Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Chapter 2 Outline

• Review of Atomic Structure

Electrons, Protons, Neutrons, Quantum
mechanics, Electron states, The Periodic Table

Interatomic bonding
First step in understanding material properties
• Atomic Bonding in Solids
Energies vs. Forces
• Periodic Table

• Primary Interatomic Bonds

Ionic
Covalent
Metallic
• Secondary Bonding (Van der Waals)

• Molecules and Molecular Solids

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering1

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Adhesive tape

Gecko
Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering3
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering4

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic Structure
All matter is composed of atoms.

Understanding the structure of atoms is

critical to understanding the nature of
biological molecules.
We can examine and describe the
structure of materials at five different
levels
1. atomic structure;
2. short- and long-range atomic
arrangements;
3. nanostructure;
4. microstructure; and
5. macrostructure. 5

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic Structure

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic Structure

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic Structure

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic Structure

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic Structure

10

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic Structure
NOTE!!!

11

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic Structure

12

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic Structure

13

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic Structure

14

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Review of Atomic Structure

Atoms = nucleus (protons and neutrons) + electrons

Charges:
Electrons (-): protons(+) 1.6 × 10-19 Coulombs.
Neutrons are electrically neutral.

Masses:
Protons and Neutrons ~1.67 × 10-27 kg.
Electron 9.11 × 10-31 kg

Atomic mass = # protons + # neutrons

Atomic number (Z) = # protons

chemical identification of element

Isotope number  # neutrons

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

1
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Atomic mass units. Atomic weight.

Atomic mass unit (amu)
1 amu = 1/12 of mass of most common isotope of C
6 protons (Z=6) and six neutrons (N=6).
The atomic mass of 12
C atom is 12 amu.

Atomic weight: A
Weighted average of atomic masses of naturally
occurring isotopes.
Atomic weight of carbon is 12.011 amu.
Atomic weight is often in mass per mole.
A mole
Amount of matter with mass in grams equal to
the atomic mass in amu
(A mole of carbon has a mass of 12 grams).

One Mole contains Avogadro’s number of atoms,

Nav = 6.023 × 1023.
Nav = 1 gram/1 amu.
Example:
Atomic weight of iron = 55.85 amu/atom = 55.85 g/mol
Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering
1
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Some simple calculations

Number density, n: (number of atoms per cm3)
Mass density, ρ (g/cm3)
Atomic mass, A (g/mol):

n = Nav × ρ / A
Calculate the number density for the
following atoms/molecules
Graphite (carbon): ρ = 2.3 g/cm3, A = 12 g/mol

Diamond (carbon): ρ = 3.5 g/cm3, A = 12 g/mol

Water (H2O) ρ = 1 g/cm3, A = 18 g/mol

Calculate the number of atoms in 100 g of

silver (Ag). ρ = 10.49 g/cm3, A = 107.8 g/mol
n = 5.58x1023
Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering
1
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Some simple calculations

• Scientists are considering using

nanoparticles of such magnetic
materials as iron-platinum (Fe-Pt) as
a medium for ultra-high density data
storage. Arrays of such particles
potentially can lead to storage of
trillions of bits of data per square
inch—a capacity that will be 10 to
100 times higher than any other
devices such as computer hard disks.
If these scientists considered iron
(Fe) particles that are 3 nm in
diameter, what will be the number of
atoms in one such particle?

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

1
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Some simple calculations

1. Aluminum foil used for storing food
weighs about 0.3 g per square inch. How
many atoms of aluminum are contained in
this sample of foil?
2. In order to plate a steel part having a
surface area of 200 in.2 with a 0.002 in.
thick layer of nickel, (a) how many atoms
of nickel are required and (b) how many
moles of nickel are required?

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

1
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Electrons in Atoms (I)

Electrons form a cloud

around the nucleus
Radius ~ 0.05 – 1nm.

Picture looks like a mini

planetary system. But
Quantum Mechanics says
this analogy is not correct

Electrons “orbits” are 'fuzzy‘

Can only discuss probability of finding it at some distance
from the nucleus.
Only certain “orbits” or shells are allowed.
Shells identified by principal quantum number n,
n related to size of radius (and energy)
n = 1, smallest; n = 2, 3 .. are larger.

Second quantum number l, defines subshells.

Two more quantum numbers characterize states within

subshells.
Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering
2
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

BOHR ATOM

21

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

WAVE MECHANICAL
MODEL OF ATOM

22
Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

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 is
determined by quantum numbers.
 
