, increase with increase in atomic number. N<P<As<Sb<Bi

Atomic Structure & Basics of Chemistry Page 37

 The first ionization energy decreases regularly down the group due to increase in size of
atoms. N>P>As>Sb>Bi
 The ionization energies of this group are much higher than those of corresponding elements of
group 14.
N>C; P>Si; As>Ge; Sb>Sn; Bi>Pb
This is due to the increase in nuclear charge and extra stable configuration (i.e. half filled p-
orbitals) of the elements of this group.
 Electropositive (or metallic) character increase on going down the group due to decrease in
ionization energies.
 The value for electronegativity also decreases gradually with increase in atomic number.

2. Oxidation states
(a) Positive Oxidation States: The outer shell electronic configuration of these elements ns2np3
hence they can have oxidation states of +3 and +5. In addition to +3 and +5 states, nitrogen
also shows +1, +2 and +4 states.
(b) Negative oxidation States: All these elements (except Bi) show -3 oxidation state e.g. in
NH3 molecule, nitrogen shows -3 oxidation state. Nitrogen also shows -1 and -2 oxidation
state in NH2OH and N2H4

3.6.4 Oxygen family (Elements of group VIA)

The VIA sub group of the periodic table contains five elements viz. Oxygen (O), Sulphur (S),
Selenium (Se), Tellurium (Te) and Polonium (Po).
1. Electronic configuration: The electronic configurations of these elements are given below:
2 4
8O = [He] 2s 2p
2 4
16S = [Ne] 3s 3p
10 2 4
34Se = [Ar] 3d 4s 4p
10 2 4
52Te = [Kr] 4d 5s 5p
14 10 2 4
84Po = [Xe] 4f 5d 6s 6p

From the above electronic configurations it is clear that these elements have ns2np4 electrons in
their outermost shell.
2. Similarities and Gradation in Physical properties
 Metallic character increases gradually from oxygen to polonium. Oxygen and sulphur are
non-metals; selenium and tellurium are metalloids while the polonium is a radioactive metal.
 Oxygen has very high ionization energy than other elements of this group, i.e. the decrease
ionization energy from oxygen to polonium is due to increase in size of the atoms and greater
metallic character down the group.

Atomic Structure & Basics of Chemistry Page 38

 Ionization energies of this group elements have lower than the corresponding 15th group
elements due to incompletely filled electronic configurations. i.e. O<N; S<P; Se<As; Te<Sb
and Po<Bi.
 The value of electronegativity decreases gradually down the group due to decrease in
effective nuclear charge.
 Oxidation states: These group elements have ns2np4 electrons in their outer shell, and they
can attain noble gas configuration either by gaining or by sharing two electrons. Thus, these
elements show two types of oxidation states.
(a) Negative oxidation states: Oxygen gives -2 oxid. states (except OF2).

3.7 IIA Group elements (Alkaline earth metals)

1. Oxides and hydroxides
Beryllium oxide, BeO, is formed by ignition of Be or its compounds in O2. It is an insoluble
white solid. The oxides of other group.2 metals are usually prepared by thermal decomposition
of the corresponding carbonate. MCO3 MO + CO2
The oxides of IIA group metal are ionic, so they react with water to produce the hydroxides.
MO + H2O  M(OH)2
However, beryllium oxide is quite different, and it exhibits amphoteric behavior.
Be (OH)2 + 2 OH- Be(OH)42-
Be (OH)2 + 2 H+  Be2+ + 2H2O
Magnesium hydroxide is a week, almost insoluble base that is used as a suspension known as
“milk of magnesia’ that is a common antacid. Calcium hydroxide is produced in enormous
quantities by the decomposition of limestone.
CaCO3  CaO + CO2
This is followed by the reaction of CaO (lime) with water. CaO + H2O  Ca(OH)2
Calcium hydroxide is known as hydrated lime or slaked lime, and it is used extensively in
some applications because it is less expensive than NaOH or KOH. It reacts with CO2 to form
CaCO3, which binds particles of sand and gravel together in mortar and cement.

Atomic Structure & Basics of Chemistry Page 39

Chapter - IV Molecular Geometry

4.1 Molecular Geometry

Molecular geometry is the three dimensional arrangement of atoms in a molecule. Molecules
geometry affects its physical and chemical properties. The geometry of the molecule ultimately
assumes minimizes the repulsion. This approach to the study of molecular geometry is called the
valence-shell electron pair repulsion (VSEPR) model. With this model, we can predict the
geometry of molecules (and ions) in a systematic way. For this purpose, it is convenient to divide
into two categories, according to whether or not the central atom has lone pairs.
1. Molecules in which the central atom has no lone pairs
For our convenient we will consider a molecule that contains atoms of only two elements of
electron pairs around the central atom A. The following table shows five possible arrangements
of electron pairs around the central atom A. Molecules in which the central atom has no lone
pairs have one of these five arrangements of bonding pairs. Let us take a close look at the
geometry of molecules with the formula AB2, AB3, AB4, AB5, and AB6.
Table.1 Geometry of simple molecules and ions in which the central atom has no lone pairs.
------------------------------------------------------------------------------------------------------------
Number of Type of Arrangement Molecular Examples
Electron pairs molecule electron pairs Geometry
------------------------------------------------------------------------------------------------------------
2 AB2 : ------ A ----- : B-----A------A BeCl2, HgCl2, BeF2,

3 AB3 BF3

4 AB4 CH4, NH4+

5 AB5 PCl5

6 AB6 SF6

Atomic Structure & Basics of Chemistry Page 40

2. Molecules in which the central atom has one or more lone pairs
Determination the geometry of a molecule is more complicated if the central atom has
both lone pairs and bonding pairs. In general, according to the VSEPR model, the repulsive
forces decrease in the following order:
Lone-pair vs lone-pair repulsion  lone-pair vs bonding pair repulsion  bonding pair vs
bonding pair repulsion
According to this,
 We designate molecules with lone pairs as ABxEy, where A is the central atom, B is a
surrounding atom and E is a lone pair on A. Both x and y are integers; x= 2,3,….. and
y=1,2,3,…….
 The simplest such molecule would be a triatomic molecule with one lone pair on the
central atom and the formula is AB2E. The following table shows, the geometry of
molecules whether the presence of lone pairs on the central atom.
Table.2 Geometry of molecules & ions in which the central atom has one or more lone pairs
---------------------------------------------------------------------------------------------------------------------
Class of Total no. of No. of bond No. of lone Geometry
-
molecule e pairs pairs pairs
---------------------------------------------------------------------------------------------------------------------
AB2E 3 2 1 Bent

AB3E 4 3 1 Trigonal
Pyramidal
AB2E2 4 2 2 Bent

AB4E 5 4 1 Distorted
Tetrahedron
AB3E2 5 3 2 T-shaped

AB2E3 5 2 3 Linear

AB5E 6 5 1 Square
Pyramidal
AB4E2 6 4 2 Square planar

---------------------------------------------------------------------------------------------------------------------

