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ATOMIC STRUCTURE & BONDING

ISSUES TO ADDRESS...
• What is the atomic structure?

• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

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 Reading

Textbook – Chapter 2
- Section 2.1 Introduction
- Section 2.2 Fundamental concepts
- Section 2.3 Electrons in atoms
- Section 2.4 The periodic table
- Section 2.5 Bonding forces and energies
- Section 2.6 Primary atomic bonds
- Section 2.8 Mixed bonding

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 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.

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 Structure of Atoms
ATOM
Basic Unit of an Element
Diameter : 10 –10 m.
Neutrally Charged

Nucleus Electron Cloud

Diameter : 10 –14 m 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 Neutron
Mass : 1.673 x 10 –24 g Mass : 1.675 x 10 –24 g
Charge : 1.602 x 10 –19 C Neutral Charge

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Atomic Structure

–Atom – electrons – 9.11 x 10-31 kg

protons
neutrons } 1.67 x 10-27 kg in nucleus

–atomic number = # of protons in nucleus of atom

= # of electrons of neutral species

–Definitions:
- Mole is abbreviated to mol and given the symbol n
1 mole is defined as the amount of substance of a system that contains the
same number of "elementary entities" (usually atoms or molecules) as there
are in exactly 12g of carbon-12 atoms.
- The Avogadro’s number is the number of "elementary entities" (usually
atoms or molecules) in one mole and is equal to 6.022 x 1023 particles.

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 Atomic Structure

– A [=] atomic mass unit = amu = 1/12 mass of 12C

Atomic wt = wt of 6.023 x 1023 molecules or atoms

Avogadro’s number

1 amu/atom = 1g/mol
C 12.011
H 1.008 etc.

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 Electronic Structure
– Electrons have wavelike and
particulate properties.
– This means that electrons are
in orbitals defined by a probability.
– Each orbital at discrete energy
level determined by quantum numbers.

Quantum # Designation Adapted from Fig. 2.1, Callister 7e.

n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = subsidiary (orbitals) s, p, d, f (0, 1, 2, 3,…, n-1)
ml = magnetic 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½

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 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 : C
Number of Electrons
Orbital letters

1s2 2s2 2p6 3s2

Principal Quantum Numbers

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

1s2 2s2 2p6 3s2 3p6 3d6 4s2

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 The Quantum-Mechanical Model and the Periodic Table

– Elements are classified according to their ground state electron configuration.

Valence
electrons

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 Valence electrons

– Valence electrons determine all of the following properties

1) Bonding
2) Chemical
3) Electrical
4) Thermal
5) Optical

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 Periodic Variations in Atomic Size

– Atomic size: half the distance between the nuclei of two adjacent atoms (metallic radius)
– Affected by principal quantum number and size of the nucleus.

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 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 0.7 to 4.1
 Example :- Electronegativity of Fluorine is 4.1
Electronegativity of Sodium is 1.

Na Te N O Fl
Electro- Electro-
positive 0 negative
K 1 W 2H Se 3 4

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 Electronegativity

• Ranges from 0.7 to 4.1,

• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

Adapted from Fig. 2.7, Callister 7e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the Chemical
Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by Cornell University).
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Bonding Force and Energy

FA(r) FA(r)

FR(r) FR(r)

Equilibrium position r0:

FA(r0) + FR(r0) = 0

E(r0) = Emin = E0

Adapted from, Callister 7e

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 Types of Bonding

PRIMARY INTERATOMIC BONDS

– Ionic bonding
– Covalent bonding
– Metallic bonding

SECONDARY BONDING OR VAN DER WAALS BONDING

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 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

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 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

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 Ionic Bonding

– Energy – minimum energy most stable

– Energy balance of attractive and repulsive terms

A B
EN = EA + ER = − −
r rn
Repulsive energy ER

Interatomic separation r

Net energy EN
Adapted from Fig. 2.8(b),
Callister 7e.

Attractive energy EA
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 Lattice Energy, Material Properties
– Ionic solids are hard, rigid and strong and brittle.
– Excellent Insulators.

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

Electron
Pair Overlapping Electron Clouds
H + H H H
H H
1s1 Hydrogen
Electrons Molecule

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 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
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 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.
– These free electrons are the reason for electric
conductivity and ductility
– Since outer electrons are shared by Positive Ion
many atoms, metallic bonds are
Non-directional

Valence electron charge cloud

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 Metallic Bonds

– Overall energy of individual atoms are lowered by metallic bonds

– Minimum energy between atoms exist at equilibrium distance r0
– 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

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 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.

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 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.

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 Question Time

What is the type of bonding for the following materials?

A. Aluminium
B. Diamond
C. Magnesium Oxide (MgO)

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 Primary Bonding
– Ionic-Covalent Mixed Bonding
 (X A −X B )2 
 − 
% ionic character =
1− e
4
 x (100%)
 
 

where XA & XB are Pauling electronegativities

Ex: MgO XMg = 1.3

XO = 3.5

 (3.5 −1.3 )2 
 − 
% ionic character = 1 − e 4  x (100%) = 70.2% ionic
 
 
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 Summary: Bonding

Type Bond Energy Materials

Ionic Large! ceramics

Covalent Variable
large-Diamond semiconductors, ceramics,
small-Bismuth polymer chains

Metallic Variable
large-Tungsten metals
small-Mercury

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 Properties From Bonding: Tm

• Bond length, r • Melting Temperature, Tm

Energy
r

• Bond energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = Tm is larger if Eo is larger.
“bond energy”

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 Properties From Bonding : α

• Coefficient of linear thermal expansion, α

length, L o coeff. thermal expansion
unheated, T1
∆L ∆L
= α (T2 -T1)
heated, T 2 Lo
• α ~ symmetry at ro

αB < α R

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 Properties From Bonding : Elastic Modulus

• Young Modulus or Elastic Modulus: EM

2
• ΕΜ ~
dF d E
= 2
dr r0 dr r
0

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 Question Time

If the potential energies for metals A and B vary with the

interatomic spacing as follows, which metal has the largest:
a) Melting temperature?
b) Coefficient of thermal expansion?

r
B
A
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 Summary: Primary Bonds

Ceramics Large bond energy

(Ionic & covalent bonding): large Tm
large E
small α

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate α

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
small E
large α

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