CHAPTER 2

ATOMIC STRUCTURE
AND BONDING
 HISTORY OF ATOM

• 17th century: Robert Boyle asserted that elements are made up of “simple
bodies” which themselves are not made up of any other bodies.
• 19th century: John Dalton stated that matter is made up of small particles
called atoms.
• 19th century: Henri Becquerel and Marie and Pierre Curie in France,
introduced the concept of radioactivity.
• Joseph J. Thompson found electrons.
• In 1910 Ernest Rutherford found protons.
• In 1932, James Chadwick found neutrons.
 STRUCTURE OF ATOMS
ATOM
Basic Unit of an Element
Diameter : 10 –10 m.
Neutrally Charged

Nucleus Electron Cloud

Diameter : 10 m
–14
Mass : 9.109 x 10 –28 g
Accounts for almost all mass Charge : -1.602 x 10 –9 C
Positive Charge Accounts for all volume

Proton
Mass : 1.673 x 10 –24 g Neutron
Mass : 1.675 x 10 –24 g 3
Charge : 1.602 x 10 –19 C
Neutral Charge
 ATOMIC NUMBER AND ATOMIC MASS

• Atomic Number = Number of Protons in the nucleus

• Unique to an element
 Example :- Hydrogen = 1, Uranium = 92

• Relative atomic mass = Mass in grams of 6.203 x 1023 ( Avagadro Number) Atoms.
• The mass number (A) is the sum of protons and neutrons in a nucleus of an atom.
 Example :- Carbon has 6 Protons and 6 Neutrons. A= 12.

• One Atomic Mass unit is 1/12th of mass of carbon atom.

• One gram mole = Gram atomic mass of an element.
• Isotope: Variations of element with same atomic number but different mass number.
One gram 6.023 x 1023
12 Grams
Mole of Carbon
Of Carbon
Carbon Atoms
 EXAMPLE PROBLEM
• A 100 gram alloy of nickel and copper consists of 75 wt% Cu and 25 wt% Ni. What are
percentage of Cu and Ni Atoms in this alloy?
Given:- 75g Cu Atomic Weight 63.54
25g Ni Atomic Weight 58.69

75 g
• Number of gram moles of Cu =  1.1803mol
63.54 g/mol
25g
• Number of gram moles of Ni =  0.4260mol
58.69 g/mol
1.1803
• Atomic Percentage of Cu =  100  73.5%
(1.1803  0.4260)
0.4260
• Atomic Percentage of Ni =  100  25.5%
(1.1803  0.4260)
 EXAMPLE PROBLEM

• An intermetallic compound has the chemical formula NixAly, where x and y are simple integers,
and consists of 42.04 wt% nickel and 57.96 wt% aluminum. What is the simplest formula of this
nickel aluminide?

• No. of moles of Ni = 42.04 g Ni / 1 mol Ni /58.71 g Ni = 0.7160 mol

• No. of moles of Al = 57.96 g Al / 1 mol Al /26.98 g Al = 2.148 mol
•  total = 2.864 mol
• mole fraction of Ni = 0.1760 / 2.864 = 0.25
•  mole fraction of Al = 2.148 / 2.864 = 0.75
• The simplest formula is Ni0.25Al0.75. or NiAl3.
 PLANCK’S QUANTUM THEORY

• Max Planck, discovered that atoms and molecules emit energy only in certain discrete
quantities, called quanta.
• James Clerk Maxwell proposed that the nature of visible light is in the form of
electromagnetic radiation.
• E = hυ = hc/λ
• Energy is always released in integer multiples of hυ

7
 ELECTRON STRUCTURE OF ATOMS: BOHR’S
THEORY
• Electron rotates at definite energy levels.
• Energy is absorbed to move to higher energy level.
• Energy is emitted during transition to lower
hclevel.
• Energy change due to transition = ΔE = 
h=Planks Constant
= 6.63 x 10-34 J.s Absorb Emit
c= Speed of light Energy Energy
(Photon) (Photon)
λ = Wavelength of light

8
Energy levels
 ENERGY IN HYDROGEN ATOM
• Hydrogen atom has one proton and one electron
• Energy of hydrogen atoms for different energy levels is given by
(n=1,2…..) 13.6 principal quantum numbers
E 2
ev
n
• Example:- If an electron undergoes transition from n=3 state to n=2 state, the
energy of photon emitted is
13.6 13.6
E   2
 2
 1.89ev
3 2
• Energy required to completely remove an electron from hydrogen atom is
known as ionization energy
EMISSION SPECTRUM OF HYDROGEN

10
 UNCERTAINTY PRINCIPLE AND
SCHRODINGER’S WAVE FUNCTIONS

• Bohr’s model fails to explain complex atoms.