Atomic Structure & Basics of Chemistry Page 41

4.2 Dipole moments
The HF is a covalent molecule with a polar bond. There is a shift of electron density from H to F
because the F atom is more electronegative than H atom. The shift of electron density is
symbolized as a crossed arrow () above the Lewis structure to indicate the direction of the
shift. For example H – F: + -
The charge separation can be represented as, H – F
Where  (delta) denotes a partial charge
 The polarity of a bond measured as dipole moment () by the product of the charge (Q)
and the distance r between the charges,  = Q x r
 The  is always positive, usually expressed in debye units (D). The conversion factor is
1D=3.336 x 10-30 C.m. Here, C is coulomb and m is meter.
 Diatomic molecules containing atoms of different elements (HCl, CO and NO) have
dipole moments and are called polar molecules.
 Diatomic molecules containing atoms of the same element (H2, O2 and F2) are non polar
molecules because they do not have dipole moments.
 Carbon dioxide (CO2) is a triatomic molecule, so its geometry is either linear or bent;
O=C=O C
Linear molecule Resultant dipole moment
(no dipole moment) (has a dipole moment)
 Experimentally it is found that CO2 has no dipole moment (DM). Therefore, we conclude
that the CO2 molecule is linear.
Let us consider the NH3 and NF3 molecule
In both cases the central N atom has a lone pair, whose charge density is away from
the N atom. We know that N is more electronegative than H and F is more electronegative
than N. For this reason, the shift of electron density in NH3 is toward N and so contributes a
larger dipole moment (DM), where as the NF bond moment are directed away from N atom
and so the contribution of the lone pair to the dipole moment. Thus, the resultant DM in NH3
is larger than that in NF3.
 DM’s can be used to distinguish between molecules that have the same formula but
different structures (called isomers). For example, the following molecules both have the
same molecular formula (C2H2Cl2), but different molecular structures:
Because cis-dichloro ethylene is a polar molecule but trans-dichloro ethylene is not, they
can readily be distinguished by a dipole moment measurement.

Atomic Structure & Basics of Chemistry Page 42

 4.3 Valence Bond Theory
 The VSEPR model provides a relatively simple and straight forward method for
predicting the geometry of molecules.
 For a more complete explanation of a chemical bond, we look to quantum mechanics.
Infact, the quantum mechanical study of chemical bonding also provides a means for
understanding the molecular geometry.
 Two quantum mechanical theories are used to describe covalent bond formation and the
electronic structure of molecules, such as valence bond (VB) theory and molecular orbital
(MO) theory.
 We discuss the VB theory by considering the formation of H2 molecule from two H
atoms. H – H  H2 molecule
(atoms)
By overlap of two 1s atomic orbitals, H-H bond formed. It means, two atomic orbitals
share a common region in space. i.e.
 In beginning the potential energy of two H atoms is zero. As the atoms approach each
other, each electron is attracted by the nucleus of the other atom. So, their potential
energy decreases (it becomes negative) as the atoms approach each other, shown in figure
(as follows),
 This trend continues until the potential energy reaches a minimum value, which has the
lowest potential energy, it is most stable. This condition corresponds to substantial
overlap of the 1s orbital and the formation of a stable H2 molecule.
 Valence bond theory states that a stable molecule forms from reacting atoms when the
potential energy of the system has decreased to a minimum.

Atomic Structure & Basics of Chemistry Page 43

Chapter. V Chemical Reactions

5.1 Chemical Equations

Process in which, a substance is changed into one or more new substances. To communicate with
one another about chemical reactions, chemists have devised a standard way to represent those
using chemical equations. In chemical equation, chemical symbols are used to show what
happens during a chemical reaction.
5.1.1 Writing chemical equations
Consider, when hydrogen gas (H2) burns in air (O2) to form water (H2O). This reaction can be
represented by the chemical equation. H2 + O2 H2O
Where, the plus sign means “reacts with” and the arrow means, “to yield”. Thus, this symbolic
expression can be read, “molecular hydrogen reacts with molecular oxygen to yield water”. The
above said reaction is not complete. So, we can balance the equation by balancing the
appropriate coefficient in front of H2 and H2O as, 2H2 + O2 2H2O
This balanced chemical equation shows that “two hydrogen molecules can combine or react with
one oxygen molecule to form two water molecules”, which is can also be read as, “2 moles of
hydrogen molecules react with 1 mole of oxygen molecules to produce 2 moles of water
molecules”. In terms of mass the equation is expressed as 4.04g of H2 react with 32g of O2 to
give 36.04g of H2O.
In the above equation, H2 and O2 are reactants, which are starting materials in a chemical
reaction. Water is the product which is the substance formed as a result of a chemical reaction. In
a chemical equation the reactants are written on the left and the products on the right of the
arrow. Reactants Products
Provide the additional information, chemists often indicate the physical states of the reactants
and products by using the letters g, l and s, denote gas, liquid and solid respectively.
2CO (g) + O2 (g) 2CO2 (g)
2HgO (s) Hg(l) + O2 (g)
The states of the reactants and products are especially useful in the laboratory. For example,
when potassium bromide (KBr) and silver nitrate (AgNO3) react in an aqueous environment, a
solid, silver bromide (AgBr) is formed. This reaction can be represented by the equation,
KBr (aq) + AgNO3 (aq) KNO3 (aq) + AgBr (s)
5.2 The mole concept
A mole is defined as the amount of substance that contains as many elementary entities (atoms,
molecules or other particles) in exactly 12g of carbon-12.
 Avogadro’s number can also determine the actual number of atoms experimentally. Thus, one
mole of carbon-12 contains 6.023x1023 atoms.
 The molar mass of a compound (in grams) is numerically equal to its molecular mass (in
amu). For example the molecular mass of water is 18.02amu so, its molar mass is 18.02g.
Thus, 1 mole of water weights 18.02g contains 6.023x1023 H2O molecule.

Atomic Structure & Basics of Chemistry Page 44

The following examples show to calculate the numbers of moles and individual atoms in a given
quantity of a compound as,
Example.1 How many moles of CHCl3 are in 198g of CHCl3?
Solution: molar mass of CHCl3 = 119.4g
1 mol of CHCl3 = 119.4g of CHCl3
so, 198g CHCl3 = ? mol of CHCl3
1 mol CHCl3
-------------------- x 198g CHCl3 = 1.66 mol CHCl3
119.4g CHCl3
Example.2 How many moles of He atoms are in 6.46g of He?
Solution: molar mass of He = 4.003g
1 mol of CHCl3 = 4.003g of He
so, 6.46g of He = ? mol of He
1 mol He
-------------------- x 6.46g He = 1.61 mol CHCl
4.003g He
Example.3 How many grams of Na2CO3 are present in 3.65mol of Na2CO3.
Solution: Molar mass of Na2CO3 = 58.47 g
1 mol Na2CO3 = 58.47g Na2CO3
3.65 mol Na2CO3 = ?
58.47g Na2CO3
------------------- x 3.65 mol Na2CO3 = 213.42g Na2CO3
1 mol Na2CO3
Example.4 Methanol burns in air according to the equation,
2CH3OH + 3O2 2CO2 + 4 H2O
If 209g of methanol are used up in a combustion process, what is the mass of H2O
produced.
Solution: molar mass of CH3OH = 32g
molar mass of H2O = 18g
32g of CH3OH produced 2 mol of H2O ---36g H2O
209g of CH3OH ---------- ?
36/32 x 209g CH3OH = 235.125g of H2O
Example.5 How many hydrogen atoms are present in 25.6g of urea, [(NH2)2CO]
1 mol of urea = 60.06g of urea
25.6g of urea = ? g of H atoms
1 mol urea 6.023x1023 molecules urea 4 H atoms
Number of H atoms = -------------- x 25.6g urea x ---------------------------------- x --------------------
60.06g urea 1 mol urea 1molecule urea

