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CHAPTER 2:
BONDING AND PROPERTIES

ISSUES TO ADDRESS...
• What promotes bonding?

• What types of bonds are there?

• What properties are inferred from bonding?

‹1›

Atom

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Atomic Structure

• Some of the following properties

1) Chemical
2) Electrical
3) Thermal
4) Optical
are determined by electronic
structure

‹3›

Atomic Structure (Freshman Chem.)

• atom – electrons mass=9.11 x 10-31 kg , Charge -1.6710-19C

protons mass=1.67 x 10-27 kg Charge +1.6710-19C

neutrons mass=1.67 x 10-27 kg . Not charged

• atomic number [ Z]= # of protons in nucleus = # of electrons of neutral

species
Z[ H]= 1 , Z[U]= 92
• A [=] atomic mass unit = amu = sum of the mass of protons and
neutrons= 1/12 mass of 12C

For a given element number of protons in any atom is the same, number of
neutrons might differ so an atom of same element may have 2
different atomic masses: These atoms are ISOTOPES

Atomic wt = wt of 6.023 x 1023 molecules or atoms

1 amu/atom = 1g/mol
Example: atomic weight of carbon‹4›
C 12.011 amu/atom= 12.011 g/mol
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Bohr’s Atomic Model

• Treats electrons as particles

revolve around the nucleus in
discrete orbitals.

•The position of any electron is

exact and defined by its orbital.

•Electrons are quantized: They

only allowed to have specific
values of energy.

‹5›

Wave Mechanical (Schrodinger)

• Electrons exhibits
both particle and wave
characteristics

• In this theory the

exact location of
electrons are not
known; only their
probability density
functions (PDF)

‹6›
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Wave Mechanical Model

– Each electron at discrete energy level is defined by 4
quantum numbers.
– These numbers describe the size, shape and spatial
orientation of an electron PDF are described by.

– Pauli described a fourth quantum number as “electron

spin”

Quantum # Designation
n = principal (energy level-shell) K, L, M, N, O (1, 2, 3, etc.)
l = azimuthal related to shape of sub-shell s, p, d, f (0, 1,
2, 3,…, n-1)
ml = magnetic ( number of energy states for each sub shell)
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›
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• Electron shells are

identified by a number and a
letter
• Number: value of n
• Letter: value of l
– F for l=3

‹9›

• Maximum number of electrons permitted in a

sub-shell is: 2(2l+1), or 2, 6, 10, 14

• Example: for Oxygen at ground zero:

8 electrons total and distributed: 1s22s22p4

‹10›
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Electron Configuration and Subshells

‹11›

SURVEY OF ELEMENTS
• Most elements: Electron configuration not stable.
Element Atomic # Electron configuration
Hydrogen 1 1s 1
Helium 2 1s 2 (stable)
Lithium 3 1s 2 2s 1
Beryllium 4 1s 2 2s 2
Boron 5 1s 2 2s 2 2p 1 Adapted from Table 2.2,
Carbon 6 1s 2 2s 2 2p 2 Callister 7e.
... ...
Neon 10 1s 2 2s 2 2p 6 (stable)
Sodium 11 1s 2 2s 2 2p 6 3s 1
Magnesium 12 1s 2 2s 2 2p 6 3s 2
Aluminum 13 1s 2 2s 2 2p 6 3s 2 3p 1
... ...
Argon 18 1s 2 2s 2 2p 6 3s 2 3p 6 (stable)
... ... ...
Krypton 36 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 (stable)

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

‹12›
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Pauli exclusion principle

• No two electrons may have the same four

quantum numbers values (n, l, ml, ms).

• These numbers are used to characterize

the energy levels and arrangement of
electrons in an atom

‹13›

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

Ne, Ar, Kr, He: Inert gases, unreactive because

outer shells are completely filled
‹14›
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Electronic Configurations
ex: Fe - atomic # =26 1s2 2s2 2p6 3s2 3p6 3d 6 4s2

4d
4p N-shell n = 4 valence
electrons
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
‹#15›

Atomic Structure

Order of filling: 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s,4d, 5p, 6s, 4f, 5d, 6p, 7s, 5f, 6d, ...