• Louis de Broglie: Particles of matter such as electrons could be treated in
terms of both particle and wave.
• λ = h / mv
• Werner Heisenberg (uncertainty principle): It is impossible to simultaneously
determine the exact position and the exact momentum of a body.
• Δx● mΔu ≥ h/4π Δx is the uncertainty in the position, and Δu is the
uncertainty in speed.
• We can only provide the probability of finding an electron with a given
energy within a given space (electron density).
 ELECTRON DENSITY

• Solution of the wave equation is in terms of a wave function, ψ (orbitals).

• The square of the wave function represents electron density.
• Boundary surface
representation.
0.1 nm
• Total probability

0.05 nm
 QUANTUM NUMBERS OF ELECTRONS OF
ATOMS
Subsidiary Quantum Number l
Principal Quantum Number (n)
• Represents sub energy levels
• Represents main energy levels.
(orbital).
• Range 1 to 7.
• Range 0…n-1.
• Larger the ‘n’ higher the energy.
• Represented by letters s,p,d and f.

n=1 s orbital
n=2 (l=0)
n=2
n=1
n=3 p Orbital
(l=1)
S, P AND D ORBITALS
 QUANTUM NUMBERS OF ELECTRONS OF
ATOMS
Magnetic Quantum Number ml.
• Represents spatial orientation of
single atomic orbital.
• Permissible values are –l to +l.
• Example:- if l=1,
ml = -1,0,+1.
I.e. 2l+1 allowed values.
• No effect on energy.
Electron spin quantum number ms.
• Specifies two directions of electron
spin.
• Directions are clockwise or
anticlockwise.
• Values are +1/2 or –1/2.
• Two electrons on same orbital have
opposite spins.
• No effect on energy.
EXAMPLE
 ELECTRON STRUCTURE OF
MULTIELECTRON ATOM
• Maximum number of electrons in each atomic shell is given by 2n2.
• Atomic size (radius) increases with addition of shells.
• Electron Configuration lists the arrangement of electrons in orbital.
 Example :-
Orbital letters Number of Electrons

1s2 2s2 2p6 3s2

Principal Quantum Numbers

 For Iron, (Z=26), Electronic configuration is

1s2 2s2 sp6 3s2 3p6 3d6 4s2
 MULTIELECTRON ATOMS
• Nucleus charge effect: The higher the
charge of the nucleus, the higher is the
attraction force on an electron and the
lower the energy of the electron.
• Shielding effect: Electrons shield each
other from the full force of the nucleus.
• The inner electrons shield the outer
electrons and do so more effectively.
• In a given principal shell, n, the lower the
value of l, the lower will be the energy of
the subshell; s < p < d <f.

Figure 2.9
 THE QUANTUM-MECHANICAL MODEL AND
THE PERIODIC TABLE
• Elements are classified according to their ground state electron configuration.
 PERIODIC TABLE

Source: Davis, M. and Davis, R., Fundamentals of Chemical Reaction Engineering, McGraw-Hill, 2003.
 PERIODIC VARIATIONS IN ATOMIC SIZE
• Atomic size: half the distance between the nuclei of two adjacent atoms (metallic
radius) OR identical (covalent radius).
• Affected by principal quantum number and size of the nucleus.
 OXIDATION NUMBER
• Positive oxidation number: The number of outer electrons that an atom can
give up through the ionization process.
 ELECTRON STRUCTURE AND CHEMICAL
ACTIVITY
• Except Helium, most noble gasses (Ne, Ar, Kr, Xe, Rn) are chemically very
stable
 All have s2 p6 configuration for outermost shell.
 Helium has 1s2 configuration

• Electropositive elements give electrons during chemical reactions to form

cations.
 Cations are indicated by positive oxidation numbers
 Example:-
Fe : 1s2 2s2 sp6 3s2 3p6 3d6 4s2
Fe2+ : 1s2 2s2 sp6 3s2 3p6 3d6
Fe3+ : 1s2 2s2 sp6 3s2 3p6 3d5
ELECTRON STRUCTURE AND CHEMICAL
ACTIVITY

• Electronegative elements accept electrons during chemical reaction.

• Some elements behave as both electronegative and electropositive.
• Electronegativity is the degree to which the atom attracts electrons to itself
 Measured on a scale of 0 to 4.1

 Example :- Electronegativity of Fluorine is 4.1

Electronegativity of Sodium is 1.