= 1.03x1024H atoms
Atomic Structure & Basics of Chemistry Page 45
Example.6 How many Cl atoms are present in 122g of MgCl
Solution: Molar mass of MgCl = 59.76g
1 mol MgCl 6.023x1023 molecules urea 1 Cl atom
Number of H atoms = -------------- x 122g MgCl x ---------------------------------- x ------------------
59.76g MgCl 1 mol MgCl 1molecule MgCl
= 1.23x1024 Cl atoms
5.3 Balancing of the chemical equations
In general, we balance chemical equations by the following steps,
 Identify all reactants and products and write their correct formulas on each sides of the
equation.
 Start to balance the equation by trying different coefficients on both sides of the equation. We
can change the coefficients but not the subscripts.
 Look the formulas containing the elements must have the same coefficient on each side, there
is no need to adjust the coefficient of these element at this point. Next, look for elements that
appear only once on each side of the equation but in unequal numbers of atoms, balance these
elements. Finally, balance the elements that appear in two or more formulas on the same side
of the equation.
 Check your balanced equation to be sure that have the same total number of each type of
atoms on both sides of the equation.
Let us consider, small amounts of oxygen gas can be prepared by heating potassium chlorate
(KClO3). The products are O2 and KCl. So, their respective equation is,
KClO3 KCl + O2
All these elements appear only once on each side of the equation, but only for K and Cl have
equal number of atoms on both sides. Thus, KClO3 and KCl must have the same coefficient. The
next step is to make the number of oxygen atoms the same on both sides of equation. We can
balance the O atoms by placing a 2 in front of KClO3 and a 3 in front of O2. We get,
2 KClO3 KCl + 3O2

Finally, we balance the K and Cl atoms by placing a 2 in front of KCl. So,

2KClO3 2KCl + 3O2
 At a final check, we can draw up balance the reactants and products,
Reactants Products
K (2) K (2)
Cl (2) Cl (2)
O (6) O (6)
Example.2 Balance the following chemical equation, C2H6 + O2 CO2 + H2O
Solution: Look at the coefficients of C,H and O on both side and change the coefficients of those
and get the balanced equation as,
C2H6 + 7/2 O2 2CO2 + 3H2O

Atomic Structure & Basics of Chemistry Page 46

However, we normally prefer to express the coefficients as whole numbers rather than fraction.
Therefore, we multiply the entire equation by 2 to convert 7/2 to, and we get fully balanced
equation as,
2 C2H6 + 7O2 4CO2 + 6H2O
We follow the above said method of balancing the chemical equation, will do the
balancing of some important examples of chemical reaction equations as,
Balance the following chemical equations.
1. Al + O2 Al2O3
Al and O appear only once on each side with unequal numbers,
2Al + 3/2O2 Al2O3
As like earlier case, we multiply the entire equation by 2, so,
4Al + 3O2 2Al2O3
2. Li + H2O LiOH + H2
Balanced equation for this, 2Li + 2H2O 2LiOH + H2
3. HCl + CaCO3 CaCl2 + H2O + CO2
Balanced equation for this, 2HCl + CaCO3 CaCl2 + H2O + CO2
4. NaOH + H2SO4 Na2SO4 + H2O
Balanced equation for this, 2NaOH + H2SO4 Na2SO4 + 2H2O
5. NaHCO3 Na2CO3 + H2O + CO2
Balanced equation for this, 2NaHCO3 Na2CO3 + H2O + CO2
6. Fe2O3 + CO Fe + CO2
Balanced equation for this, Fe2O3 + 3CO 2Fe + 3CO2

5.4 Amount of reactants and products

Stoichiometry is the quantitative study of reactants and products in a chemical reaction. Whether
the units given for reactants (or products) are moles, grams, liters or some other units, we use
moles to calculate the amount of product formed in a reaction. This approach is called the mole
method, which means simply that the stoichiometric coefficients in a chemical equation can be
interpreted as the number of moles of each substance. For example the Haber synthesis of
ammonia production as,
N2 + 3H2 2NH3
We read this equation as “1 mole of N2 gas combine with 3 moles of hydrogen gas to
form 2 moles of NH3.
Based on the mole method 3 types of stoichiometric calculations are followed as,
 Moles of reactant moles of product
 Mass of reactant moles of reactant moles of product
 Mass of reactant moles of reactant moles of product mass of product

Atomic Structure & Basics of Chemistry Page 47

The mole method consist the following steps,
 Write correct formulas for all reactants and products and balance the resulting equation.
 Convert the known quantities of given substances (reactants) into moles
 Use the coefficients in the balanced equation to calculate the number of moles of unknown
quantities (products)
 Convert the unknown quantities to whatever units are required (typically grams)
 Check that your answer is reasonable in physical terms.
In stoichiometry we use the symbol , which means “stoichiometrically equivalent to” or simply
“equivalent to”. In the case of balanced equation for the ammonia synthesis, 1 mol of N2 reacts
with 3 mol of hydrogen. So, 1 mole of N2 is equivalent to 3 moles of H2 as,
1 mol of N2  3 mol of H2
We can write the unit factor as,
1 mol of N2 3 mol of H2
-------------- = -------------------
3 mol of H2 1 mol of N2
The following examples illustrate the use of the five-step method in solving some typical
stoichiometry problems.
Example.1 All alkali metals react with water to produce hydrogen gas and the corresponding
alkali metal hydroxide. A typical reaction is that between Li and H2O.
2Li (s) + 2H2O (l) 2LiOH (aq) + H2 (g)
(a) How many moles of H2 will be formed by the complete reaction of 6.23 moles of Li with
H2O.
(b) How many grams of H2 will be formed by the complete reaction of 80.57g of Li with water.
Solution: (a) The balanced equation is given in the problem
No conversion is needed, because the amount of starting material, Li is given in moles.
Since 2 moles Li produce 1 mol H2 or 2 mol Li  1 mol H2, we calculate moles of H2
produced as follows,
moles of H2 produced = 1 mol H2 / 2 mol Li x 6.23 mol Li
= 3.12 mol H2
Check our answer started with 6.23 moles of Li and produced 3.12 moles of H2.
Since 2 moles of Li produce 1 mol of H2, 3.12 moles is reasonable quantity.
(b) The reaction is same as earlier.
The number moles of Li = 80.57g Li x 1 mol Li/ 6.941 g Li = 11.61 mol Li
2 mol Li  1 mol H2, we calculate the number of moles of H2 as follows,
moles of H2 produced = 1 mol H2 / 2 mol Li x 11.61 mol Li = 5.805 mol H2
From the molar mass of H2 (2.016g) we calculate the mass of H2 produced

