CE 241

Materials Science

ATOMIC STRUCTURE, BONDING,

PROPERTIES
Atomic structure, bonding, and properties

• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

1
Review your chemistry notes !!!
(if necessary )

2
 Classification of materials
• Metals: Metallic bond
• Ceramics: Ionic / Covalent bonds
• Polymers: Covalent and Secondary bonds
• Semiconductors: Covalent or covalent / ionic
bonds

3
 Atomic structure
Atoms, Elements, Molecules, Compounds

4
 Atomic structure
Molecule:
- formed by chemical bonding of two or more atoms.
- smallest unit of a chemical that retains the overall chemical
properties.

Compound:
- formed by chemical combination of different elements in
defined proportions.
- can be chemically decomposed into simpler substances.

5
Atomic Structure (from freshman chem.)
• atom – electrons – 9.11 x 10-31 kg
protons
neutrons } 1.67 x 10-27 kg

• atomic number = # of protons in nucleus of atom

= # of electrons of neutral species

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

Atomic wt = wt of 6.023 x 1023 molecules or atoms

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

6
 Electronic Structure
• Electrons have wavelike and particulate properties.
– Means electrons are in orbitals defined by a probability.
– Each orbital at discrete energy level 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

7
 Electron energy states
Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.
4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister 7e.
2p L-shell n = 2
2s

1s K-shell n = 1
8
 Survey of elements
• Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s1
Helium 2 1s2 (stable)
Lithium 3 2
1s 2s 1
Beryllium 4 1s22s2
Boron 5 1s22s22p 1
Carbon 6 1s22s22p 2 Adapted from Table 2.2,
... ... Callister 7e.

Neon 10 1s22s22p 6 (stable)

Sodium 11 2 2 6
1s 2s 2p 3s 1
Magnesium 12 1s22s22p 63s2
Aluminum 13 1s22s22p 63s23p 1
... ...
Argon 18 1s22s22p 63s23p 6 (stable)
... ... ...
Krypton 36 1s22s22p 63s23p 63d 10 4s24p6 (stable)

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

9
 Electron configurations
• Valence electrons – those in unfilled shells
• Filled shells more stable
• Valence electrons most available for bonding and
tend to control the chemical properties

– example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

10
 Electron configurations
e.g. atomic # = 26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d
4p N-shell n = 4
valence
3d electrons

4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister 7e.
2p L-shell n = 2
2s

1s K-shell n = 1

11
The periodic table (of the elements)
• Columns: Similar Valence Structure

inert gases
give up 1e
give up 2e

accept 2e
accept 1e
give up 3e

H He
Li Be O F Ne Adapted from
Na Mg S Cl Ar Fig. 2.6,
Callister 7e.
K Ca Sc Se Br Kr
Rb Sr Y Te I Xe
Cs Ba Po At Rn
Fr Ra

Electropositive elements: Electronegative elements:

Readily give up electrons Readily acquire electrons
to become + ions. to become - ions.
12
 Electronegativity
• Ranges from 0.7 to 4.0,
• 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.

13
 Important observation
• Valence electrons determine all of the
following properties
1) Chemical
2) Electrical
3) Thermal
4) Optical
5) …

14
 Interatomic bonding
 Atoms/Molecules link to form materials
 When this linkage is self-sufficient, the resultant will be a gas, a
liquid or a solid.

e.g.
Atoms bond to form long chains → Polymers
Atoms bond in regular 3-D arrays → Metals

 Bonding b/w atoms

result of the tendency of all systems to take up their lowest
energy state
possession of 8 electrons in their outer most shell

15
 Interatomic bonding

 Atoms of the elements having 5, 6, 7 e- in their outermost shell

accept 3, 2, 1 electrons respectively.

 Those having 1, 2 or 3 e- give up their outermost shell electrons

to remain with 8 e- in their underlaying shell.

 Atoms having 4 valence electrons may behave in either way.

 Valence electrons: The electrons in the outermost shell.

16
 Atomic bonding

Atomic
Bonding

Secondary
Primary Bonds
Bonds

van der
Ionic Covalent Metallic
Waals

17
 Ionic bonding

 11Na & 17Cl

attracted to each other by electrostatic force

an ionic compound (NaCl) forms

18
 Ionic 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]

19
 Ionic bonding
• Occurs between + and - ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction
20
 Coulombic
interaction
Cation Anion
Ionic Bonds are non-directional ! Note the relative sizes of ions
Na+ shrinks and Cl- expands

Na+ 21
Cl-
 Properties of ionic bonds
1. Force of attraction electrostatic (Coulombic)
2. non-directional (each + ion is surrounded by as many –
ions as possible)
3. strong, stable, brittle
4. High melting point (as the # of e- involved in the bond
increases, melting point increases)
5. Poor electrical conductivity
6. between atoms of different electronegativity values (one
high, one low).
- obviously, can form only b/w different atoms.

