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Atomic Structure and

Interatomic Bonding
ISSUES TO ADDRESS...
What promotes bonding?
What types of bonds are there?
What properties are inferred from bonding?

Adapted from the Textbook Material

Chapter 2 - 1

Chapter 2 - 2

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Basic concepts

Fundamental Concept

Atoms are made of protons, neutrons and

electrons

me=0.00091094x10-27= 9.1094x10-31kg = 0.511MeV

mp = 1.6726 x 10-27 kg = 938.272 MeV
mn = 1.6749 x 10-27 kg = 939.566 MeV =
mn = mp + 1.293 MeV

proton & electron charge 1.6022 x

However p are +ve and e are ve

10-19

Atomic Weight

Atomic number (Z) describes the number of

protons in the nucleus
Atomic mass (A) of an element is
approximately equal to the number of neutrons
and protons the element has

Atomic Mass Unit (amu)

Remember elements have isotopes elements can

have different numbers of neutrons (e.g. 12C, 13C,
14C)

Chapter 2-

Measure of atomic mass

1/12 the mass of C12 atom

Mole

Atomic weight is the weighted average of the

element based on the relative amounts of its
isotopes (e.g. 1 mol/carbon = 12.0107 g/mol,
NOT 12 g/mol!)

Weighted average of the atomic masses of an atom's

naturally occurring isotopes

Quantity of a substance corresponding to 6.022X1023 atoms

or molecules
1 amu/ atom (or molecule) = 1g/mol
Chapter 2-

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Electrons In Atoms
Bohr Atomic Model (old view)

Examples
How many grams are there in one amu of a material?

The two major isotopes of carbon:

98.93% of 12C with an atomic weight of 12.00000 amu, and
1.07% of 13C with an atomic weight of 13.00335 amu.

Confirm that the average atomic weight of C is 12.011 amu.

Early outgrowth of
quantum mechanics
Electrons revolve around
nucleus in discrete orbitals
Electrons closer to nucleus
travel faster then outer
orbitals
Principal quantum number
(n); 1st shell, n=1; 2nd shell,
n=2; 3rd shell, n=3

Sum the product of the isotope atomic weight and the percent abundance.
(12 amu)*(.9893)+(13.00335 amu)*(.0107) = 12.011 amu
Chapter 2-

Chapter 2-

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Quantum NumbersHydrogen atom

Bohr Atom

Wave-mechanical atom

c02f03

Chapter 2-

Chapter 2-

c02f02

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Atomic Models

Atomic Models

Quantum numbers

Wave-Mechanical
Model

Electron exhibits both

wave-like and particle-like
characteristics
Position is now considered
to be the probability of an
electron being at various
locations around the
nucleus, forming an
electron cloud

The size, shape, and spatial orientation of an

electrons probability density are specified by
three of these quantum numbers.

Principal quantum number n, represents a

shell

Quantum number l, signifies the subshell

s, p, d, f have 1, 3, 5, 7 states respectively

Quantum number ms, is the spin moment

Chapter 2-

Lowercase italics letter s, p, d, f; related to

the shape of the subshell

Quantum number ml , represents the

number of energy state

K, L, M, N, O correspond to n=1, 2, 3, 4,
5....

Each electron is a spin moment (either up

or down)
(+1/2) and (-1/2)
Each state can hold no more than 2
Chapter 2electrons which must have opposite spins

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Electron Configuration

Electron configuration
represents the manner in
which the states are
occupied
Valence electrons

Energy

Occupy the outermost

shell
Available for bonding
Tend to control chemical
properties

Ex. Silicon (Si)

Chapter 2-

Chapter 2-

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Examples
When some elements covalently
bond, they form sp hybrid bonds,
e.g., C, Si, Ge

Give the electron configurations for the following:

C
1s2 2s2 2p2

Br
1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5

c02tf02

Mn+2
1s2 2s2 2p6 3s2 3p6 3d5
F1s2 2s2 2p6
Cr
Chapter 2-

1s2 2s2 2p6 3s2 3p6 4s1 3d5

Chapter 2-

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Electronic Structure
Electrons have wave-like and particle-like (old view)
properties.
We can better say that the wave-particle nature is the real
thing; individual wave and particle states are limiting cases;
usually observed in measurements (collapse of the wave
function)
To better understand electronic structure, we assume
Electrons reside in orbitals.
Each orbital at discrete energy level is determined by
quantum numbers.