Atomic Structure & Basics of Chemistry Page 48

 Mass of H2 produced = 2.016g H2 / 1 mol H2 x 5.805 mol H2 = 11.70 g H2
Check our answer – Because the molar mass of H2 is smaller than that of Li and two moles of
Li are needed to produce one mole of H2, we expect the answer to be smaller than 80.57g.
Example.2 The reaction between nitric oxide (NO) and oxygen to form nitrogen dioxide (NO2)
is a key step in photochemical smog formation.
2NO(g) + O2(g) 2NO2(g)
(a) How many moles of NO2 formed by the complete reaction of 0.254 mole of O2?
(b) How many grams of NO2 formed by the complete reaction of 1.44g of NO?
Solution (a) According to our balanced equation, 1 mol O2  2 mol NO2
Moles of NO2 formed = 2 mol NO2 / 1 mol O2 x 0.254 mol O2
= 0.508 mol NO2 produced
Since 1 mol of O2 produced 2 mol NO2. So, we expect 0.254 mol O2 produce 0.508 mol of NO2
as doubled is reasonable.
(b) We convert 1.44g of NO into moles.
So, mol NO=1 mol NO/30g NO x 1.44g NO = 0.048mol NO
2 mol NO produce 2 mol NO2 i.e., 2 mol NO  2 mol NO2
so, 0.048 mol NO produced 0.048 mol NO2
Mass of NO2 produced = 46g NO2 / 1 mol NO2 x 0.048 mol NO2 = 2.208g NO2
Because the molar mass of NO2 is larger than NO and two moles of NO produce two moles
of NO2, we expect the answer to be larger than 1.44g.
Example.3 In the case of Haber process of NH3 production, nitrogen react with hydrogen gas as,
N2 + 3H2 2NH3
Work out the followings,
(a) How many moles of NH3 formed by the complete reaction of 6.38 moles of N2?
(b) How many moles of H2 used in this reaction?
(c) How many grams of N2 used for the production of 114g of NH3?
Solution
(a) 1 mol N2  2 mol NH3
so, 6.38 mol N2 produced 12.76 mol NH3.
(b) 1 mol NH3 = 17 g of NH3
208g NH3 contains = 1 mol NH3 / 17g NH3 x 208g NH3
= 12.24 mol NH3
According to balanced equation, 3 mol H2 used for the production of 2 mol of NH3
3 mol of H2  2 mol NH3
No of moles of H2 used for production of 12.24 mol NH3 = 3 mol H2/2 mol NH3 x 12.24 mol
NH3 = 18.36 mol H2

Atomic Structure & Basics of Chemistry Page 49

(c) 1 mol NH3 = 17 g of NH3
114g NH3 contains = 1 mol NH3 / 17g NH3 x 114g NH3
= 6.71 mol NH3
According to balanced equation, 1 mol. N2 used for the production of 2 mol of NH3
1 mol of N2  2 mol NH3
No of moles of N2 used for production of 6.71 mol NH3 = 1mol N2/2 mol NH3 x 6.71 mol
NH3
= 3.36 mol N2
1 mol of N2 = 28g of N2
so, 3.36mol N2 = 28g N2 / 1 mol N2 x 3.36 mol N2
= 94.08g of N2 used.
--------------------……………….----------------------
5.5 Limiting Reagents
Reactants are added to a reaction vessel in different amounts given by the chemical equation. In
such cases only one of the reactants may be completely consumed at the end of the reaction,
called limiting reagents. Whereas some amounts of other reactants will remain unreacted (not
completely consumed) is often referred as an excess reagent.
For example, sulfur hexafluoride (SF6) is formed by burning sulfur in an atmosphere of fluorine
as S (l) + 3F2 (g) SF6 (g)
This reaction says that 1mol of S reacts with 3 moles of F2 to produce 1 mol SF6. Suppose that 4
moles of S are added to 20 moles of F2.
Since 1 mol S  3 mol F2, the number of moles of F2 needed to react with 4 moles of S is,
4 mol S x 3 mol F2 / 1 mol S = 12 mol F2
But there are 20 moles of F2 available, more than needed to completely react with S. Thus
S must be the limiting reagent and F2 the excess reagent. The amount of SF6 produced depends
only on how much S was originally present.
Exercise.1 Urea is prepared by reacting NH3 with CO2, 2NH3 (g) + CO2 (g) (NH2)2CO (aq)
+ H2O(l)
In one process, 637.2g of NH3 are allowed to react with 1142g of CO2. (a) Which of two
reactants is the limiting reagent? (b) Calculate the mass of (NH2)2CO formed. (c) How much of
the excess reagent (in grams) is left at the end of the reaction?
Solution: (a) Molar mass of NH3 and CO2 are 17.03g and 44.01g
mol of NH3 = 1 mol NH3 / 17.03g NH3 x 637.2g NH3 = 37.42 mol NH3
mol of CO2 = 1 mol CO2 / 44.01g NH3 x 1142g CO2 = 25.95mol CO2
From the balanced equation, we see 2 mol NH3  1 mol CO2. So, number of moles of NH3
needed to react with 25.95 mol CO2 is, 2 mol NH3 / 1 mol CO2 x 25.95 mol CO2 = 51.90
mol NH3
Atomic Structure & Basics of Chemistry Page 50
Since there are only 37.42 mol of NH3 present, not enough to react completely with CO2. Hence
NH3 must be the limiting reagent and CO2 is an excess reagent.
(b) The amount of urea, (NH2)2CO produced is determined by the amount of limiting reagent
present, so
mass of (NH2)2CO = 1 mol urea/2mol NH3 x 37.42 mol NH3 x 60.06 g urea/ 1mol urea
= 1124g urea
(c) The number of moles of the excess reagent left at the end of the reaction is,
25.95 mol CO2 – [37.42 mol NH3 x 1 mol CO2 / 2mol NH3] = 7.24 mol CO2
and mass left over = 44.01g CO2 / 1 mol CO2 x 7.24 mol CO2
= 319 g CO2
5.6 Reaction Yield
Theoretical yield: The amount of limiting reagent present at the beginning of reaction
determines the theoretical yield of the reaction. It is the maximum obtainable yield, predicted by
the balanced equation.
Actual yield: In practically, the actual yield or the amount of product actually obtained from a
reaction is almost always less than the theoretical yield.
Percent yield: It is described as the proportion of the actual yield to the theoretical yield. It is
calculated as, actual yield
% yield = --------------------------- x 100 %
Theoretical yield
Percent yield ranged from a fraction of 1-100%

