LECTURE 2

Atomic, Structure & Bonding

Dr. Norfhairna Baharulrazi
Atomic, Structure &
Bonding
 Learning Outcome
Week Topic Learning Outcome

2 Atomic Structure and It is expected that students are able

Bonding in Solids: to:
•Types of atomic and •Describe types of atomic bond –
molecular bond ionic, covalent, metallic
•Atomic Structure (2.1, 2.2).
•Periodic Variations and •Describe types of molecular bond –
Trends in Periodic Table permanent dipole and fluctuating
(2.4). dipole
•Primary Bonds (2.5).
•Secondary Bonds (2.6). •Explain the correlations of electronic
structure and bonding of atoms to
materials property.

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 Characteristics of Atom
• Atomic number (Z) : number of protons in the nucleus of an atom.

• Atomic mass : Mass of an atom, expressed in atomic mass unit (amu)

• One amu = 1/12 mass of a 12C atom. Amu gives the relative measure of
mass of one atom with respect to C atom.

• Mass number (A) : sum of protons and neutrons in a nucleus of an atom.

• Isotopes: Atoms of same element, with the same Z but different A

• One mole or gram-mole (mol): amount of an element containing 6.023 ×

1023 atoms.

• Atomic weight or molar mass: Mass in gram of one mole of element.

One 12C atom has atomic mass of 12 amu; one mole of 12C has a mass of
12g and contains 6.023 × 1023 atoms; also called relative atomic mass.

One gram 6.023 x 1023

12 Grams
Mole of Carbon
of Carbon
-5- Carbon Atoms
 Electronic Structure of Atoms
• Electron Configuration lists the arrangement of electrons in orbital.

E.g.:
Electron Configurations
for Magnesium (Z = 12)

Principal Quantum Numbers

or Shell Numbers, n

3s2
2 electrons in valence shell 1s2 2s2 2p6 3s2
2s2 2p6
Orbital letters
10 electrons in filled shells
1s2
Number of Electrons
12Mg
Core charge: 12 – 10 = +2

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2.4 Periodic Table

Source: Davis, M. and Davis, R., Fundamentals of Chemical Reaction Engineering, McGraw-Hill, 2003.
 Periodicity Concept Map
Trends in properties of the
Chemical Refer atoms as one moves in various
periodicity to the directions within the periodic
table

Major properties
Ionization energies
and trends to
know are
Electron affinities
Metallic
element
Electronegativities
Which are
defined in Covalently-
Atomic radii bonded atoms
different
ways for
Atoms in ionic
-8- solids
 Trends in Periodic Table
More nonmetallic character

More negative electron affinity

Increasing ionization energy

Periodic table

Increasing atomic radius

More metallic character

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 Trend in Atom Size
• Size of an atom is measured in terms of its radius.

• Size depends on electronic structure–increases with shell addition–

increases as Z increases.
Metallic radius Half the distance between the nuclei of two adjacent
atoms in a metallic crystal.

rNa
Covalent radius Half the distance between the nuclei of identical
atoms that are bonded together in a molecule.

rCl
Ionic radius The effective radius of ions in solids.

rNa rClˉ
+

van der Waals radius The effective radius of adjacent atoms which are
not chemically bonded in a solid, but are
presumably in "contact”.
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 Various Atomic Radius

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 Trend in Ionization Energy
• The energy needed to remove one electron from an atom–work must be
done to overcome the electrostatic attraction between electrons and
nucleus.

• Term refers to the formation of positive ions. Groups 1A and 2A readily

lose electrons (to obtain complete valence)–have low ionization energy.

• Inversely related to atomic radius.

• Decreases as atomic size (radius) increases.

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 Trends in Electron Affinity
• Tendency of an atom to accept one or more electrons and releases
energy in the process.

• Increases going across the Periodic Table.

• Groups 6A and 7A have high electron affinities because it is easier for them
to accept 1–2 electrons to obtain complete valence than to lose 6–7
electrons.