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)

Quantum #

1s2 2s2 2p2

Designation

n = principal (energy level-shell)

l = angular (orbitals)
ml = magnetic

K, L, M, N, O (1, 2, 3, etc.)
s, p, d, f (0, 1, 2, 3,, n -1)
1, 3, 5, 7 (-l to +l)

ms = spin

, -
Chapter 2 - 15

valence electrons

Chapter 2 - 16

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Periodic Table

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

3d 6 4s2

4d
4p

Energy

N-shell n = 4 valence
electrons

3d

4s

3p
3s

M-shell n = 3

Adapted from Fig. 2.4,

Callister & Rethwisch 3e.

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 2 - 17

Elements classified according to electron configuration

Elements in a given column or group have similar valence electron
structures as well as chemical and physical properties
Group 0 inert gases, filled shells and stable
Group VIIA halogen
Group IA and IIA - alkali and alkaline earth metals
Groups IIIB and IIB transition metals
Groups IIIA, IVA and VA characteristics between the metals and
nonmetals

Chapter 2-

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The Periodic Table

Atomic Bonding
accept 2eaccept 1einert gases

give up 1egive up 2egive up 3e-

Columns: Similar Valence Structure

He

Li Be

Ne

Na Mg

Cl

Ar

Se

Br

Kr

Te

Xe

Ca Sc

Rb Sr

Cs Ba

Valence electrons determine all of the

following properties

Po

Adapted from
Fig. 2.6,
Callister &
Rethwisch 8e.

At Rn

Fr Ra

Electropositive elements:
Readily give up electrons
to become + ions.

Electronegative elements:
Readily acquire electrons
to become - ions.
19

Chapter 2-

1)
2)
3)
4)
5)
6)

Chemical
Electrical
Thermal
Optical
Deteriorative
etc.

Chapter 2 - 20

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Bonding in Solids
Bonding forces and energies
Far apart: atoms dont know about each other
As they approach one another, exert force on one another
Forces are

Atomic Bonding in Solids

Attractive (FA) slowly changing with distance

Repulsive (FR) typically short-range

Net force is the sum of these

FN = FA + FR
At some point the net force is zero; at that position a state of
equilibrium exists

Chapter 2-

Chapter 2-

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When 0 = FA + FR,
equilibrium exists.
The centers of the
atoms will remain
separated by the
equilibrium spacing
ro.

Bonding Forces and

Energies

Bonding in Solids
Bonding forces and energies

We are more accustomed to thinking in terms of potential energy

instead of forces in that case

E Fdr

Setting our ZERO ENERGY reference at infinite

This spacing also
corresponds to the
minimum of the
potential energy
curve. The energy
that would be
required to
separate two
atoms to an infinite
separation is Eo

FN = FA +
FR
Figure 2.8

EN = EA +
ER
Chapter 2-

E N FA dr FR dr
E N E A ER

The point where the forces are zero also corresponds to the minimum
potential energy for the two atoms (i.e. the trough in Figure 2.8), which
makes sense because dE/dr = F =0 at a minimum.

The interatomic separation at that point (ro) corresponds to the potential

energy at that minimum (Eo, it is also the bonding energy)

The physical interpretation is that it is the energy needed to separate the atoms
Chapter 2infinitely far apart

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Bonding Forces and Energies

A number of material properties depend on Eo,
the curve shape, and bonding type
Material with large Eo typically have higher melting
points
Mechanical stiffness is dependent on the shape of its
force vs. interatomic separation curve
A materials linear coefficient of thermal expansion
is related to the shapeof its Eo vs. ro curve

Chapter 2-

Examples
Calculate the force of attraction between ions X+ and an Y-, the
centers of which are separated by a distance of 2.01 nm.

&

Chapter 2-

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Primary Interatomic Bonds

Types of primary bonds found in solids

Ionic
Covalent
Metallic

As you might imagine, the type of bonding influences

properties why?
Bonding involves the valence electrons!!!

Ionic Bonding

Occurs between + and - ions.