Exercise.1 Urea is prepared by reacting NH3 with CO2, 2NH3 (g) + CO2 (g) (NH2)2CO (aq) +
H2O (l)
In one process, 637.2g of NH3 are allowed to react with 1142g of CO2. (a) Which of two
reactants is the limiting reagent? (b) Calculate the theoretical yield of (NH2)2CO in grams (c)
Calculate the percent yield if 640g of urea actually obtained.
Solution: (a) calculate the number of moles of NH3 and CO2 initially present from their molar
mass of NH3 and CO2 are 17.03g and 44.01g respectively.
mol of NH3 = 1 mol NH3 / 17.03g NH3 x 637.2g NH3 = 37.42 mol NH3
mol of CO2 = 1 mol CO2 / 44.01g NH3 x 1142g CO2 = 25.95mol CO2

From the balanced equation, we see 2 mol NH3  1 mol CO2. So, number of moles of
NH3 needed to react with 25.95 mol CO2 is, 2 mol NH3 / 1 mol CO2 x 25.95 mol CO2 = 51.90
mol NH3. Since there are only 37.42 mol of NH3 present, not enough to react completely with
CO2. Hence NH3 must be the limiting reagent and CO2 is an excess reagent.
(b) From the amount of limiting reagent we can calculate the theoretical yield of urea, (NH2)2CO
as,

Atomic Structure & Basics of Chemistry Page 51

 From the balanced equation, 2 mol NH3  1 mol urea
Theoretical yield = 1 mol urea/2mol NH3 x 37.42 mol NH3 x 60.06 g urea/ 1mol urea
= 1124g urea
(c) Therefore, % yield = actual yield / Theoretical yield x 100%
= 640g / 1124g x 100%
= 56.94%
Example.2 Titanium is a protective material, which is used in aircraft, spaces, bicycle spare parts
etc., Titanium is prepared by the reaction of TiCl4 with molten magnesium between 9500C and
11500C.
TiCl4 (g) + 2Mg (l) Ti (s) + 2MgCl (l)
In industrial operation 3.54x10 g of TiCl4 reacted with 1.13x107g Mg (a) Calculate the
7

theoretical yield of Ti in grams. (b) Calculate the percent yield if 7.91x106 g of Ti is actually
obtained.
Solution: First we find out limiting reagent, from this to calculate the theoretical yield.
(a) Calculate the number of moles of TiCl4 and Mg initially present.
moles of TiCl4 = 3.54x107g TiCl4 x 1 mol TiCl4 / 189.7g TiCl4 = 1.87x105 mol TiCl4
moles of Mg = 1.13x107g Mg x 1mol Mg / 24.31g Mg = 4.65x105 mol Mg
Next, we must determine which of the two substances is the limiting reagent. From the balanced
equation, 1 mol TiCl4  2 mol Mg; therefore the number of moles of Mg needed to react with
1.87x105 moles of TiCl4 is,
1.87x107 mol TiCl4 x 2 mol Mg/1 mol TiCl4 = 3.74x105 mol Mg
Since 4.65x105 mol of Mg are present more than is needed to react with the amount of TiCl4. So,
Mg must be the excess reagent and TiCl4 is the limiting reagent.
The equation shows that, 1 mol TiCl4  1 mol Ti ; thus the theoretical mass of Ti formed is,
1.87x105 mol TiCl4 x 1 mol Ti/1 mol TiCl4 x 47.88g Ti/ 1 mol Ti = 8.95x106g Ti
(b) The % yield of this reaction,
% yield = actual yield / Theoretical yield x 100%
= 7.91x106g / 8.93x106g x 100% = 88.6%
Example.3 Industrially, vanadium metal, which is used in steel alloys, can be obtained by
reacting vanadium(V) oxide with calcium at high temperature.
5Ca + V2O5 5CaO + 2V
In one process 1540g of V2O5 react with 1960g of Ca. (a) Calculate the theoretical yield of V. (b)
Calculate the percent yield if 803g of V are obtained.
Solution: (a) Calculate the number of moles of V2O5 and Ca initially present,
Moles of V2O5 = 1 mol V2O5 / 181.88g V2O5 x 1540g V2O5 = 8.46 mol V2O5
Moles of Ca = 1 molCa/40.08g Ca x 1960g Ca = 48.9 mol Ca

Atomic Structure & Basics of Chemistry Page 52

We must determine the limiting reagents. From the balanced equation 5 mol Ca  1mol V2O5;
therefore the number of moles of Ca needed to react with 8.46 mol V2O5,
= 5 mol Ca/1 mol V2O5 x 8.46 mol V2O5 = 42.3 mol Ca
But we have 48.9 mol Ca is more than needed to react with V2O5. So, we conclude that Ca is an
excess reagent and V2O5 is a limiting reagent.
The equation shows, 1molV2O5  2 mol V. Thus, theoretical mass of V formed is,
8.46 mol V2O5 x 2mol V/1 mol V2O5 x 50.94g V/1 mol V = 862.63 g V
(b) The % yield of this reaction = actually yield / Theoretical yield x 100%
= 803g/862.33 x 100%
= 93.12%
---------------------------------………………….-------------------------
5.7 Precipitation Reactions
One common type of reaction occurs in aqueous solution is the precipitation reaction, which
results in the formation of an insoluble solid that separates from the solution. Precipitation
reactions usually involve ionic compounds.
For example, aqueous lead nitrate (Pb(NO3)2 reacts with aqueous sodium iodide (NaI) produce
insoluble yellow precipitate lead iodide (PbI2), sodium nitrate remains in solution as,
Pb(NO3)2 (aq) + 2NaI (aq) ------------ PbI2 (s) + 2NaNO3 (aq)

Yellow in solution
Precipitate
5.7.1 Solubility
How can we predict whether a precipitate will form when a compound is added to a solution or
when two solutions are mixed? It depends on the solubility of the solute, which is defined as the
maximum amount of solute that will dissolve in a given quantity of solvent at a specific
temperature.
A substance is said to be soluble if a fair amount of it visibly dissolves when added to water. If
not, the substance is described as slightly soluble or insoluble. All ionic compounds are strong
electrolytes, but they are not equally soluble. Following table classifies a number of common
ionic compounds as soluble or insoluble.

Atomic Structure & Basics of Chemistry Page 53

Table: Solubility rules for common ionic compounds in H2O at 250C

Soluble compounds Exceptions

Compounds containing alkali metal ions (Li+, Na+,K+,Rb+, Nitrates (NO3-) bicarbonates
Cs+) and the ammonium ion (NH4+). (HCO3-) and Chlorates (ClO3-)
Halides (Cl-, Br-,I-) Halides of Ag+, Hg22+ and Pb2+
Sulfates (SO42-) Sulfates of
Ag+,Ca2+,Sr2+,Ba2+,Hg2+& Pb2

Insoluble compounds Exceptions

Phosphates (PO43-), Chromates (CrO42-) Compounds containing alkali metal

Sulfides (S2-) ions and ammonium ion.

