KC2303 Material Technology

Chapter 2

Atomic Structure and Bonding

2-1

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

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

Proton
Mass : 1.673 x 10 24 g Charge : 1.602 x 10 19 C 2-2

Neutron
Mass : 1.675 x 10 24 g 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.

Example :- Carbon has 6 Protons and 6 Neutrons. Atomic Mass = 12.

One Atomic Mass unit is 1/12th of mass of carbon atom. One gram mole = Gram atomic mass of an element.

Example :-

One gram Mole of Carbon

2-3

12 Grams Of Carbon

6.023 x 1023 Carbon Atoms

Atomic and Molecular Bonds

Primary Atomic Bonds

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
Secondary Atomic and Molecular Bonds

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.

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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

Cation +ve charge

Electrostatic Attraction

Anion -ve charge

IONIC BOND
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Ionic Bonding - Example

Ionic bonding in NaCl
3s1 Sodium Atom Na
I O N I C B O N D

3p6

Chlorine Atom Cl

Sodium Ion Na+

Chlorine Ion Cl -

Figure 2.10

2-15

Ion Arrangements in Ionic Solids

Ionic bonds are Non Directional, anion attract surrounding cations with the same magnitude 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.

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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 CsCl BaO

Lattice energy = 766 KJ/mol Melting point = 801oC Lattice energy = 649 KJ/mol Melting Point = 646oC Lattice energy = 3127 KJ/mol Melting point = 1923oC

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Contribution to Material Stability

Strong bonding-unbreakable, high melting

temperature Brittle-electrons no space to change position even though large force applied Thermally less stable and less conductiveelectrons in one position and cannot move

Covalent Bonding
Cooperative sharing of valence electrons between two

adjacent 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
Overlapping Electron Clouds

Electron Pair

H + H
1s1 Electrons

H H
Hydrogen 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
Bond Energy=160KJ/mol

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

O + O

HH

O=O
Bond Energy=28KJ/mol

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

N + N

N N

Bond Energy=54KJ/mol

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Covalent Bonding-Characteristics
Electron sharing between orbitals

Lots of sharing from outer orbitals, larger covalent

bond energy. Double bond energy is higher than single bonded ones. Single covalent bond indicates two atoms with a pair of electron valence is also called saturated bond. Multiple covalent bond (doble bond and triple bond) is reactive bond and non-saturated bond. Involves non metallic atoms and is localized, directional bond

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
Figure 2.18

Tetrahedral arrangement in diamond

Figure 2.19

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Carbon Containing Molecules

In Methane, Carbon forms four covalent bonds with Hydrogen. Molecules are very weekly bonded together resulting Methane Figure 2.20 molecule in low melting temperature (-183oC). Carbon also forms bonds with itself. Molecules with multiple carbon bonds are more reactive.

Examples:-

C C
H H Ethylene
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Acetylene

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.

C C C C C

H
Figure 2.23

C
H Structure of Benzene Simplified Notations

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Metallic Bonding

Atoms in metals are closely packed in crystal structure. Atoms are so close together that their 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

2-28

Figure 2.24

Metallic Bonds (Cont..)

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

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Secondary Bonding (Van der Waals Bonding)

Attraction without electron transfer or electron sharing Secondary bonds are due to attractions of electric dipoles in

atoms or molecules (electric dipole moment is created when two equal and opposite charges are separated) Dipoles are created when positive and negative charge centers exist.

Dipole moment= =q.d +q d

permanent and fluctuating.

-q

q= Electric charge d = separation distance

Figure 2.26

There two types of bonds

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Fluctuating Dipoles

Weak secondary bonds in noble gasses; i.e argon gas Both 2 atoms cannot share electron sinceouter orbital fully occupied. Dipoles are created due to asymmetrical distribution of electron charges. Electron cloud charge changes with time.

Symmetrical distribution of electron charge 2-31

Figure 2.27 Asymmetrical

Distribution (Changes with time)

Permanent Dipoles

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

Examples:- Symmetrical

CH4

Arrangement Of 4 C-H bonds

No Dipole moment

CH3Cl

Asymmetrical Tetrahedral arrangement

Creates Dipole

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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
Figure 2.28

H
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Hydrogen Bond