Requires electron transfer.
Large difference in electronegativity required.
Example: NaCl

Na (metal)
unstable
electron
Na (cation)
stable

Chapter 2-

Cl (nonmetal)
unstable

+
Coulombic
Attraction

Cl (anion)
stable

Chapter 2 - 28

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Ionic bond:

metal

nonmetal

Primary Interatomic Bonds

Ionic bonding

donates
electrons

Sodium chloride (NaCl)

accepts
electrons

Sodium gives up one its electrons to chlorine sodium becomes

positively charged, chlorine becomes negatively charged

The attraction energy is electrostatic in nature in ionic solids

(opposite charges attract)
The attractive component of the potential energy (for 2 point
charges) is given by

Dissimilar electronegativities
ex: MgO

Mg

1s2 2s2 2p6 3s2

[Ne] 3s2

Mg2+ 1s2 2s2 2p6

[Ne]

1s2 2s2 2p4

EA

Z1e Z 2e 1

4 o
r

The repulsive term is given by

O2- 1s2 2s2 2p6

[Ne]
Chapter 2 - 29

ER

B
, n ~ 8 12
rn

Chapter 2-

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Primary Interatomic Bonds

IONIC BONDING
Ionic bonding is non-directional magnitude of the bond is equal in
all directions around the ion
Many ceramics have an ionic bonding characteristic
Bonding energies typically in the range of 600 1500 kJ/mol
Often hard, brittle materials, and generally insulators

Chapter 2-

Chapter 2-

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Ionic Bonding

Examples: Ionic Bonding

Predominant bonding in Ceramics

Energy minimum energy most stable

NaCl
MgO
CaF 2
CsCl

Energy balance of attractive and repulsive terms

EN = EA + ER =

A
r

B
rn

Repulsive energy ER

Interatomic separation r
Net energy EN
Adapted from Fig. 2.8(b),
Callister & Rethwisch 3e.

Give up electrons
Attractive energy EA

Acquire electrons

Adapted from Fig. 2.7, Callister & Rethwisch 3e. (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.
Chapter 2 - 33

Chapter 2 - 34

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Covalent bonding

Covalent Bonding

Sharing of electrons between adjacent atoms

Most nonmetallic elements and molecules containing
dissimilar elements have covalent bonds
Polymers!

Bonding is highly directional! : between specific atoms

and may exist only in the direction between one atom
and another that participates in electron sharing
Number of covalent bonds possible is guessed by the
number of valence electrons
Typically is 8 N, where N is the number of valence
electrons
Carbon has 4 valence es 4 bonds (ok!)
Chapter 2-

similar electronegativity share electrons

bonds determined by valence s & p orbitals
dominate bonding
Example: CH4
H

C: has 4 valence e-,

needs 4 more

CH 4

H: has 1 valence e-,

needs 1 more

Electronegativities
are comparable.

shared electrons
from carbon atom

H
shared electrons
from hydrogen
atoms

Adapted from Fig. 2.10, Callister & Rethwisch 3e.

Chapter 2 - 36

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EXAMPLES: COVALENT BONDING

H2
H
2.1
Li
1.0

Be
1.5

Na
0.9
K
0.8

Mg
1.2
Ca
1.0

Rb
0.8

Sr
1.0

Cs
0.7

Ba
0.9

Fr
0.7

Ra
0.9

column IVA

H2O
C(diamond)

SiC
Ti
1.5

Cr
1.6

Fe
1.8

F2
He
-

O
2.0

C
2.5

Ni
1.8

Zn
1.8

Ga
1.6

Si
1.8
Ge
1.8

Bonding in Solids

As
2.0

Sn
1.8
Pb
1.8

F
4.0

Ne
-

Cl
3.0
Br
2.8

Ar
Kr
-

I
2.5

Xe
-

At
2.2

Rn
-

Cl2

GaAs

Adapted from Fig. 2.7, Callister 6e. (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.