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 Trends in Oxidation Numbers
• The charge an atom would carry if the
molecule or compound were completely ionic
(composed of ions).

• The number of electrons an atom can give up

through ionization process is called positive
oxidation number.

• The number of electrons an atom can gain is

the negative oxidation number.

• Oxidation number of an atom is zero in a

neutral substance that contains atoms of
only one element. Thus, atoms in O2, O3, P4,
S8, and Al metal all have an oxidation number
of 0.

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 Electronegativity
• Electronegativity of an atom denotes its relative electron-attracting power
in a chemical bond - an indication of its ability to compete with another
atom in attracting a shared electron pair to it.

• Electronegativity is expressed on a numerical scale of 0−4.0.

• Electronegative atom tends to attract bonded electrons to itself; readily

accepts electrons during a chemical reaction to form anion. Anion is
indicated by negative oxidation number.

• Electropositive atom (low electronegativity) has a very weak attraction

for electrons; gives up electrons to form cation. Cation is given by
positive oxidation number.

• Electronegativity values are useful in predicting the type of bonding most

likely between two atoms.

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 Electronegativity & Periodic Table

Increasing EN Highest
Electronegativity

Increasing EN
Lowest
Electronegativity

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 Metals, Metalloids & Nonmetals
• Elements in the Periodic Table can be broadly classified into metals and
nonmetals. Metalloids can behave either as a metal or a nonmetal.

• Reactive metals (metals):

• Elements with low ionization energy and little to no electron affinity.
• Electropositive i.e. natural tendency to lose electrons and form cation
• All elements in Groups 1A and 2A (except H).

• Reactive nonmetals (nonmetals):

• Elements with high ionization energy and very high electron affinity.
• Electronegative i.e. natural tendency to accept electrons and form
anion
• All elements in Groups 6A and 7A are exclusively nonmetallic.

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 Metals, Metalloids & Nonmetals
• Metalloids:
• Elements that can behave either as a metal or as a nonmetal.
• Have intermediate electronegativity.
• Certain elements in Groups 3A, 4A and 5A.
a. Group 3A: Boron is a metalloid but the rest are metals.
b. Group 4A: C is a nonmetal, Si and Ge are metalloids; Sn and Pb are metals.
c. Group 5A: N and P are nonmetals; As and antimony (Sb) are metalloids;
bismuth (Bi) is a metal.

• Noble gases (special class of nonmetals)

• Chemically inert elements (Group 8A) – very stable.
• Have complete valence (s2 and s2p6 configurations).
• Very high ionization energy and no electron affinity
• No electronegativity – nonreactive.

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 Example: Problems 1
Example: Problems 2
The most abundant isotopes of iron, Fe, are;

56Fe (91.754%), with an atomic mass of 55.934 amu.

54Fe (5.845%), with an atomic mass of 53.939 amu

57Fe (2.119%), with an atomic mass of 56.935 amu

58Fe (0.282%), with an atomic mass of 57.933 amu

844 amu
a. Find the average atomic mass of Fe. 55
.

b. What is the relative atomic mass of iron. 85 AH g

.

c. How many atoms are there in 55.849 grams of Fe? 6. 023×023 atoms
"
d. How many are there in 1 gram of Fe. 1. 078 ✗10 atoms
23g
-

e. What are the mass in grams of one atom of Fe? 9- 273×10

f. Based on the answer in part e, what is the mass in

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grams on one amu? 1- 66 NO
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 Example: Problems 2
Example: Problems 2 1,00gram
75%4 {o%Hi
"
1.1802×6-023×10
7.1048×023 A 100-gram alloy of nickel and copper consists of
76%-5--1.1802 not
-4260×6.023×1023
←

°
"
75 wt% Cu and 25 wt% Ni. What are percentage
of Cu and Ni Atoms in this alloy?
yggcu
5%69=0.4260 my
Hi
=
2.5608×10 259
iii. 73.4710 Example: Problems 3
Hi ? 26.53%
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?
Assume wog
0-7163 not I
4204g Ni
-

57.96g Al
-
2.1483mg 3

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Atomic, Structure &
Bonding
Types of Atomic Bond
• A bond is the interaction between two or more atoms that allow them to form a
substance different from the independent atoms. This interaction involves the outer
electrons of the atoms. These electrons are transferred from one atom to another or shared
between them (primary bond).