Quantum # Designation
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

23
Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

The energy level to which each electron

belongs is identified by four quantum
numbers.
1. principal quantum number n=1,2...
– reflects the grouping of electrons into
sets of energy levels known as shells
2. The azimuthal or secondary quantum
number l (orbitals)
– describe the energy levels within each
shel l=0, 1, 2, . . . , n-1
3. the magnetic quantum number ml
– specifies the orbitals associated with a
particular azimuthal quantum number
within each shell ml= 2l +1 (-l and +l)
4. The spin quantum number ms

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

2
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

The Aufbau Principle

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

2
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Electron Energy States

Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N-shell n = 4

3d

4
s
Energy 3p M-shell n = 3
3
s
Adapted from Fig. 2.4,
Callister & Rethwisch
2p 8e.
L-shell n = 2
2
s

1 K-shell n = 1
s
26
Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s1
Helium 2 1s2 (stable)
Lithium 3 1s22s1
Beryllium 4 1s22s2
Boron 5 1s22s22p1 Adapted from Table
2.2, Callister &
Carbon 6 1s22s22p2 Rethwisch 8e.
... ...

Neon 10 1s22s22p6 (stable)

Sodium 11 1s22s22p63s1
Magnesium 12 1s22s22p63s2
Aluminum 13 1s22s22p63s23p1
... ...

Argon 18 1s22s22p63s23p6 (stable)

... ... ...
Krypton 36 1s22s22p63s23p63d104s24p6 (stable)

• Why? Valence (outer) shell usually not filled completely.

27
Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Electron Configurations
• Valence electrons – those in unfilled
shells
• Filled shells more stable
• Valence electrons are most available
for bonding and tend to control the
chemical properties

– example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

28
Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3d 6 4s2
3p6

4d valence
4p N-shell n = 4 electrons

3d

4
s
Energy 3p M-shell n = 3
3
s
Adapted from Fig. 2.4,
Callister & Rethwisch
8e.
2p
L-shell n = 2
2
s

1 K-shell n = 1
s

29
Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Elements

30

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Periodic Table of the

Elements

31

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Periodic Table

Elements in same column share similar properties.

Group number  number of electrons available
for bonding 0.9025 2.718

0: Inert gases (He, Ne, Ar...) filled subshells: chem. inactive

IA: Alkali metals (Li, Na, K…) one electron in outer shell
eager to give up electron – chem. active
VIIA: Halogens (F, Br, Cl...) missing one electron in outer
shell - want to gain electron - chem. active
Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering
3
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Periodic Table - Electronegativity

Figure 2.7 from text

Electronegativity - how willing atoms are to

accept electrons
Subshells with one electron - low electronegativity
Subshells with one missing electron -high
electronegativity
Electronegativity increases from left to right

Metals are electropositive – can give up their few

valence electrons to become positively charged ions

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

3
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Electrons in different
shells

34
Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Binding Energy and Interatomic

Spacing
• Interatomic Spacing:The equilibrium
distance between atoms is caused by a
balance between repulsive and attractive
forces.
• Binding energy: the energy required to
create or break the bond.

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

3
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Bonding Energies and Forces

repulsion
Potential Energy, E

attraction
equilibrium
Typical potential between two atoms
Repulsion when they are brought close together
Related to Pauli principle
(As electron clouds overlap energy increases)

Attractive part: at large distances

(Depends on type of bonding)

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

3
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Bonding Energies and Forces

a0
Potential Energy

Ut=Ur+Ua

E0
E0 – bond energy
F= dE/da
a0 –equilibrium distance
a0
at a0, dE/da = 0,  Fa = Fr

Tensile
(+)
Force

Compressive
(-)

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

3
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Effect of binding energy on

Properties
• Materials with high binding
energy have
→ high strength
→ high melting temp.
→ modulus of elasticity
→ low coefficient of thermal
expansion

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

3
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

3
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

The electron volt (eV)

Energy unit convenient for atomic bonding

Electron volt –
energy lost / gained when an electron is taken
through a potential difference of one volt.
E=qV

For q = 1.6 x 10-19 Coulombs

V = 1 volt

1 eV = 1.6 x 10-19 J

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

4
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Elements

41

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Ionic bond – metal + nonmetal

donates accepts
electrons electrons
 
Dissimilar electronegativities  

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

[Ne] 3s2 

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

[Ne] [Ne]

42
Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Elements

43

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Chemical Bonds

44

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Types of Bonding
Primary Bonding: e- are transferred or shared
Strong (100-1000 KJ/mol or 1-10 eV/atom)
Ionic:
Example - Na+Cl
Strong Coulomb interaction between
a positive atom (lost an electron, Na+) and
a negative atom (an extra electron, Cl-)

Covalent: electrons shared between the atoms.

Example - H2

Metallic:
Atoms lose some electrons from valence band
Those electrons are shared by all the material

Secondary Bonding: no e- transferred or shared

Interaction of atomic/molecular dipoles
Weak (< 100 KJ/mol or < 1 eV/atom)
 Fluctuating Induced Dipole (inert gases, H2, Cl2…)
 Permanent dipoles (polar molecules - H2O, HCl...)