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Atomic Structure

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EXAMPLE
• Silicon: Z=14
–The maximum number of electrons in a subshell is
given by: 2(2l+1) or
– s for l=0, with nmax=2
– p for l=1, with nmax=6
– d for l=2 , with nmax=10
– f for l=3 , with nmax=14, Since Z=14, there is no
need for the F Shell
• The order of the subshell is given as: 1s, 2s, 2p,
3s,3p, 4s, 3d,4p,…
• The solution is then: [1s22s22p6]3s23p2

• For, germanium: [1s22s22p63s23p63d10]4s24p2

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Orbital Shapes and Sizes

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Hybridization
• Under special conditions the s and p orbitals combine to form a
hybrid spn orbitals, where n indicates the number of the p orbitals
involved.

• 1s22s22p2 (Carbon) means that there are

– Two electrons in the 1s orbital
– Two in the 2s orbital
– And 2 in the 2p orbital

Hybridization:

– The 2p3 configuration in C6 atom (1s22s12p3)

– 1s: has a binding energy of -283.9(eV)
– 2sp3 has an energy level of -6.5 (eV)

Motive: SP3 lower energy state for the valance electrons.

Common in Polymers.
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Hybridization

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The Periodic Table

• 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.
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Electronegativity (EN)

• The relative tendency of an element to gain, or

attract, an electron

• Increases from left to right in the periodic

table

• Electronegativity Difference (ΔEN) between

two elements is an important parameter
determining the type of bonding between two
elements
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Electronegativity
• Ranges from 0.9 to 4.1,
• Large values: tendency to acquire electrons.

Smaller electronegativity Larger electronegativity

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Atomic Bonding
• Primary Bonding ( Chemical bonds) Forces
(when an actual transfer or sharing of the
outer electrons occur)
1. Ionic
2. Covalent
3. Metallic

• Secondary Bonding ( Physical bonds) Forces

(subtle attraction between positive and
negative charges).
1. Van der Waals
2. Hydrogen Bonding

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Bond Force Curve

• Interatomic Forces
– attractive forces (FA)
– repulsive forces (FR)

• When the atoms reach

a critical distance (r0),
the attractive and
repulsive forces cancel
each other and the
atoms are at their
equilibrium distance.
• At equilibrium FA =- FR;
net force is zero 26
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Bonding Energy Curve

• Sometimes it is easier
to deal with potential
energies (E) rather
than forces. The
relation of Energy to
Force is as follows:

r
E N  

F N dr

r r
 

F A dr  

F R dr

 E A  E R

• Equilibrium is reached
by minimizing EN 27

Ionic Bonding
• Occurs between + and – ions

• Requires electron transfer.

• Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction
Large difference in electronegativity required. NaCl (Na
has valance +1 and Cl has valance
‹#› -1), ΔEN 3.16- 0.93=2.23
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Ionic Bonding
Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stabl
Attraction e
• Both Na+ and Cl- are more stable (called ions).

• Na+ now has a full outer orbital shell (cation)

• Cl- now has a full outer orbital shell by accepting an electron

(anion)

• The ionic bond is the result of the coulombic attraction

between the oppositely charged species.

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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]

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Ionic Bonding
• Attractive and repulsive energies are functions
of interatomic distance “r” and may be
represented as follows:
A
E A  
r
B
E R 
r n

– A and B are constants depending upon the

system.
– The value of n is usually taken as 12.
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Ionic Bonding
• Energy – minimum energy most stable
– Energy balance of attractive and repulsive terms
A B
EN = EA + ER = - + n
r r
Repulsive energy ER

Interatomic separation r

Net energy EN
Adapted from Fig.
2.10(b), Callister &
Rethwisch 9e.

Attractive energy EA
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Examples: Ionic Bonding

• Predominant bonding in Ceramics
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.
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NaCl

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Characteristics of Ionic Bonding

1. Non-directional Bond - strength of bond
equal in all directions

2. Low electrical conductivity – Entire ion

must move to conduct electricity

3. Brittle (ceramics -Alkali halides, LiF,

NaCl, and Oxides- Li2O and Na2O,…)

4. High bonding energies (~600 - 1500

kJ/mol) reflected in High Melting
Temperature

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Covalent Bonding
• Similar electronegativity  share electrons
• bonds determined by valence – s & p orbitals

Example: H2
H2
Each H: has 1 valence e-,
needs 1 more
H H
Electronegativities
are the same.
shared 1s electron shared 1s electron
from 1st hydrogen from 2nd hydrogen
atom atom

Fig. 2.12, Callister & Rethwisch 9e.

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Bond Hybridization
• Carbon can form sp3
hybrid orbitals; think of
it as an overlap

Fig. 2.14, Callister & Rethwisch 9e.