• Two types of atomic bond: strong primary bond and weak secondary bond.
Types of Atomic Bond
• Primary bonds are chemical bonds and three types of
primary bonds possible between two types of atoms:
• ionic (metal-nonmetal)
• covalent (nonmetal-nonmetal)
• metallic (metal-metal)
• Secondary bonds are physical bond. Do not involve
interaction between outer electrons. Can be divided into:
• fluctuating dipoles
• permanent dipoles
 Atomic Bonding (Cont..)
• Ionic bonds : Strong electrostatic attraction between oppositely charged
particles - transfer of electrons between metal and nonmetal.

• Covalent bonds : Pairs of electrons that are more or less evenly shared
between two nonmetal atoms - large interactive force.

• Metallic bonds : Non-directional bonds formed by sharing of electrons

between metal atoms. Loosely held outer electrons surrounding packed
cations. Important for understanding properties of pure metallic elements
and mixture of metals (alloys).

• 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

temporary unequal distribution of electron densities.
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 Driving Force for Atomic Bonding
• Primary bonding–to achieve stable state (s2 or s2p6
noble-gas electron configuration).

• By bonding with other atom(s) through transfer or sharing

valence electron, the potential energy of every atom
involved in the bonding is lowered, resulting in a more
stable state.

• Secondary bonding already has very low energies.

Driving force for secondary bond formation is the
attraction of electric dipoles contained in atoms or
molecules.

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Primary Bonds

1. Ionic (metal-nonmetal)
2. Covalent (nonmetal-nonmetal)
3. Metallic (metal-metal)
Three Models of Chemical Bonding
Ionic Bonding
 Ionic Bond Formation
• Ionic bond forms through electron transfer from metals to nonmetals.

• The result is complete outer shells of noble-gas electron configuration in both

atoms.
72.0
• Ionic bond occurs between atoms having large electronegativity differences.
Example: Groups 1A or 2A (reactive metals) and Groups 6A or 7A (reactive
nonmetals).

• When metal loses its electron and forms a cation, its radius reduces.

• When nonmetal gains this electron and forms an anion, its radius increases.

• These ions are bonded together by electrostatic (Coulombic) attraction forces

in a solid crystal.

• This electrostatic attraction is called IONIC BOND - electrical in nature as it

involves attraction between opposite charges.

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 Ionic Bond in NaCl - example
Transfer of
3s1 electron
Sodium atom, Na Chlorine atom, Cl
Electropositive Eelectronegative
(2,8,1) (2,8,7)

–
Loses an electron
Sodium cation, Na+ + Gains an electron
Chlorine anion, Cl–
Size decrease Size decrease
Neon configuration Strong Argon configuration
(2,8) electrostatic (2,8,8)
(Coulombic
attraction,)

NaCl (Na+ Cl–)

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Example Problem 4
Use partial orbital diagrams and Lewis symbols to
depict the formation of Na+ and O2− ions from the
atoms, and determine the formula of the compound
formed.
 Ion Arrangement in Ionic Solids

CsCl

Cl–
An ionic compound has Na+
alternating positively and
negatively charged particles
in a pattern that extends in NaCl
all three dimensions.

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Ionic Radii

Size decrease Size Increase

 Ionic Bond Formation

• Ionic compounds e.g. NaCl are composed of positively and negatively charged ions held
together by electrostatic attractions in a crystal lattice.
• Solid ionic compounds do not contain molecules. Instead, because opposite charges attract
one another, the ions stack themselves in crystals such that positive ions are surrounded
by negative ions, and vice versa.
• This combination of attraction and repulsion, acts in all three directions, causes each ion to be
fixed in its location in the crystal lattice. This is the basis for ionic packing arrangement in
ionic solid.
• Since electrostatic forces are nondirectional, structure of ionic solid is determined purely by
geometry. Two main factors determine the ionic packing arrangement: size of the ions and
electrical neutrality.
• As cation-to-anion radius ratio decreases, fewer anions can pack around a cation.
• Ionic solid must be electrically neutral. In both NaCl and CsCl solids, there is one cation for
every Cl− ion in the overall solid. In CaCl2, for every Ca2+ ion there must be two Cl− ions.