22
 Properties of ionic bonds
• 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

23
 Examples of ionic bonding
NaCl
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

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.

• Predominant bonding in Ceramics

24
 Covalent bonding
• similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals dominate
bonding
• e.g. CH4
shared electrons
H
C: has 4 valence e-, CH 4
from carbon atom
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
Electronegativities H from hydrogen
are comparable. atoms

Adapted from Fig. 2.10, Callister 7e.

25
 Covalent bonding
e- are shared b/w atoms.

elements showing covalent bond obey (8-N) rule

When N=7, such as Cl

8-7=1 → the atoms pair off as diatomic molecules.

Cl + Cl Cl Cl

26
 Covalent bonding
 When N=6 such as S
6
16S : 1s2 2s2 2p6 3s2 3p4 8-6=2

 each atom has two closest neighbors so they form long chains.

S O, Se, Te behave like S.

S

S S

27
 Covalent bonding
 When N=5, such as

33As : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p3

8-5=3 → They require 3 closest neighbors so they form

sheets of atoms.

 When N=4, such as 6C : 1s2 2s2 2p2

8-4=4 → They form 3-D structures.

28
Ethylene
molecule

29
 Properties of covalent bonds
1. based on electron sharing.
2. directional (each atom is surrounded by a definite
amount of other atoms)
3. hard and strong (slightly less than ionic)
4. Very high melting point.
5. Poor electrical conductivity.
6. Forms b/w atoms with high electronegativity.
- not limited to elements
- many compounds are covalent, like HCl, H2O.

30
 Metallic bonding
occurs in electronegative atoms where they want to
give away electrons

can be considered as a special type of covalent bond

instead of sharing particular valance electrons, general
sharing of valance e- is responsible for the bond.

Valance electrons are detached from atoms, and

spread in an “electron cloud” that holds the ions
together.

31
 Metallic bonding
 The positive metal ions are arranged regularly in a
“crystal lattice” and a cloud of valance electrons
surround them.

Electron cloud

Metal ions

32
 Properties of metallic bonds
1. based on electron sharing. Electrons are
shared among all atoms.
2. Non directionality - desire for the largest
number of nearest neighbors.
3. High thermal and electrical conductivity
- Since the valance e- are not bound to any particular
atom
4. Moderately lower melting point.
5. Weakest primary bond.
6. Forms between atoms with low
electronegativity.
33
 Mixed bonding ?
• Ionic-Covalent Mixed Bonding
 (X A -X B )2 
- % ionic character =  - 
x (100 %)
4
1- e
 
 

where XA & XB are “Pauling electronegativities”

3.5
 3

electronegativity
2.5

Difference in
2
1.5
e.g. MgO XMg = 1.3 1

XO = 3.5 0.5
0
0 20 40 60 80 100

 (3.5 -1.3)2  % ionic

 - 
% ionic character  1 - e 4  x (100%)  70.2% ionic
 
  34
 Secondary bonding
Arises from interaction between dipoles
• Fluctuating dipoles
asymmetric electron eg: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding bonding
Adapted from Fig. 2.13, Callister 7e.
• Permanent dipoles-molecule
induced
- general case: + - secondary + -
bonding
Adapted from Fig. 2.14,
secondary Callister 7e.
- e.g. liquid HCl H Cl H Cl
bonding

- e.g. polymer

35
Secondary bonding (mainly van der Waals)

universal to all atoms and molecules

very weak  may be neglected when primary

bonds exist

describes a dipolar attraction b/w neutral atoms.

36
Secondary bonding (mainly van der Waals)
 Since electrons move around nucleus (electronic charge is in
motion), it is possible for electrons to be located
unsymmetrically with respect to nucleus at a moment.
 In this way a dipole will be formed.
 Van der Waals bonding is a result of an attraction b/w opposite
poles of these dipoles.

Dipole: Pair of equal and

opposite electric charges.

37
 Hydrogen bonding
 valance electrons of water molecule spend more of its time
around the O atom than the H atom
a dipole is formed
oxygen end develops a partial negative charge (because of
the negative charge on the electrons).
hydrogen end of develops a partial positive charge.