Molecules with nonmetals

Molecules with metals and nonmetals
Elemental solids (RHS of Periodic Table)
Compound solids (about column IVA)

Chapter 2- 11

Many materials have bonding that is both ionic and

covalent in nature (very few materials actually exhibit pure
ionic or covalent bonding)
Easy (empirical) way to estimate % of ionic bonding
character:

% ionic character 1 exp (0.25)( X A X B ) 2 x100

XA, XB are the electronegativities of atoms A and B involved

Chapter 2-

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Primary Interatomic Bonds

Bonding in Solids

Metallic Bonding
Found in metals and their alloys
1 to 3 valence electrons that form a
sea of electrons or an electron
cloud because they are more or
less free to drift through the entire
metal
Nonvalence electrons and atomic
nuclei form ion cores
Bonding energies range from weak
to strong
Good conductor of both electricity
and heat
Most metals and their alloys fail in
a ductile manner

Metallic bonding
Most metals have one, two, or at most three valence electrons
These electrons are highly delocalized from a specific atom have
a sea of valence electrons

Ion
Cores
+

+
-

+
+

+
+
-

Sea of Valence
Electrons Chapter 2-

Free electrons shield positive core of

ions from one another (reduce ER)
Metallic bonding is also nondirectional
Free electrons also act to hold
structure together
Wide range of bonding energies,
typically good conductors (why?)
Chapter 2-

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Secondary Bonding or van der

Walls Bonding
Also known as physical bonds
Weak in comparison to primary or chemical
bonds
Exist between virtually all atoms and molecules
Arise from atomic or molecular dipoles
bonding that results from the coulombic attraction
between the positive end of one dipole and the
negative region of an adjacent one
a dipole may be created or induced in an atom or
molecule that is normally electrically symmetric
Chapter 2 -

Secondary Bonding or van der

Waals Bonding
Fluctuating Induced Dipole Bonds
A dipole (whether induced or instantaneous)
produces a displacement of the electron distribution
of an adjacent molecule or atom and continues as a
chain effect
Liquefaction and solidification of inert gases
Weakest Bonds
Extremely low boiling and melting point
Atomic nucleus
Atomic nucleus

Instantaneous

Electron
cloud

Electron
cloud

Fluctuation
Chapter 2 -

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Secondary Bonding or van der Waals Bonding

Polar Molecule-Induced Dipole Bonds
Permanent dipole moments exist by virtue of an
asymmetrical arrangement of positively and negatively
charged regions
Polar molecules can induce dipoles in adjacent nonpolar
molecules
Magnitude of bond greater than for fluctuating induced
dipoles

Secondary Bonding or van der

Waals Bonding
Permanent Dipole Bonds
Stronger than any secondary bonding with induced
dipoles
A special case of this is hydrogen bonding: exists
between molecules that have hydrogen as one of the
constituents

Atomic nucleus
Electron Cloud

Hydrogen Bond

H
Polar
Molecule

Induced
Dipole

Chapter 2 -

Cl

Cl
Chapter 2 -

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MATERIAL OF IMPORTANCE
Water

c02f16

Many molecules do not have a

symmetric distribution/arrangement
of positive and negative charges
(e.g. H2O, HCl)

c02tf03

Chapter 2-

Chapter 2-

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Properties From Bonding: Tm

Bond length, r

Melting Temperature, Tm
Energy

r
Bond energy, Eo

ro

Energy

smaller Tm

unstretched length

ro

Eo =
bond energy
Chapter 2-

larger Tm
Tm is larger if Eo is larger.

Chapter 2 - 48

c02uf01

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Properties From Bonding : a

Coefficient of thermal expansion, a
coeff. thermal expansion
length, L o
unheated, T1

heated, T 2

Elastic modulus
F
DL
=E
Ao
Lo

DL
= a ( T2 -T1)
Lo

DL

PROPERTIES FROM BONDING: E

Elastic modulus, E

E ~ dF/dr|ro elastic modulus

a ~ symmetric at ro
Energy
unstretched length

ro
Eo
Eo

a is larger if Eo is smaller.

larger a
smaller a
Chapter 2 - 49

Chapter 2- 16

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Summary: Primary Bonds

Ceramics
(Ionic & covalent bonding):

Metals
(Metallic bonding):

Polymers
(Covalent & Secondary):

Summary: Bonding

Large bond energy

large Tm
large E
small a

Variable bond energy

moderate Tm
moderate E
moderate a

Directional Properties
Secondary bonding dominates
small Tm
small E
large a

Chapter 2 - 51

Comments

Type

Bond Energy

Ionic

Large!

Nondirectional (ceramics)

Covalent

Variable
large-Diamond
small-Bismuth

Directional
(semiconductors, ceramics
polymer chains)

Metallic

Variable
large-Tungsten
small-Mercury

Nondirectional (metals)

Secondary

smallest

Directional
inter-chain (polymer)
inter-molecular
Chapter 2 - 52

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