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 Bonding Energies
• Lattice energies and melting points of ionic solids are high.
• Lattice energy decreases as the size of ion increases (moving down the group). Melting
point correspondingly decreases.
• Lattice energy increases significantly when ions involved have higher ionic charges
(+2 ion > +1 ion).

The lattice energy and melting point values for various ionic solids

* All values are negative for bond formation (energy is released)

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 Ionic Bond & Material Properties
High melting points
Ionic solids have high melting temperatures.
Reason: Ionic bonds possess large bond energies.

Electrical conductivity
Ionic solids do not conduct electricity.
Reason: valence electrons are tightly held in their place and cannot participate in the
conduction process.

Ionic materials conduct electricity when melted or dissolved in water.

Reason: in the molten or aqueous state ions are free to move, as opposed to being fixed to
their lattice sites like in ionic solids. Electrical conduction occurs through ionic diffusion
(movement of ions).

Chemical Inertness
Ionic solids are chemically inert (stable) - they are essentially metals that already reacted with
their environment, e.g. alumina (Al2O3) and silica (SiO ).

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 Electrical Conductance & Ion Mobility

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 Ionic Bond & Material Properties
Mechanical properties

• Hard (do not dent); rigid or stiff (do not bend, no springiness); strong(difficult to
deform permanently – hard to break). These properties are due to strong
electrostatic forces holding the ions together.

• Brittle – deform little before fracture for e.g. ceramics and glass.

Fracture mechanism of ionic solids. A large applied force puts like ions
against one another. Like charges repel, and break the ionic bonds and the solid.
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Covalent Bonding
Covalent Bonding: Introduction
A covalent bond :

• Is a pair of electrons shared between two atoms in a molecule–called

bonding pair or shared pair.
• Occurs between elements with small differences in electronegativity–
usually close by in Periodic Table.
• Occurs between nonmetals but can also occur in ionic and metallic
solids (leads to mixed bonding)
• Localized sharing of electrons – nonmetal atoms share outer s and p
electrons so that each atom attains noble-gas configuration.
• Orbital overlap.
• Most common form of bonding found in nature: from diatomic hydrogen
(simplest molecule) to biological materials to synthetic macromolecules
(complex)
• Very strong bond.
 Covalent Bonding in H2 Molecule
1s1 Electrons Electron
Pair

H + H H H OR H H
Hydrogen Hydrogen Hydrogen
atom atom Molecule

Highest probability of
finding bonding electrons
is in the overlapping area
between two nuclei–thus
covalent bond can be
described by orbital
overlap and is directional.
Electron-pair
covalent bond

Bonding interaction–
overlapping electron clouds
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Covalent Bonding: Introduction
• When two H-atoms approach one other, nucleus of one H-atom attracts the electron
cloud of the other H-atom. Attraction leads to decrease in energy.
• As both atoms get closer to each other, their electron clouds start to interact and overlap
(share electrons).

• As atoms come much closer, electron-electron and

nucleus-nucleus repulsion become significant.
Atoms repel against each other. Repulsion force
increases the system’s energy.
• Eventually atoms reach an equilibrium point where
attraction forces are balanced against repulsion
forces; the atoms will form a bond by sharing their
electrons, both complete their outer electron structure Potential energy versus separation
and reach the lowest state of energy. distance for two atom hydrogen
atoms. The equilibrium interatomic
• The distance between the nuclei when energy is distance ao in the hydrogen
minimum is called bond length. molecule occurs at the minimum
potential energy Emin .
 Covalent Bond Formation H2

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 Distribution Electron Density in H2

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 Covalent Bonding – Diatomic Molecules

Other diatomic molecules such as Cl2, O2 and N2 share outer p electrons to

attain noble-gas configuration. The number of covalent bonds formed in a
molecule (bond order) is 8 − N, where N = number of outer electrons.

