Chapter 2: Atomic Structure &

Interatomic Bonding
Chapter Overview
Atomic structure and electron configuration
What types of bonds are there?
What properties are inferred from bonding?

Chapter 2 - 1

Atomic Structure
atom

electrons 9.11 x 10-31 kg

protons
-27 kg
1.67
x
10
neutrons

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 6.022 x 1023 molecules or atoms
1 amu/atom = 1g/mol
C
H

12.011
1.008 etc.
Chapter 2 - 2

Atomic Structure: Bohr Model

Orbital electrons revolve
around nucleus
Electron energy is
quantized to specific
values
Electron may change
energy state, but electron
must jump to other shells
(absorb/emit energy)

Chapter 2 - 3

Bohr vs. Wave Mechanical Model

a)

b)

Chapter 2 - 4

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)

l = subsidiary (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 - 5

Electronic Structure

Chapter 2 - 6

Ref: http://www.colourbox.com/vector/illustration-of-central-nucleus-are-surrounded-by-a-cloud-of-vector

A crude analogy!
Ref: http://www.clipart.dk.co.uk/289/subject/Physics/Earth

Some History Behind the Atom

Electrons have kinetic energy and potential energy.

These forces have to balance!
Chapter 2 - 7

Spectroscope schematic diagram.

Chapter 2 - 8

Ref: http://www.m2c3.com/chemistry/VLI/M1_Topic2/M1_Topic2_print.html

Bohr Theory

Bohr Theory
Back to the solar system analogy?
But this posed two problems:
1. It seems impossible for an electron to continue
to move around the nucleus without falling into
it, and
2. Why can an electron of hydrogen be excited to
only specific energy levels?

Chapter 2 - 9

Max Planck

Quanta
The emission and
absorption of energy
take place in quanta
amounts.

Ref: http://www.dpreview.com/galleries/9538025536/photos/888416

Chapter 2 - 10

Quantum Theory of Radiation

The quantum theory states that
radiation of frequency n comes in
discrete packets, or quanta, the form of
which accounts for the characteristic
line spectra of atoms.
DE = Ef Ei = hn
where h is Plancks constant
Chapter 2 - 11

The Photoelectric Effect

When specific frequencies of light shine
on the surface of certain metals (alkali
metals) electrons, called
photoelectrons, are given off. This
phenomenon is called the
photoelectric effect, about which
experiments have established the
following:
Chapter 2 - 12

The Photoelectric Effect

1

For a given metal, there is a threshold frequency

no below which no electrons are given off.
2 When the incident radiation has a frequency
higher than no, the photelectrons produced have
kinetic energy. The maximum kinetic energy of the
electrons, mv2 (m=mass, v=velocity), is directly
proportional to frequency n.
3 If the light intensity is increased, the number of
photoelectrons increases but their maximum kinetic
energy is unaffected.

Chapter 2 - 13

The Photoelectric Effect

In plain English, we have two more problems!
1. Bohrs model only explains the
hydrogen atom, and
2. Discrepancies begin to appear in the
energy levels suggested by Bohr.

Chapter 2 - 14

Heisenburg

Electron movements are far

more complicated.

The Heisenburg Uncertainty Principle

(1923)

Ref: http://en.wikipedia.org/wiki/Werner_Heisenberg

Chapter 2 - 15

Heisenburg
This in turn presented two more problems!
1. How to calculate the energies of the
various electrons around the atom, and
2. How to determine the size and shape of
the electron cloud surrounding the
nucleus.

Chapter 2 - 16

Wave Mechanics
Ref: http://micro.magnet.fsu.edu/optics/timeline/people/huygens.html

Could an electron be a wave?

VS.

What is waving??
Chapter 2 - 17

Wave Mechanics

Who is this?
What was his contribution to atomic structure?
Chapter 2 - 18

Wave Mechanics

Einstein showed that the properties of

empty space are such that it is possible
for empty space to become distorted and
thereby permit the existence of waves.

Chapter 2 - 19

Wave Mechanics

Ref: http://clearscience.tumblr.com/post/3764564296/we-talked-about-frets-on-a-guitar-and-how-when-you

Chapter 2 - 20

..

Schrodinger
Schrodinger observed that
standing waves on a guitar are
quantized.
Quantum states of electrons
could correspond to standing
waves!