Hydroxides (OH-) Compounds containing alkali

metal ions andBa2+

Exercise.1 Classify the following compounds as soluble or insoluble (a) Silver sulfate (Ag2SO4)
(b) Calcium carbonate (CaCO3) and (c) Sodium phosphate (Na3PO4)
Solution: According to solubility rules,
(a) Ag2SO4 is insoluble
(b) This is a carbonate and Ca is a IIA group metal. Therefore, CaCO3 is insoluble.
(c) Sodium is an alkali metal (groupIA). So, Na3PO4 is soluble.
Exercise.2 Classify the following ionic compounds as soluble or insoluble: (a) CuS (b) Ca(OH)2
and (c) Zn (NO3)2
Solution: According to solubility rules,
(a) CuS is insoluble
(b) Ca(OH)2 is a hydroxide and Ca is a IIA group metal. Therefore, Ca(OH)2 is insoluble in
water.
(c) Zn(NO3)2 is a nitrates, which is soluble in water.

-------------------------------……………..---------------------------------

Atomic Structure & Basics of Chemistry Page 54

5.8 Molecular equations and Ionic equations
The equation describing the precipitation reaction is called a molecular equation. A molecular
equation is useful because it identifies the reagents, but does not accurately describe what
actually happened at the microscopic level. When ionic compounds dissolve in water, they break
apart into their component cations and anions. The equations should show the dissociation of
dissolved ionic compounds into ions. Therefore, returning to write the reaction between sodium
iodide and lead nitrate as,
Pb2+ (aq) + 2NO3- (aq) + 2Na+ (aq) + 2I- (aq) PbI2 (s) + 2Na+ (aq) + 2NO3- (aq)
The above equation is an example of an ionic equation, which shows dissolved species as free
ions.
An ionic equation includes spectator ions, or ions that are not involved in the overall
reaction, in this case the Na+ and NO3- ions. Spectator ions appear on both sides of the equation
and are unchanged in the chemical reaction. So they can be cancelled, we write the net ionic
equation, which shows only the species that actually take part in the reaction,
Pb2+ (aq) + 2I- (aq) PbI2 (s)
Look at another example, BaCl2(aq) + Na2SO4(aq) BaSO4 (s) + 2NaCl (aq)
(White
precipitate)
The ionic equation for the reaction is,
Ba2+ (aq) + 2Cl- (aq) + 2Na+ (aq) + SO42- (aq) BaSO4 (s) + 2Na+ (aq) + 2Cl- (aq)
Canceling the spectator ions (Na+ and Cl-) on both sides of the equation and net ionic equation,
Ba2+ (aq) + SO42- (aq) BaSO4 (s)

Exercise.1 Predict the products of the following reaction and write net ionic equation for the
reaction.
K3PO4 (aq) + Ca(NO3)2 (aq) ?
Solution
 Fix the charges on cations and anions, when these ionic compounds dissolve in water,
they
Produce the K+, PO43-,Ca2+ and NO3-. According to solubility rule Ca2+ and PO43- can form an
insoluble, calcium phosphate [Ca(PO4)2]. Therefore, this is a precipitation reaction. The other
product, KNO3 is soluble and remains in solution. The molecular reaction is,
2K3PO4 (aq) + 3Ca(NO3)2 (aq) KNO3 (aq) + Ca3(PO4)2 (s)
and the ionic equation for this is,
6K+ (aq) + 2PO43- (aq) + 3Ca2+ (aq) + 6NO3- (aq) Ca3(PO4)2 (s) + 6K+ (aq) + 6NO3- (aq)
Canceling the spectator ions and obtain the net ionic equation,
3Ca2+ (aq) + 2PO43- (aq) Ca3(PO4)2 (s)
----------------------………………….--------------------------

Atomic Structure & Basics of Chemistry Page 55

Practice Exercise.1 Predict the precipitate produced by the following reaction and write a net
equation for the reaction.
Al(NO3)3 (aq) + NaOH (aq) ?
Solution
They produce the Al3+, NO3-, Na+ and OH-, when dissolved in water. According to
solubility rules, Al3+ and OH- ions can form insoluble compound, Al(OH)3. Therefore this is a
precipitation reaction. The NaNO3 remains in solution. Therefore the molecular reaction is,
3Al(NO3)3 (aq) + 9NaOH (aq) ----------- 3Al(OH)3 (s) + 9NaNO3
The ionic equation,
3Al3+ (aq) + 9NO3- (aq) + 9Na+ (aq) + 9OH-(aq) 3Al(OH)3(s )+ 9Na+ (aq) + 9NO3-(aq)
Canceling the spectator ions, Na+ and NO3-, get net ionic equation as,
3Al3+ (aq) + 9OH- (aq) 3Al(OH)3 (s)

Some other exercises: Write net ionic equation for the followings,
1. 2AgNO3 (aq) + Na2SO4 (aq) ?
Balanced molecular reaction equation,
2AgNO3 (aq) + Na2SO4 (aq) Ag2SO4(s) + 2NaNO3 (aq)
Ionic equation, 2Ag (aq) +SO4 (aq) +2Na+(aq) +2NO3-(aq)
+ 2-
Ag2SO4 (s)+ 2Na+(aq) +2NO3-(aq)
Net ionic equation, 2Ag+(aq) +SO42-(aq) Ag2SO4 (s)
2. BaCl2 (aq) + ZnSO4 (aq) ?
Balanced molecular reaction equation, BaCl2 (aq) + ZnSO4 (aq) BaSO4(s) + ZnCl2 (aq)
2+ - 2+ 2-
Ionic equation, Ba (aq) +2Cl (aq) +Zn (aq) +SO4 (aq) BaSO4(s)+ Zn2+(aq) +2Cl-(aq)
Net ionic equation, Ba2+(aq) + SO42-(aq) BaSO4(s)
3. (NH4)2CO3 (aq) + CaCl2 (aq) ?
Balanced molecular reaction equation, (NH4)2CO3 (aq) + CaCl2 (aq) 2NH4Cl (aq) + CaCO3(s)
+ 2- 2+ -
Ionic equation, 2NH4 (aq) + CO3 (aq) + Ca (aq) + 2Cl (aq) CaCO3(s) + 2NH4+(aq) + 2Cl-(aq)
Net ionic equation, Ca2+(aq) + CO32-(aq) CaCO3(s)
4. Na2S (aq) + ZnCl2 (aq) ?
Balanced molecular reaction equation, Na2S (aq) + ZnCl2 (aq) ZnS (s) + 2 NaCl(aq)
+ 2- 2+ -
Ionic equation, 2Na (aq) + S (aq) + Zn (aq) + 2Cl (aq) ZnS (s) + 2Na+(aq) + 2Cl-(aq)
Net ionic equation, Zn2+(aq) + S2-(aq) ZnS (s)
5. 2K3PO4 (aq) + 3Sr(NO3)2 (aq) ?
Balanced molecular reaction equation, 2K3PO4 (aq)+3Sr(NO3)2 (aq) Sr3(PO4)2(s) + 6KNO3(aq)
Ionic equation, 6K+(aq)+2PO43-(aq)+3Sr2+(aq)+6NO3-(aq) Sr3(PO4)2(s)+6K+(aq)+6NO3-(aq)
Net ionic equation, 3Sr2+(aq)+ 2PO43-(aq) Sr3(PO4)2(s)