• Example: Cl2 molecule. Outer electrons = 3s2 3p5. N = 7 8 − N = 1 i.e.

can form only one covalent bond (single bond). Bond order is 1

Cl + Cl Cl Cl Cl Cl

Chlorine E.C. Shared pair

atom 2,8,7 of electron Single bond

(Argon configuration)

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 Covalent Bonding – Diatomic Molecules
• O2 molecule. Outer electrons = 2s2 2p4. N = 6
8 − N = 2 i.e. can form two covalent bonds (double bond)
Bond order is 2
XX XX

+ O = OX OR O=O
X
O X
X O
X
X

(2,6) (2,6) (2,8) (2,8)

Two oxygen atoms Neon configuration

• N2 molecule. Outer electrons = 2s2 2p3. N = 5

8 − N = 3 i.e. can form three covalent bonds (triple bond)
Bond order is 3

N + N N N OR N N (Lone pair of
electrons)
(2,5) 2,8 2,8

3 pairs of shared N2
electrons
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 Nonpolar vs. Covalent Bonds
Pure (Nonpolar) Covalent Bond
• Electronegativity difference of the atoms is 0.5 to zero (no dipole).
• Atoms share the bonding electrons equally.
• Between atoms of the same element (e.g. diatomic molecules H2, N2, F2) or atoms
of different elements with similar electronegativities (e.g. C and H in methane CH4)

Polar Covalent Bond

• Significant electronegativity difference (from about 0.5 to 2.0 difference).
• Unequal sharing of valence electrons between bonded atoms – the shared
electrons lean toward the more electronegative element (creates a dipole)
• As difference in electronegativity increases, polarity of the bond increases, and if
the difference is very large, bond becomes ionic.

F2 ∆=0 (nonpolar covalent)

• Example:
HBr ∆=0.7 (polar covalent)
HF ∆=1.9 (highly polar covalent)
NaF ∆=3.1 (ionic)
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 Bonding Between The Models

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 BoundaryRangesforClassifyingTheIonicCharacterofChemicalBonds

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 Electron Density Distributions in H2, F2 and HF

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 Bond Length, Bond Order and Bond Energy
• Bond order: number of shared pairs (covalent bonds) formed in a
molecule.

• Bond energy: energy required to overcome the attraction force between

the nuclei and the shared pair of electrons.

• Bond length: the distance between the nuclei of two bonded atom at the
point of minimum energy (equilibrium) in a covalent bond.

• Relationship between bond order, bond length and bond energy:

• Bond order higher, bond length decreases; bond energy
increases - because attraction force is strong between nuclei
and multiple shared pairs.

C–C 370 kJ/mol 0.154 nm

C=C 680 kJ/mol 0.13 nm
CΞC 890 kJ/mol 0.12 nm
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Example Problem 5

a. Use a polar arrow to indicate the polarity of each

bond: N–H, F–N, I–Cl.

b. Rank the following bonds in order of increasing

polarity: H–N, H–O, H–C.
 Covalent Bonding in Carbon
• Carbon has electronic configuration 1s2 2s2 2p2
Ground State arrangement
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 sp3 covalent
1s bonds are
sp3 formed
Four ½ filled sp3 orbitals
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 valence shell electron
Structure of Diamond
~

pair repulsion

• Carbon forms four sp3 tetrahedral covalent bonds (four single

bonds)with other C atoms.
• This network covalent structure gives diamond extremely high
hardness, high bond strength (711 kJ/mol) and high melting
temperature (3550 °C).
• Diamond is a network covalent solid because all C atoms are bonded
through covalent bonds in the form of an ordered network.

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 Other sp3 Covalent Bond
• Carbon also forms four sp3 tetrahedral covalent bonds with different atoms, e.g.
methane molecule CH4.