Psi space
Ref: http://scienceworld.wolfram.com/biography/Schroedinger.html

Chapter 2 - 21

..

Schrodinger

Psi space
Ref: http://cnx.org/content/m42606/latest/

Chapter 2 - 22

Electronic Structure
The wave structure of the electron can be
described by the following function:
y = R(r) F(f) Q(q)

Permitting the classification of nodes as one of

three kinds
spherical nodes (R)
planar nodes (F)
conical nodes (Q)
Chapter 2 - 23

Electronic Structure

Ref: http://chemwiki.ucdavis.edu/@api/deki/files/8855/Single_electron_orbitals.jpg
Chapter 2 - 24

Electronic Structure

Chapter 2 - 25

Electronic Structure

Chapter 2 - 26

Electronic Structure

Chapter 2 - 27

Electronic Structure

Chapter 2 - 28

Electronic Structure

Comparison of the (a) Bohr model and the

(b) wave mechanical model.
Chapter 2 - 29

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 #

Physical meaning

n = principal (energy level-shell)

l = subsidiary (orbitals)
ml = magnetic

size (1, 2, 3, etc.)

shape (0, 1, 2, 3,, n-1)
spatial orientation (-l to +l)

ms = spin

, -
Chapter 2 - 30

Electronic Structure

Chapter 2 - 31

Electronic Structure
The electronic configuration of an atom shows
the way in which the electrons in the atom
occupy, in order of increasing energy, the
available orbitals and spin states.
The electron configuration for any atom follows
three principles:

Chapter 2 - 32

Electronic Structure
1. Aufbau principle: In general, electrons
occupy the lowest energy orbitals available
before entering the higher energy orbitals.
2. Hund principle: Equal energy orbitals are
each occupied by a single electron before the
second electron of opposite spin (s) enters the
orbital. i.e. For each of the three 2p orbitals
(2px, 2py and 2pz) will hold a single electron
before any receives a second electron.
Chapter 2 - 33

Electronic Structure
3. Pauli exclusion principle: No more than two
electrons can occupy the same energy level and
these two must have opposite spins. i.e. They
must have different quantum numbers.

Chapter 2 - 34

Electron Energy States

Electrons...

have discrete energy states

tend to occupy lowest available energy state.
4d
4p
3d

N-shell n = 4

4s
Energy

3p
3s

M-shell n = 3
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 2 - 35

Orbit Filling

Aufbau Principle
Chapter 2 - 36

The Periodic Table

Ref: chemwiki.ucdavis.edu

Chapter 2 - 37

SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Element
Hydrogen
Helium
Lithium
Beryllium
Boron
Carbon
...

Atomic #
1
2
3
4
5
6

Electron configuration
1s 1
1s 2
(stable)
1s 2 2s 1
1s 2 2s 2
1s 2 2s 2 2p 1
1s 2 2s 2 2p 2
...

Adapted from Table 2.2,

Callister & Rethwisch 8e.

Neon
Sodium
Magnesium
Aluminum
...

10
11
12
13

1s 2 2s 2 2p 6
(stable)
1s 2 2s 2 2p 6 3s 1
1s 2 2s 2 2p 6 3s 2
1s 2 2s 2 2p 6 3s 2 3p 1
...

Argon
...
Krypton

18
...
36

1s 2 2s 2 2p 6 3s 2 3p 6
(stable)
...
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.

Chapter 2 - 38

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

Chapter 2 - 39

Electron Configurations
Valence electrons determine all of the
following properties
1)
2)
3)
4)

Chemical
Electrical
Thermal
Optical

Chapter 2 - 40

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
3s

M-shell n = 3
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 2 - 41

give up 1egive up 2egive up 3e-

Columns: Similar Valence Structure

accept 2eaccept 1einert gases

The Periodic Table

He

Li Be

F Ne

Na Mg

Cl Ar

K Ca Sc
Rb Sr

Cs Ba

Se Br Kr
Te

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

Xe

Po At Rn

Fr Ra

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

Electronegative elements:
Readily acquire electrons
to become - ions.
Chapter 2 - 42

Electronegativity
Ranges from 0.7 to 4.0,
Large values: tendency to acquire electrons.