(Adapted from J.E. Brady and F. Senese, Chemistry:
Matter and Its Changes, 4th edition. Reprinted with
permission of John Wiley and Sons, Inc.)

Fig. 2.13, Callister & Rethwisch 9e.

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Covalent Bonding: Carbon sp3

• Example: CH4

C: has 4 valence e-,

needs 4 more
H: has 1 valence e-,
needs 1 more

Electronegativities of C and H
are comparable so electrons
are shared in covalent bonds.
Fig. 2.15, Callister & Rethwisch 9e.
(Adapted from J.E. Brady and F. Senese, Chemistry:
Matter and Its Changes, 4th edition. Reprinted with
permission of John Wiley and Sons, Inc.)

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Characteristics of Covalent Bonding

1. Directional Bond - strength of bond not equal

in all directions
2. Low electrical conductivity
3. Very Hard
4. Can be either very strong or very weak
bonds, depending upon the atoms involved in
the bond. This is also reflected in the
melting temperature of the compound
• ex: diamond (strong bond) -- Tm> 3350°C
bismuth (weak bond) -- Tm ~ 270°C

Most common form of bonding in polymers

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Metallic Bonds
• Electrons are shared to
form a bond

• Most common in bonding of

metals and their alloys.
• Proposed model of metallic
bonding
– metals usually have, at most, 3
valence electrons, all of which
form an “electron sea”, which
drift through the entire metal.

– Base electrons form net-positive

ion cores, which attract the
free electrons from the “sea” as
needed to maintain neutrality.

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Characteristics of Metallic Bonding

1. Non-directional Bond - strength of

bond equal in all directions
2. Good electrical conductivity – Cloud
of electrons are free to move to
conduct electricity
3. Ductile
4. Opaque

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Mixed Bonds (Ionic/covalent)

• In compounds involving more than one

element, ionic bonds are favored when
the (DEN) is large.

• The transition from pure ionic to pure

covalent is gradual. Calculations by Pauli
illustrate that a 50-50 mixture occurs at
a DEN of 1.7.

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Mixed Bonds( Metallic/covalent)

• The bonds in Group IA metals are predominately metallic,

however, moving across the periodic table to the right,
increases the valence and the covalent character of the
bond.

• When some metals are mixed, they form intermetallic

compounds with characteristic metal atom ratios, AxBy.
Examples include: AlLi, Ni3Al, Al3V, AlSb, CuZn, Ti3Al and
Mg2Si.

• Depending upon the DEN, they are either a mixture of

metallic/covalent or metallic/ionic. These materials are
often brittle but are stable at high temperatures.

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Ionic-Covalent Mixed Bonding

• Ionic-Covalent Mixed Bonding

% ionic character = x (100%)

where XA & XB are Pauling electronegativities

Ex: MgO XMg = 1.3
XO = 3.5

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Secondary Bonding
Arises from interaction between dipoles
• Fluctuating dipoles -atoms induced
asymmetric electron ex: liquid H 2
clouds H 2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.20,
bonding
Callister & Rethwisch 9e.

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.22,
Callister & Rethwisch 9e.
secondary
-ex: liquid HCl H Cl bonding H Cl

-ex: polymer secondary bonding

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Van der Waals bonding

– weak bonds in comparison with other forms of

bonding (~10 kJ/mol)

– evident between all atoms, including inert

gases and especially between covalently
bonded molecules.

– Bonds are created through both atomic and

molecular dipoles

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Hydrogen bonding

– special type of secondary bond between

molecules with permanent dipoles and hydrogen
in the compound.
• Ex: HF, H2O, NH3
– these secondary bonds can have strengths as
high as ~50 kJ/mol and will cause increases in
melting temperature above those normally
expected.

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Summary: Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Covalent Variable Directional

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

Metallic Variable
large-Tungsten Nondirectional (metals)
small-Mercury
Secondary smallest Directional
inter-chain (polymer)
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inter-molecular
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Data from bond-energy curve

• Bonding Energy (EN)

• Interatomic Spacing (ro)

• Melting Temperature( Tm)

• Coefficient of Thermal Expansion (CTE)

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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 : 

• Coefficient of thermal expansion, 
length, L o coeff. thermal expansion
unheated, T1
L L
= (T2 -T1)
heated, T2 Lo

•  ~ symmetry at ro
Energy
Materials with high bond
unstretched length
ro energy-deep and symmetric
r wells should -have low
large  coefficient of thermal
E
expansion
o
E small 
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o

Summary: Primary Bonds

Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small a

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate a

Polymers Directional Properties

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

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