Na Te N O Fl
Electro- Electro-
positive 0 K 1 W
negative
2H Se 3 4
28
 TRENDS IN ELECTRON AFFINITY

• Electron affinity: Tendency to accept one or more electrons and release

energy.
• Electron affinity increases (more energy is released after accepting an
electron) as we move to the right across a period and decreases as we move
down in a group.
• Groups 6A and 7A have in general the highest electron affinities.
 METALS, METALLOIDS, AND NONMETALS

• Reactive metals: (or simply metals): Electro positive materials, have the
natural tendency of losing electrons and in the process form cations.
• Reactive nonmetals (or simply nonmetals): Electronegative, they have the
natural tendency of accepting electrons and in the process form anions.
• Metalloids: Can behave either in a metallic or a nonmetallic manner.
• Examples:
• In group 4A, the carbon and the next two members, silicon and germanium, are
metalloids while tin and lead, are metals.
• In group 5A, nitrogen and phosphorous are nonmetals, arsenic and antimony are
metalloids, and finally bismuth is a metal.
 PRIMARY BONDS

• Bonding with other atoms, the potential energy of each bonding atom is lowered
resulting in a more stable state.
• Three primary bonding combinations : 1) metal-nonmetal, 2) nonmetal-
nonmetal, and 3) metal-metal.
• Ionic bonds :- Strong atomic bonds due to transfer of electrons
• Covalent bonds :- Large interactive force due to sharing of electrons
• Metallic bonds :- Non-directional bonds formed by sharing of electrons
• Permanent Dipole bonds :- Weak intermolecular bonds due to attraction
between the ends of permanent dipoles.
• Fluctuating Dipole bonds :- Very weak electric dipole bonds due to asymmetric
distribution of electron densities.
 IONIC BONDING
• Ionic bonding is due to electrostatic force of attraction between cations and
anions.
• It can form between metallic and nonmetallic elements.
• Electrons are transferred from electropositive to electronegative atoms

Electropositive Electronegative
Electron
Element Atom
Transfer

Electrostatic
Cation Attraction Anion
+ve charge -ve charge

IONIC BOND
 IONIC BONDS
• Large difference in electronegativity.
• When a metal forms a cation, its radius reduces and when a nonmetal forms an
anion, its radius increases.

The electronegativity variations

 IONIC BONDING - EXAMPLE
• Ionic bonding in NaCl
3s1
3p6 Chlorine
Sodium Atom
Atom Cl
Na

I
O
N Chlorine Ion
I Cl -
Sodium Ion
C
Na+
B
O
N Figure 2.10
D
 IONIC FORCE FOR ION PAIR
• Nucleus of one ion attracts electron of another ion.
• The electron clouds of ion repulse each other when they are sufficiently close.
• These two forces will balance each other when the equilibrium interionic
distance, a0, is reached and a bond is formed

Force versus separation

Distance for a pair of
oppositely charged ions

Figure 2.11
35
 ION FORCE FOR ION PAIR
 Z e  Z e  Z Z e
2

F 
4  a  4  a 

1 2 1 2
attractive 2 2
0 0

Z1,Z2 = Number of electrons removed or

added during ion formation
e = Electron Charge, a = Interionic seperation distance
ε = Permeability of free space (8.85 x 10-12c2/Nm2)
nb
(n and b are constants)
F repulsive

n 1
a
2
Z Z e  nb
F net  1 2

4  a  a
0
2 n 1
 INTERIONIC FORCE - EXAMPLE
• Force of attraction between Na+ and Cl- ions

Z1 = +1 for Na+, Z2 = -1 for Cl-

e = 1.60 x 10-19 C , ε0 = 8.85 x 10-12 C2/Nm2 Na+ Cl-

a0 = Sum of Radii of Na+ and Cl- ions

= 0.095 nm + 0.181 nm = 2.76 x 10-10 m
2 19

 Z Z e 
( 1)( 1)(1.60  10 C )
2

F 1 2
 3.02  10 9 N a0
attraction
4  a  4 (8.85 x 10 C /Nm2)(2.76 x 10
0
2 -12 2 -10
m)
 INTERIONIC ENERGIES FOR ION PAIRS
• Net potential energy for a pair of oppositely
2
charged ions = ZZe b
E  1 2

net
4  a 
0
2
a
n

Attraction Repulsion
Energy Energy

Energy Energy
Released Absorbed

• Enet is minimum when ions are at equilibrium seperation distance a0

ION ARRANGEMENTS IN IONIC SOLIDS
• Ionic bonds are Non Directional
• Geometric arrangements are present in solids to maintain electric
neutrality.
 Example:- in NaCl, six Cl- ions pack around central Na+ Ions

Ionic packing
In NaCl
and CsCl
Figure 2.13

CsCl NaCl

• As the ratio of cation to anion radius decreases, fewer anion surround

central cation.
 BONDING ENERGIES
• Lattice energies and melting points of ionically
bonded solids are high.
• Lattice energy decreases when size of ion increases.
• Multiple bonding electrons increase lattice energy.