Atomic Structure & Basics of Chemistry Page 56

6. Mg(NO3) 2 (aq) + 2NaOH (aq) ?
Balanced molecular reaction, Mg(NO3)2(aq)+2NaOH (aq) Mg (OH)2(s)+2NaNO3(aq)
Ionic equation, Mg2+(aq)+2NO3-(aq)+2Na+(aq)+2OH-(aq) Mg(OH)2(s) + 2Na+(aq) + 2NO3-(aq)
Net ionic equation, Mg2+(aq)+2OH-(aq) Mg(OH)2(s)

5.9 Acid-base neutralization

The neutralization reaction between acid and base produce water and a salt.
Acid + base salt + water
For example, HCl (aq) + NaOH (aq) NaC l(aq) + H2O (l)
The ionic equation,
H+(aq) + Cl-(aq)+Na+(aq) + OH-(aq) Na+(aq) + Cl- (aq) + H2O (l)
Therefore the reaction can be represented by the net ionic equation,
H+(aq)+OH- (aq) H2O (l)
+ -
Both Na and Cl are spectator ions.
5.10 Oxidation-Reduction Reactions
Acid-base reactions can be characterized as proton transfer processes, the class of
reactions called oxidation-reduction or redox reactions is considered as electron-transfer
reactions. Many important redox reactions take place in water, but not all redo reactions occur in
aqueous solution. Consider the formation of CaO from Ca and O2.
2Ca(S) + O2 (g) 2CaO (s)
Calcium oxide (CaO) is an ionic compound made up of Ca2+ and O2- ions.
In this reaction, 2Ca atoms give up or transfer four electrons to two ‘O’ atoms. For our
convenient this process separate into two steps, one involving the loss of 4 electrons and the
other being the gain of four electrons by an O2 molecule.
2Ca 2Ca2+ + 4e-
O2 + 4e- 2O2-
Each of these steps is called a half-reaction. The sum of the half-reactions gives the overall
reaction: 2Ca + O2 + 4e- 2Ca2+ + 2O2- + 4e-
so, 2Ca + O2 2Ca2+ + 2O2-
Finally the Ca2+ and O2- ions combine to form CaO as,
2Ca2+ + 2O2- 2CaO
 The term oxidation reaction refers to the half-reaction that involves loss of electrons.
 A reduction reaction is a half reaction that involves gain of electrons.
 In the formation of CaO, Ca is oxidized. If said to be act as a reducing agent, because it
donates electrons to oxygen and causes O2 to be reduced.

Atomic Structure & Basics of Chemistry Page 57

 O2 is reduced and acts as an oxidizing agent because it accepts electrons from calcium.
Another example of redox reaction,
Zn (s) + CuSO4 (aq) ZnSO4 (aq) + Cu (s)
2+ 2+
Ionic equation, Zn (s) + Cu (aq) Zn (aq) + Cu (s)
Oxidation and reduction half-reactions are,
Zn Zn2+ + 2e- (oxidation)
Cu2+ + 2e- Cu (reduction)
+
Similarly, metallic Cu reduces Ag in a solution of silver nitrate, AgNO3
Cu (s) + 2AgNO3 (aq) Cu(NO3)2 (aq) + 2Ag (s)
+ 2+
or Cu (s) + 2Ag (aq) Cu (aq) + 2Ag (s)
5.10.1 Oxidation Number
An atom’s oxidation number, also called oxidation state, signifies the number of charges
the atom would have in a molecule if electrons were transferred completely.
For example, let us consider the formation of HCl and SO2 as,
H2(g) + Cl2(g) ------------ 2HCl(g)
S(s) + O2(g) -------------- SO2(g)
The numbers above the element symbols are the oxidation numbers.
 Oxidation numbers enable us to identify elements that are oxidized and reduced at a
glance.
 The elements that show an increase in oxidation number (hydrogen and sulfur in above
example) are oxidized chlorine and oxygen is reduced.
 The HCl and SO2 are neutral in terms of charges, so charges must be cancel.
5.10.1.1 Assignment of oxidation numbers
 In free elements each atom has an oxidation number of zero. Thus each atom in H2, Br2,
Na, Be, K, Cl2, I2, O2 and P4 etc. has the same oxidation number, zero.
 For ions composed of only one atom (mono atomic ions ) the oxidation number is equal
to charge on the ion. Thus, Li+ has an oxidation number +1; for Ba2+ - +2; for Fe3+ - +3;
I- = -1; Al3+ = +3; O2- = -2 and so on.
 The oxidation number of oxygen in most of the compounds is –2 (e.g. MgO and H2O),
but in hydrogen peroxide (H2O2) and peroxide ion (O22-), it is –1.
 The oxidation number of hydrogen is +1, but in the case of hydrides like LiH, NaH,
CaH2, its oxidation number is –1.
 All the halogens have the oxidation number –1. But, when combined with oxygen, for
example in oxyacids and oxoanions, they have positive oxidation numbers.
For e.g. in KClO3, the oxidation number of chlorine is +5 and in NaOCl, the oxidation
number of chlorine is +1.

Atomic Structure & Basics of Chemistry Page 58

  In a neutral molecule, the sum of the oxidation numbers of all the atoms must be zero. In
a polyatomic ion, the sum of oxidation numbers of all the elements in the ion must be
equal to the net charge of the ion. For e.g., in NH4+, the oxidation number of N is –3 and
that H is +1. Thus the sum of the oxidation numbers is –3+4(+1) = +1, which is equal to
the net charge of the ion.
 Oxidation numbers do not have to be integers. For e.g., the oxidation number of ‘O’ in
the superoxide ion, O2- is –1/2.

Exercise.1 Assign the oxidation numbers to all the elements in the following compounds and
ion.
(a) Li2O : Li = +1 (b) HNO3 : H+ = +1
O2- = -2 O2- = -2 so, N = +5
(c) Cr2O72- (e) MnO4-
Sum of oxidation number = -2 sum of oxidation number
For O = -2 for O = -2
Cr = x Mn = x
Therefore, -2 = 2(x) + 7(-2) Therefore, -1 = 1x + 4(-2)
- 2 = 2x –14 -1+8 = x
2x = 12 x = +7
x = +6
Therefore, the oxidation number of Cr is +6. Therefore oxidation numner of Mn is +7.

(d) PF3
Sum of oxidation number = 0
For F = -1
P =x
So, 0 = 1x + 3(-1)
X = +3
Therefore, oxidation number of P is +3.