Smaller electronegativity

Larger electronegativity

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (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 - 43

Atomic Bonding
Primary Bonding: Ionic, Covalent, Metallic
Secondary Bonding: van der Waals, Hydrogen
(dipole)

Chapter 2 - 44

Ionic Bonding
Ionic bond metal

donates
electrons

nonmetal
accepts
electrons

Coulombic (Electrical) Bond Forces

Dissimilar electronegativities
ex: MgO

Mg
Mg2+

1s2 2s2 2p6 3s2

[Ne] 3s2
1s2 2s2 2p6
[Ne]

1s2 2s2 2p4

O2- 1s2 2s2 2p6

[Ne]
Chapter 2 - 45

Ionic Bonding

Occurs between + and - ions.

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

Na (metal)
unstable

Cl (nonmetal)
unstable

electron
Na (cation)
stable

+
Coulombic
Attraction

Cl (anion)
stable

Chapter 2 - 46

Ionic Bonding
Energy minimum energy most stable
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 8e.

Attractive energy EA
Chapter 2 - 47

Examples: Ionic Bonding

Predominant bonding in Ceramics

NaCl
MgO
CaF 2
CsCl

Give up electrons

Acquire electrons

Adapted from Fig. 2.7, Callister & Rethwisch 8e. (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 - 48

Covalent Bonding
similar electronegativity share electrons
bonds determined by valence s & p orbitals
dominate bonding
Example: CH4
C: has 4 valence e-,
needs 4 more
H: has 1 valence e-,
needs 1 more
Electronegativities
are comparable.

CH 4
H

shared electrons
from carbon atom

H
shared electrons
from hydrogen
atoms

Adapted from Fig. 2.10, Callister & Rethwisch 8e.

Chapter 2 - 49

Primary Bonding
Ionic-Covalent Mixed Bonding

(X A -X B )2

4
1e

x (100%)

Pauling
electronegativities

% ionic character =

where XA & XB are

Ex. 1: MgO

XMg = 1.2
XO = 3.5

( 3.5-1.2 )2

4
% ionic character 1 - e
x (100%) 73.4% ionic

Chapter 2 - 50

Metallic Bonding
Found in metals and their alloys.
Metallic materials have one, two or at most three
valence electrons.
In general, the fewer the valence electrons an atom
has and the more loosely they are held, the more
metallic the bonding.
Time-averaged, fluctuating, covalent bonding.
Can exist only among a large aggregate of atoms.
Covalent bonds can occur between as few as two
atoms.
Delocalized as an electron cloud.
Chapter 2 - 51

Metallic Bonding
Viewed as timeaveraged covalent
bonds. Alternating
sharing of electrons
with all of its
immediate
neighbours is
indicated for atoms
having 2p orbitals on
the average.
Chapter 2 - 52

SECONDARY BONDING
Arises from interaction between dipoles
Fluctuating dipoles
asymmetric electron
clouds

+
secondary
bonding

ex: liquid H 2
H2
H2

H H

H H
secondary
bonding

Adapted from Fig. 2.13,

Callister & Rethwisch 8e.

Permanent dipoles-molecule induced

-general case:
-ex: liquid HCl
-ex: polymer

H Cl

secondary
bonding

secondary
bonding

H Cl

Adapted from Fig. 2.15,

Callister & Rethwisch 8e.

secondary bonding
Chapter 2 - 53

Summary: Bonding
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 - 54

Quiz-What Bonding Type is

Dominant?

Fe
CaCl2

H2O-H2O

H2-H2

SiC
Si

Liquid Al
Chapter 2 -

Material Properties from Bonding

Chapter 2 - 56

Properties From Bonding: Tm

Bond length, r

Melting Temperature, Tm
Energy

r
Bond energy, Eo

ro

Energy

r
smaller Tm

unstretched length
ro

Eo =
bond energy

larger Tm

Tm is larger if Eo is larger.

Chapter 2 - 57

Properties From Bonding : a

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

DL
= a (T2 -T1)
Lo

DL

heated, T 2

a ~ symmetric at ro
Energy
unstretched length
ro

E
o

E
o

a is larger if Eo is smaller.

larger a
smaller a
Chapter 2 - 58

Summary: Primary Bonds

Ceramics
(Ionic & covalent bonding):

Metals
(Metallic bonding):

Polymers
(Covalent & Secondary):

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 - 59

Chapter 2: Atomic Structure &

Interatomic Bonding

End of Chapter

Chapter 2 - 60