 Negative end of each water molecule is attracted by a positive

end of another water molecule

38
 Summary
Type Bond Energy Comments

Ionic Large! Non-directional (ceramics)

Covalent Variable Directional

large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Non-directional (metals)
small-Mercury

Secondary smallest Directional

inter-chain (polymer)
inter-molecular
39
40
 Summary
• Metals: Metallic bond
• Ceramics: Ionic / Covalent bonds
• Polymers: Covalent and Secondary bonds
• Semiconductors: Covalent or covalent / ionic
bonds

41
Properties rel. with bonding – melting point
• 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”
42
Prop’s rel. with bonding – coeff. of thermal
expansion

• a ~ slope at ro

l l
larger larger α  less resistance to expansion

smaller α
43
Summary: primary bonds

44
 Atomic bonding in solids

• bonding energy

• interatomic spacing

45
 Interatomic spacing
For two ions to come closer to each other, two types of
forces are in effect.

Attractive Forces (+) pull atoms together

Repulsive Forces (-) develop when atoms are brought into
close proximity (~nm). There is mutual electronic
repulsion between the two atoms because of the
electrons around an atoms.

46
 x0
Tensile (+)

Fa(x): Attractive force

Ft(x): Total force
Force

x,Interatomic Spacing
ompressive

Fr(x): Repulsive
force

47
-)
 Remember ?
Coulomb's law describes the magnitude of the electrostatic force
between two electric charges. The Coulomb's law formula is:
F = Ke * q1 * q2 / r2
where:
q1: Charge of object 1
q2: Charge of object 2
r: Distance between the two objects
F: Force between the two objects. A positive force implies a
repulsive interaction, while a negative force implies an attractive
interaction
Ke = Coulomb Constant, 8.988 * 109 N.m2.C-2

48
 Interatomic spacing

Forces of attraction (Fa)→Attractive forces btw. atoms

decrease with interatomic spacing, x.
(is inversely proportional with x)

Forces of repulsion (Fr)→As atoms come closer, repulsive

forces dominate.
(is inversely proportional to a higher power of x than Fa)

49
 Interatomic spacing
 Total force SF = Fa+Fr
 When Fa=Fr → Equilibrium point → @ x=x0

 x0
 also known as equilibrium spacing
 a very specific distance for a given pair of atoms or
ions
 A large amount of force is needed to change (stretch
or compress) that distance.
 Therefore, generally atoms can be assumed as hard
balls when atomic arrangements are considered.

50
 Bonding energy
• Sometimes it is more convenient to work with the potential
energies between two atoms instead of forces.

E   Fdx

For atomic systems

x
En   Fdx

where En, Ea, Er are the net,
x0
attractive and repulsive
En   ( Fa  Fr )dx

energies for two isolated and
En  Ea  Er adjacent atoms.

51
 @ x  x0
x0

Eb   Fdx


Eb is the bonding energy that

represents the energy required
to separate two atoms to an
infinite separation. Eb
52
 Bonding energy and material properties
 magnitude of the bonding energy and the shape of E-x curve vary
from material to material and they both depend on the atomic
bonding.

 Many material properties depend on atomic relationships (Eb,

curve shape and bond type).
Melting point
Hardness
Modulus of Elasticity=dF/dx at x=x0
Thermal expansion
Conductivity of metals

53
54
 Factors affecting atomic radius
1. Temperature: As T increases, x0 also increases.
2. Ionic Value: An electropositive atom (Fe+2) has a smaller
radius than a neutral atom (Fe).
Similarly an
electronegative
atom (O-2) has a
higher radius than
a neutral atom
(O).

55
 Factors affecting atomic radius
3. Surrounding Atoms: As the number of
surrounding atoms around a bond increases, the
interatomic distance increases due to the
repulsive forces developed by electrons.
4. Covalency: As the number of shared electrons
increases, atoms will attract each other more and
the radius decreases.

56
e.g. r: Interatomic distance in nm (*10-9 m)
A B A: -7.2 * 10-20 [J (nm)2]
U= + [J]
rm rn
B: 9.4 * 10-25 [J (nm)10]
m = 2, n = 10
-7.2 * 10-20 9.4 * 10-25
U= +
r2 r10
Find r0 where the bond is most stable? Energy is minimum
Calculate the net energy?

dU U = A r-m + B r-n
=0
dr dU
= -m A r-m-1 – n B r-n-1
dr

57
dU
= -2 * (-7.2*10-20) * r-3 – 10*(9.4*10-25)*r-11 = 0
dr

14.4*10-20 9.4*10-25
= → r8 = 6.53*10-5
r 3 r11
r = 0.299 nm

-7.2*10-20 + 9.4*10-25
Umin = = -6.40*10-19 [J]
(0.299)2 (0.299)10

58
59