 Example :-
NaCl Lattice energy = 766 KJ/mol
Melting point = 801oC
CsCl Lattice energy = 649 KJ/mol
Melting Point = 646oC
BaO Lattice energy = 3127 KJ/mol
Melting point = 1923oC
 BONDING ENERGY

• Consider production of LiF: result in the release of about 617 kJ/mole.

• Step 1. Converting solid Li to gaseous Li (1s22s1): 161 kJ/mole of energy. 
• Step 2. Converting the F2 molecule to F atoms: 79.5 kJ/mole. 
• Step 3. Removing the 2s1 electron of Li to form a cation, Li+: 520 kJ/mole. 
• Step 4. Transferring or adding an electron to the F atom to form an anion, F-:
-328 kJ/mole. 
• Step 5. Formation of an ionic solid from gaseous ions: lattice energy ,
unknown=-617 kJ – [161 kJ + 79.5 kJ + 520 kJ – 328 kJ] = -1050 kJ
 LATTICE ENERGY, MATERIAL PROPERTIES

• Ionic solids are hard, rigid and strong and brittle.

• Excellent Insulators.
 COVALENT BONDING
• In Covalent bonding, outer s and p electrons are shared between two atoms
to obtain noble gas configuration.
• Takes place between elements
with small differences in
electronegativity and close by
in periodic table. Overlapping Electron Clouds

• In Hydrogen, a bond is formed between 2 atoms by sharing their 1s1 electrons

Electron
Pair

H + H H H
1s1 Hydrogen
Electrons Molecule
 COVALENT BONDING - EXAMPLES

• In case of F2, O2 and N2, covalent bonding is formed by sharing p electrons

• Fluorine gas (Outer orbital – 2s2 2p5) share one p electron to attain noble gas configuration.

F + F F F F F
H Bond Energy=160KJ/mol

• Oxygen (Outer orbital - 2s2 2p4) atoms share two p electrons

O + O O O O=O
Bond Energy=28KJ/mol

• Nitrogen (Outer orbital - 2s2 2p3) atoms share three p electrons

N + N N N N N
Bond Energy=54KJ/mol
 BOND LENGTH, BOND ORDER AND BOND
ENERGY
• For a given pair of atoms, with higher bond order, the bond length will
decrease; as bond length decreases, bond energy will increase (H2, F2,
N2 )
• Nonpolar bonds: sharing of the
bonding electrons is equal
between the atoms and the bonds.
• Polar covalent bond: Sharing of
the bonding electrons is unequal
(HF, NaF).
 COVALENT BONDING IN CARBON
Ground State arrangement

• Carbon has electronic configuration 1s2 2s2 2p2 Indicates

carbon
Forms two
1s 2s 2p Covalent
Two ½ filed 2p orbitals bonds

• Hybridization causes one of the 2s orbitals promoted to 2p orbital.

• Result four sp3 orbitals.
Indicates
four covalent
1s 2p bonds are
Four ½ filled sp3 orbitals formed
 STRUCTURE OF DIAMOND
• Four sp3 orbitals are directed symmetrically toward corners of regular
tetrahedron.
• This structure gives high hardness, high bonding strength (711KJ/mol) and
high melting temperature (3550oC).

Carbon Atom Tetrahedral arrangement in diamond

 CARBON CONTAINING MOLECULES
• In Methane, Carbon forms four covalent bonds with Hydrogen.
• Molecules are very weekly
Methane
bonded together resulting molecule
in low melting temperature
(-183oC).
• Carbon also forms bonds with itself.
• Molecules with multiple carbon bonds are more reactive.
 Examples:-
H H
C C H C C H
H H Acetylene
Ethylene
 COVALENT BONDING IN BENZENE
• Chemical composition of Benzene is C6H6.
• The Carbon atoms are arranged in hexagonal ring.
• Single and double bonds alternate between the atoms.

H C H
C C

C C H
H
C
H
Structure of Benzene Simplified Notations
 METALLIC BONDING

• Atoms in metals are closely packed in crystal structure.