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

4
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Ionic Bonding (I)

Mutual ionization by electron transfer
(remember electronegativity table)
• Anion = negatively charged atom
• Cation = positively charged atom
Ions are attracted by strong coulombic interaction
• Oppositely charged atoms attract
• An ionic bond is non-directional

Example: NaCl
Na has 11 electrons, 1 more than needed for a full outer
shell (Neon)

11 Protons Na 1S2 2S2 2P6 3S1 donates e-

11 Protons Na+ 1S2 2S2 2P6 10 e- left

Cl has 17 electron, 1 less than needed for a full outer shell

(Argon)
17 Protons Cl 1S2 2S2 2P6 3S2 3P5 receives e-
17 Protons Cl- 1S2 2S2 2P6 3S2 3P6 18 e-

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

4
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Chemical Bonds

47

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Ionic Bonding (II)

e-
Na Cl Na+ Cl-

• Electron transfer reduces energy of the system

• Na shrinks and Cl expands

Ionic bonds: very strong, nondirectional bonds

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

4
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Chemical Bonds

single double< triple

bond
< bond bond
49

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Chemical Bonds

50

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Chemical Bonds

Electronegativity is an atom’s
affinity for electrons.

Differences in electronegativity
dictate how electrons are
distributed in covalent bonds.
- nonpolar covalent bonds = equal
sharing of electrons
- polar covalent bonds = unequal
sharing of electrons

51

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Covalent Bonding (I)

Electrons shared between the atoms.

Valence electrons spend more time between nuclei
than outside  bonding.

Covalent bonds- HIGHLY directional in direction of

greatest orbital overlap

Example: Cl2 molecule. ZCl =17 (1S2 2S2 2P6 3S2 3P5)
N’ = 7, 8 - N’ = 1  can form only one covalent bond

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

5
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Covalent Bonding (II)

Example: Carbon Zc = 6 (1S2 2S2 2P2)
N’ = 4, 8 - N’ = 4  can form up to four covalent
bonds
ethylene molecule:

polyethylene molecule:

ethylene mer

diamond:
(each C atom has four
covalent bonds with four
other carbon atoms)

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

5
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Covalent Bonding (III)

2-D schematic of the “spaghetti-like” structure
of solid polyethylene

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

5
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Metallic Bonding
Valence electrons are detached from atoms
Spread in an 'electron sea'
that "glues" the “ions” together

Metallic bond is non-directional  atoms pack closely

Electron cloud from valence electrons

ion core

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

5
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Chemical Bonds

56

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Secondary Bonding (I)

Secondary = physical bond
(as opposite to chemical bond that involves e- transfer)
Interaction of dipoles
Is weak, ~0.1 eV/atom or ~10 kJ/mol.

_ _ -two dipoles attract

+ +

Permanent dipoles exist in some molecules

polar molecules: e.g. HCl, H2O
Due to asymmetry of positive and negative regions
Strongest among secondary bonds.

Polar molecule induces a dipole in adjacent non-polar

molecule.
Attraction between the permanent and induced dipoles.

Fluctuations of electron density distribution in one

atom A is felt by the electrons of an adjacent atom:
Mutual dipoles induced (van der Waals)
This bond is the weakest (He-Ne, H2 - H2).

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

5
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Secondary Bonding (II)

Example: hydrogen bond in water. The H end of the
molecule is positively charged and can bond to the
negative side of another H2O molecule (the O side of the
H2O dipole)

H H

-
+ +
Dipole

“Hydrogen bond” – secondary bond formed between

two permanent dipoles in adjacent water molecules.

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

5
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Secondary Bonding (III)

Hydrogen bonding in liquid water
from a molecular-level simulation

Molecules: Primary bonds inside, secondary bonds

among each other

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

5
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Secondary Bonding (IV)

The Crystal Structures of Ice

Hexagonal Symmetry of Ice Snowflakes

Figures by Paul R. Howell

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering
6
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Summary (I)

Examples of bonding in Materials:

Metals: Metallic
Ceramics: Ionic / Covalent
Polymers: Covalent and Secondary
Semiconductors: Covalent or Covalent / Ionic

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

6
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Summary (II)

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

6
Introduction To Materials Science, Chapter 2, Atomic Structure -Interatomic Bonding

Summary (III)
Make sure you understand language and concepts:
 Atomic mass unit (amu)
 Atomic number
 Atomic weight
 Bonding energy
 Coulombic force
 Covalent bond
 Dipole (electric)
 Electron state
 Electronegative
 Electropositive
 Hydrogen bond
 Ionic bond
 Metallic bond
 Mole
 Molecule
 Periodic table
 Polar molecule
 Primary bonding
 Secondary bonding
 Van der Waals bond
 Valence electron

Addis Ababa Institutes of Technology, School of Mechanical & Industrial Engineering

6