• Covalent molecules – also called molecular compounds (gas, liquid or solid).

• Covalent bonds between atoms in the molecule are strong and difficult to
break; but the bond between molecules is weak and breaks easily. Covalent
molecules have low melting and boiling points.

• Example: methane has low melting point at −183°C.

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 Other sp3 Tetrahedral Bond (cont..)

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 Carbon Containing Molecules
• Carbon also forms multiple bonds with itself.
• Double and triple bonds are chemically more reactive.
• Multiple carbon-carbon bonds in carbon-containing
molecules are referred to as unsaturated bonds.

Addition of ethylene molecules to form polyethylene:

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 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.

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 Covalent Bonding - summary
• Covalent molecules (gas molecules, liquid molecules, and molecular solids) have low melting and
boiling points. Covalent bonds between atoms in the molecule are very strong and difficult to break;
but the bond between molecules is weak and breaks easily.

• Molecular solids are brittle (like ionic solids). In each molecule, the bonds between the atoms are
strong but the bonds between molecules are usually weak. This makes many molecular solids brittle.

• Covalent network solids typically have high strength, high hardness, and high melting points. Atoms
are continuously connected to each other through covalent bond in a 3-D tetrahedral network.
Diamond melts at 3550°C, quartz melts at 1550°C because of high bond energies of covalent bond.

• Covalent network solids are brittle because the bonds between the atoms are highly directional and
strongly resist motion when the crystal structure is deformed.

• In covalent solids the number of neighbors (packing efficiency) around an atom depend on the bond
order (the number of shared pairs). The number of neighbors cannot exceed four.

• Covalent solids and molecules are poor conductors of electricity both in solid and in molten state,
because electrons are tightly bonded in shared pairs and no ions are available for charge transport.

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Metallic Bonding
Introduction to Metallic Bonding
Metals are the major elements in the Periodic Table. Useful properties are:
strong (difficult to break), malleable/ductile (can be hammered into thin
sheets), and excellent conductors of electricity and heat.

The high strength of metals suggests that metal atoms are held together by
very strong bonds. But, these bonds also allow atoms to move because
metals are ductile. Metals conduct electricity, which means electrons are
free to move.

Metallic bond is different from ionic and covalent bond because:

• Pure metals are composed of identical atoms; there will be no electron
transfer between atoms – no ions.
• Metals have only 1 to 3 valence electrons; they cannot form covalent
bond because the number of electrons available for sharing is not enough
to produce octet structure.
 Formation of Metallic Bonding
• Atoms in metals are closely packed in crystal structure.
• All atoms contribute their valence electrons to form a “sea of electrons” or “electron charge
cloud”. These valence electrons are delocalized, move freely among atoms, and do not belong to
any specific atom. Hence, they are called free electrons.
• These free electrons are reason for electrical conductivity and ductility.
• Attraction force between positive ion core (metal cations) and negative electron cloud is
referred to as metallic bonding.

• Metallic bond is three-dimensional, similar to ionic

bond.
• Since there are no ions involved, there is no
electrical neutrality restriction.
• Also, the metallic cations are not fixed in place as
they are in ionic solids.
• There are no shared localized electron pairs
between atoms; therefore metallic bonds are
weaker than covalent bonds.
• Since valence electrons are mutually shared by
many atoms, metallic bonds are non-
directional.
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 Metallic Bond and Material Properties
• Bond energies and melting point of metals vary greatly depending on the number of
valence electrons and the percent metallic bonding.
• Fewer the number of valence electrons, attraction force between positive on core
and electron cloud decreases – bond is more metallic – melting point decreases.
• Increased number of valence electrons increases percent of covalent bonding –
increase bond energy and melting point.

Bond energies, melting points, and electron configurations of the fourth-period metals
of the periodic table.