Exercise.2 Arrange the following species in order of increasing order of oxidation number of
the sulfur atom; H2S , S8, H2SO4, S2-, HS-1, SO2, SO3.
In H2S, the oxidation number of S is –2
In S8 =0
In H2SO4 = +6
In S2- = -2
-1
In HS = -2
In SO2 = +4
In SO3 = +6

So, the increasing order as, H2S / S2- / HS-1  S8  SO2  SO3 / H2SO4

Atomic Structure & Basics of Chemistry Page 59

5.10.2 Types of redox reactions
There are four types redox reactions, combination reactions, decomposition reactions,
disproportionation reactions and displacement reactions.
Combination reaction
A combination reaction may be represented by,
A + B ----------- C
Combination reactions are reactions in which two or more substances combine to form a single
product. For e.g. S(s) + O2(g) ------------- SO2(g)
H2(g) + Cl2(g) ------------ 2HCl(g)
3Mg(s) + N2(g) ------------ Mg3N2(s)
Decomposition reactions
This is the opposite of combination reactions. Specifically, a decomposition reaction is the
breakdown of a compound into two or more components.
C ------------- A + B
If A or B is an element, then the reaction is redox in nature. For e.g.,
2 HgO(s) ------------- 2Hg(l) + O2(g)
2 KClO3(s) ------------ 2KCl(s) + 3O2(g)
2 NaH(s) ---------------- 2 Na(s) + H2(g)
Disproportionation reaction
A special type of redox reaction is the disproportionation reaction. In this case, an element in one
oxidation state is simultaneously oxidized and reduced. One reactant in a disproportionation
reaction always contains an element that can have at least three oxidation states.
 The decomposition of H2O2 is an example of a disproportionation reaction,
2H2O2 (aq) -------------- 2H2O (l) + O2(g)
Here the oxidation number of oxygen in the reactant (-1) both increase to zero in O2 and
decreases to –2 in H2O.
 Another example, is the reaction between molecular chlorine and NaOH solution,
Cl2 + 2 OH-(aq) ----------- ClO-(aq) + Cl-(aq) + H2O(l)
This reaction describes the formation of household bleaching agents, for it is the
hypochlorite ion (ClO-).
Displacement reaction
In a displacement reaction, an ion ( or atom) in a compound is replaced by an ion ( or atom) of
another element.
i.e., A + BC ------------------ AC + B
Three subcategories are, hydrogen displacement, metal displacement and halogen displacement.
1. Hydrogen displacement reaction
All alkali metals and some alkaline earth metals (Ca, Sr & Ba), which are most reactive of
the metallic elements will displace hydrogen from cold water.
2 Na(s) + 2H2O(l) ---------- 2 NaOH (aq) + H2 (g)
Ca(s) + 2H2O (l) ------------ Ca(OH)2(aq) + H2 (g)
Atomic Structure & Basics of Chemistry Page 60
Less reactive metals, such as Al and Fe, react with steam to give hydrogen gas,
2 Al(s) + 3H2O(g) ------------- Al2O3 (s) + 3H2 (g)
2 Fe (s) + 3H2O(g) -------------- Fe2O3 (s) + 3H2 (g)
Many metals including those that do not react with water, are capable of displacing hydrogen
from acids. For example,
Zn(s) + 2HCl(aq) ---------------- ZnCl2 (aq) + H2 (g)
Mg (s) + 2HCl (aq) --------------- MgCl2 (aq) + H2 (g).
2. Metal displacement reactions
A metal in a compound can be displaced by another metal in the elemental state.
For example, vanadium is obtained by treating vanadium(V) oxide with metallic calcium.
V2O5 (s) + 5 Ca (l) -------------- 2V(l) + 5 CaO (s)
Similarly, titanium is obtained from TiCl4 according to the reaction,
TiCl4 (g) + 2 Mg (l) ------------ Ti (s) + 2 MgCl2 (aq)
An easy way to predict whether a metal or hydrogen displacement reaction will actually occur
is to refer to an activity series (sometimes called electrochemical series) shown in following
figure. Basically, an activity series is a convenient summary of the results of many possible
displacement reactions.

According to this series, any metal above hydrogen will displace it from water or from an acid,
but metals below hydrogen will not react with either water or an acid. In fact, any species listed
in the series will react with any species below it. For e.g., Zn is above Cu, so Zn metal will
displace Cu ions from copper sulphate as, Zn (s) + CuSO4 (aq) -------- ZnSO4 (aq) + Cu (s)

Atomic Structure & Basics of Chemistry Page 61

3. Halogen Displacement Reactions
The halogens behavior in halogen displacement reactions, F2  Cl2  Br2  I2
The power of these elements as oxidizing agents decreases as we move down from
fluorine
to iodine, so molecular fluorine can replace Cl-, Br- and I- ions in solution. The halogen
displacement equations are,
Cl2 (g) + 2 KBr (aq) ------------ 2KCl (aq) + Br2 (l)
Cl2 (g) + 2 NaI (aq) ------------ 2NaCl (aq) + I2 (l)
Molecular bromine can displace iodide ion in solution as,
Br2 (l) + 2 KI (aq) ------------- 2KBr (aq) + I2 (s)
Reversing the roles of the halogens produces no reaction. Thus, bromine cannot displace
chloride ions and iodine cannot displace bromide and chloride ions.

-----------------……………….-------------------
5.10.3 Balancing of Redox reactions
1. Balance the following redox reaction by using ion-electron method in basic medium.
MnO4- + I- MnO2 + I2
Divide into two half reactions
I- I2 (oxidation)
-
MnO4 MnO2 (reduction)
Balance the I atoms in the oxidation half reaction, 2I- I2
In the reduction half reaction, we add two H2O molecules on the right side to balance the O
atoms, MnO4- MnO2 + 2H2O
To balance the H atoms, we add 4H+ ions on the left side, we get,
MnO- + 4H+ MnO2 + 2H2O
Since the reaction occurs in basic medium and there are foir H+ ions we added. So, add
four OH- on both sides, MnO- + 4H+ + 4OH- MnO2 + 2H2O + 4OH-
Balance the charges of two half reactions, 2I- I2 + 2e-
MnO- + 4 H2O + 3e- MnO2 + 2H2O +
-
4OH
Equalize the number of electrons; we multiply the oxidation half reaction by 3 and reduction
half reaction by 2.
6I- 3I2 + 6e-
2MnO- + 4 H2O + 6e- 2MnO2 + 8OH-
----------------------------------------------------------------
Combine both half reactions, 2MnO4- + 6I- + 4H2O 2MnO2 + 3I2 + 8OH-
----------------------------------------------------------------

Atomic Structure & Basics of Chemistry Page 62

 Finally, checked the coefficient of elements shows that the equation is balanced in terms of
both atoms and charges.

Example.2 Balance the following redox in acidic medium by ion-electron method

H2S + HNO3 H2SO4 + NO2 + H2O
Write the ionic equation for the above reaction,
H2S + H+ + NO3- 2H+ + SO42- + H2O
Split into two half reactions, H2S H2SO4 (oxidation)
(-2) (+6)
-
NO3 NO2 (reduction)
(+5) (+4)
Balance the ‘O’ and ‘H’ atoms in the above two half reactions,
H2S + 4H2O H2SO4 + 8H+
NO3- + 2H+ NO2 + H2O
Balance the charges on both half reactions,
H2S + 4H2O H2SO4 + 8H+ + 8e-
NO3- + 2H+ + e- NO2 + H2O
Compare the both half reactions and equalize their charges, so, multiply the reduction
equation by 8, and if any common ions, molecules and charges are there cancel it, we get,
H2S + 4H2O H2SO4 + 8H+ + 8e-
8NO3- + 16H+ + 8e- 8NO2 + 8H2O
------------------------------------------------------------
H2S + 8HNO3 H2SO4 + 8NO2 + 4H2O
----------------------------------------------------------

Atomic Structure & Basics of Chemistry Page 63

View publication stats