• Loosely bounded valence electrons are attracted towards nucleus of other atoms.
• Electrons spread out among atoms forming electron clouds. Positive Ion
• These free electrons are
reason for electric
conductivity and ductility
• Since outer electrons are
shared by many atoms,
metallic bonds are
Non-directional

Valence electron charge cloud

• Overall energy of individual atoms are lowered by metallic bonds
• Minimum energy between atoms exist at equilibrium distance a0
• Fewer the number of valence electrons involved, more metallic the bond is.
 Example:- Na Bonding energy 108KJ/mol,
Melting temperature 97.7oC

• Higher the number of valence electrons involved, higher is the bonding energy.
 Example:- Ca Bonding energy 177KJ/mol,
Melting temperature 851oC

51
 METALLIC BONDS AND MATERIAL
PROPERTIES
• The bond energies and the melting point of metals vary greatly depending on
the number of valence electrons and the percent metallic bonding.
 METALLIC BONDS AND MATERIAL
PROPERTIES
• Pure metals are significantly more malleable than ionic or covalent networked
materials.
• Strength of a pure metal can be significantly increased through alloying.
• Pure metals are excellent conductors of heat and electricity.
 SECONDARY BONDING
• Secondary bonds are due to attractions of electric dipoles in atoms or
molecules.
• Dipoles are created when positive and negative charge centers exist.

Dipole moment=μ =q.d

+q -q
Figure 2.26 q= Electric charge
d = separation distance

d
• There two types of bonds permanent and fluctuating.
 FLUCTUATING DIPOLES
• Weak secondary bonds in noble gasses.
• Dipoles are created due to asymmetrical distribution of electron charges.
• Electron cloud charge changes with time.

Symmetrical Asymmetrical
distribution Distribution
of electron charge (Changes with time)
 PERMANENT DIPOLES

• Dipoles that do not fluctuate with time are called Permanent dipoles.

Symmetrical No Dipole
 Examples:- CH4 Arrangement moment
Of 4 C-H bonds

Asymmetrical
Creates
CH3Cl Tetrahedral
Dipole
arrangement
 HYDROGEN BONDS

• Hydrogen bonds are Dipole-Dipole interaction between polar

bonds containing hydrogen atom.
 Example :-
 In water, dipole is created due to asymmetrical arrangement of hydrogen atoms.
 Attraction between positive oxygen pole and negative hydrogen pole.

105 0
O
Hydrogen
H Bond
 EXERCISES
1. What are the similarities and differences among protons, neutrons, and electrons? Compare in detail.
2. Define a) atomic number, b) atomic mass, c) atomic mass unit (amu), d) mass number, e) isotopes, f)
mole, g) relative atomic mass, h) average relative atomic mass, and i) Avogadro’s number.
3. Sterling silver contains 92.5 wt% silver and 7.5 wt% copper. Copper is added to silver to make the
metal stronger and more durable. A small sterling silver spoon has a mass of 100 grams. Calculate the
number of copper and silver atoms in the spoon.
4. A monel alloy consists of 70 wt % Ni and 30 wt % Cu. What are the atom percentages of Ni and Cu in
this alloy?
5. Write the electron configurations of the following elements by using spdf notion:
(a) yttrium, (b) hafnium, (c) samarium, (d) rhenium.
6. Rank the following atoms in (a) increasing atomic size and (b) decreasing first ionization energy. Use
only the periodic table to answer the questions. i) K, Ca, Ga ii) Ca, Sr, Ba iii) I, Xe, Cs
7. Rank the following atoms in (a) increasing atomic size and (b) decreasing first ionization energy,. Use
only the periodic table to answer the questions. i) Ar, Li, F, O, Cs C ii) Sr, H, Ba, He, Mg, Cs
8. The first ionization energies of two atoms with electronic configurations (a) 1S 22s22p6 and (b)
1s22s22p63s1 are given to be 2080 kJ/mol and 496 kJ/mol. Determine which IE1 belongs to which
electronic structure and justify your answer.
9. Calculate the attractive force between a pair of Ba2+ and S2- ions that just touch each other. Assume the
ionic radius of the Ba2+ ion to be 0.143 nm and that of the S2- ion to be 0.174 nm.
10. Describe the properties (electrical, mechanical, etc…) of materials that are exclusively made up of a)
ionic bonds, b) covalent bonds, and c) metallic bonds. Name a material for each type.
11. What are secondary bonds? What is the driving force for formation of such bonds? Give example of
materials in which such bonds exist.
12. Define the following terms: a) dipole moment, b) fluctuating dipole, c) permanent dipole, d) van der
Waals bonds, and e) hydrogen bond.
THE END

Thank you