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 Melting Points of the Group 1A(1) & Group 2A(2) Metals

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 Metallic Bond and Material Properties
Strength
Pure metals are significantly more malleable (soft and deformable) than ionic or covalent solids.
Strength of a pure metal can be significantly increased through alloying. This is possible because
metallic bond is unsaturated. So, a metal can form bonds with many other different metal atoms.

High density
Metal atoms are closely packed in crystal lattice. As a result, metals have high density.

Electrical conductivity
Pure metals are excellent conductors of electricity because metals have free electrons. This is
impossible in ionic or covalent solids because their valence electrons are tightly held in place by the
nuclei.

Thermal conductivity
Metals are excellent conductors of heat because metal atoms are closely packed next to each
other, thus heat can be transferred via conduction across the metal rapidly and efficiently.

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 Metallic Bond and Material Properties
Ductility
When force is applied to a metal, the ions in the metal solid can slip past
each other with relative ease, without destroying the metal crystal.

Stress

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 Mixed Bonding
Chemical bonding of ions or atoms can involve more than one type of
primary bond. The following combinations are common:

• Ionic-Covalent Mixed Bonding:

• Most covalent molecules have some degree of ionic bonding, and vice-
versa.
• The greater the electronegativity difference of the elements
involved in ionic-covalent mixed bond, the more ionic is the bond.
• Percent ionic character is calculated using Pauling’s equation.

• Metallic-Covalent Mixed Bonding:

• Commonly observed in transition metals – the high melting points of
metals are due to metallic-covalent mixed bond.
• Group 4A: Transition from pure covalent bond in C, to some metallic
character in Si and Ge, to pure metallic in Sn and Pb.
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 Mixed Bonding
Ionic Character (Pauling Equation)
(where X is electronegativity value)

XA: electronegativities of
the atom A
XB: electronegativities of
the atom B

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 BoundaryRangesforClassifyingTheIonicCharacterofChemicalBonds
(PreviousSlide..)

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Secondary Bonds

1. Fluctuating Dipoles
2. Permanent Dipoles
Secondary Bonds
• Two types of secondary bonds between atoms or molecules involving electric dipoles:
fluctuating dipoles and permanent dipoles. They are also known as VAN DER
WAALS BONDS (FORCES).

• Electric dipoles are created within an atom (or a molecule) when positive and negative
charge centers exist.

• Electric dipoles interact with each other by electrostatic (Coulombic) forces.

Thus, atoms (or molecules) containing dipoles are attracted to each other by these
forces.

• These forces are electrical in nature, like the ionic bond, but much weaker.
Fluctuating Dipoles
 Fluctuating Dipole Bond – Noble Gas
• Very weak attraction forces developed between “complete” atoms (noble gases).

• These bonding forces arise because asymmetrical distribution of electron

charge in these atoms creates electric dipoles.

• Electron charge distribution constantly changes with time, creating a

“fluctuating” dipole in that atom.

• A dipole in one atom induces opposite dipoles in nearby atom. The attractive
forces are very weak but strong enough to hold two noble gas atoms together –
creating weak interatomic nondirectional bonds.

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 Fluctuating Dipole Bonds – Noble Gas

• Liquefaction of noble gases at high pressures and solidification at low

temperatures are due to fluctuating dipole bonds.

• Strength of bonds increases with increasing size of noble-gas atom,

because electrons have more freedom to create stronger dipole moments –
higher mp and bp.

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 Fluctuating Dipole Bonds – Covalent Molecule
• Weak secondary bonds also form between symmetrical covalently bonded
molecules having noble-gas configuration (s2 and s2p6). Example: H2, Cl2,
hydrocarbon series like alkane (CH4).

• Even in a symmetric molecule, at any instant, there will be temporary random

inequality in electron distribution in the molecule (asymmetric charge distribution). This
creates a temporary dipole in that molecule.

• A dipole in one molecule induces opposite dipoles in neighboring molecules. The

forces of attraction are very weak but strong enough to hold the molecules together -
creating weak intermolecular nondirectional bonds. The forces operate only when
molecules are very close to each other.

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 Bonding Between Ar & H2 Electric Dipoles

- +
Argon atom Argon Electric Dipole

Van der waals

bond

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Permanent Dipoles
Concept Map: Permanent Dipole
 Permanent Dipole Bond
• A permanent electric dipole is created due to permanent unequal electron charge
distribution in the molecule.
• E.g. CH3Cl has a permanent dipole; CH4 and CCl4 are symmetrical and have no
dipole. Permanent dipole is stable and does not fluctuate with time.
• Weak bonding forces (i.e. permanent dipole bonding) are created when molecules
interact with each other.
• These bonds, formed by electrostatic (Coulombic) attraction of the dipoles are
directional in nature. They are stronger than fluctuating dipole bond.
• Permanent dipole bonds are important in the bonding of polar covalent bond
molecules such as water and various hydrocarbons.

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 Hydrogen Bonding
• Hydrogen bond is a special class of permanent dipole bond that forms between
polar molecules containing hydrogen.

• Hydrogen bonding occurs when a polar bond containing hydrogen atom (O−H or
N−H) interacts with the electronegative atoms O, N, F or Cl.

• In water molecule, a permanent dipole is created due to asymmetrical arrangement

of H atoms at an angle of 105° with respect to the O atom.

• In hydrogen bonding between water molecules, negative side of one molecule is

attracted by coulombic forces to positive side of nearby water molecule.

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 Hydrogen Bond in Polymers

Hydrogen bonding is important for strengthening the bonding between polymer molecular
chains. In PVC, dipole-dipole interactions are due to the polarity of the carbon-chlorine
bonds. Cl is more electronegative than C, and attracts the electrons in the bond
towards itself. That makes Cl atoms slightly negative and C atoms slightly positive. These
permanent dipoles add to the attractions due to the temporary dipoles.

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 Secondary Bond
• The intermolecular forces in polymers can be affected by dipoles in the monomer units and play
a large part in determining a polymer's properties. These stronger forces typically result in higher
strength and higher melting points.

• Polymers containing amide (N−H) or carbonyl groups (C=O) can form hydrogen bonds
between adjacent chains; the partially positively charged hydrogen atoms in N-H groups of one
chain are strongly attracted to the partially negatively charged oxygen atoms in C=O groups on
another. These strong hydrogen bonds result in the high tensile strength and melting point of
nylons (190-350°C).

• PVC have dipole-dipole bonding between the Cl atoms in C=Cl groups and the hydrogen
atoms in H-C groups. Dipole bonding is not as strong as hydrogen bonding, so PVC’s melting
point and strength (100-260°C) is lower than nylon.

• Ethylene, is symmetrical and has no permanent dipole. Attractive forces between PE chains
arise from weak van der Waals forces. As two polymer chains approach their electron clouds
repel each other. This lowers the electron density on one side of a polymer chain, creating a
slight positive dipole on this side. This charge is enough to attract the second polymer chain.
Van der Waals forces are quite weak, so PE has a lower melting temperature compared to nylon
and PVC.

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Summary
Summary: Bonding and Material
Tetrahedron of Structure, Bonding and Material Type

Examples of bonding in materials:

Metals: Metallic
Ceramics: Ionic/ Covalent
Polymers: Covalent and Secondary
Semiconductors: Covalent or Covalent / Ionic
 Summary: Compound, Ion, Molecule
There are two fundamental types of compounds: ionic and molecular.

Ionic compounds are composed of positively and negatively charged ions held together
by electrostatic attractions casually referred to as ‘ionic bonds.’ Molecular compounds
are composed of molecules, which are groups of atoms joined together by pairs of
shared electrons. Solid ionic compounds do not contain molecules. Instead, because
opposite charges attract one another, the ions stack themselves in crystals such that
positive ions are surrounded by negative ions, and vice versa.

An ionic compound has A molecular compound

alternating positively and has discrete groups of
negatively charged particles atoms joined together to
in a pattern that extends in form molecules.
all three dimensions.
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 Summary: Bond Energy & Melting Temperature
Bonding energies and melting temperatures for various substances

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