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Chapter 2: Atomic Structure &

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

Chapter 2 - 1

Ionic Bonding
Balance of attractive and repulsive forces between
two atoms
State of equilibrium at r0 no net force

Bonding energy:
E required to separate
two atoms from this
equilibrium state to an
infinite separation
Adapted from Fig.
2.10(a), Callister &
Rethwisch 9e.

Chapter 2 - 2

Atomic Structure
Subatomic particle mass: electrons 9.11 x 10-31 kg
protons
-27
neutrons 1.67 x 10 kg

atomic number = # of protons in nucleus of atom


= # of electrons in neutral species
# of neutrons may vary => isotopes
atomic mass unit = a.m.u. = 1/12 mass of 12C
Atomic wt = wt of 6.022 x 1023 atoms => mole
C
H

12.011 g/mol
1.008 g/mol etc.
Chapter 2 - 3

Bohr Atomic Model


protons & neutrons

Fig_2-1

Chapter 2 - 5

Chapter 2 - 5

Electronic Structure: Wave-mechanical Model


Electrons have wavelike and particulate properties.
=> Quantum physics

Two of the wavelike characteristics are


electrons are in orbitals defined by a probability.
each orbital at discrete energy level is determined by
4 quantum numbers.
Quantum #
n = principal (energy level-shell)
~ Bohr model
= subsidiary (orbital shape)
azimuthal

Designation
K, L, M, N, O (1, 2, 3, etc.)
s, p, d, f (0, 1, 2, 3,, n-1)

Chapter 2 - 6

s orbital

p orbital

Chapter 2 - 7

Quantum #

Designation

n = principal (energy level-shell)


~ Bohr model
= subsidiary (orbital shape)
ml = magnetic (- to +)
ms = spin moment (, -)

K, L, M, N, O (1, 2, 3, etc.)
s, p, d, f (0, 1, 2, 3,, n-1)
Number of orbitals 1, 3, 5, 7
Number of electrons 2, 6, 10, 14

Table_2-1
Chapter 2 - 8

Chapter 2 - 9

SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Atomic #
Element
Hydrogen
1
Helium
2
Lithium
3
Beryllium
4
Boron
5
Carbon
6
...
Neon
10
Sodium
11
Magnesium
12
Aluminum
13
...

Electron configuration
1s 1
1s 2
(stable)
1s 2 2s 1
1s 2 2s2
1s 2 2s 2 2p 1
1s 2 2s 2 2p 2
...

Argon
...
Krypton

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)

18
...
36

Adapted from Table 2.2,


Callister & Rethwisch 9e.

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
...

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


Chapter 2 - 10

Electron Configurations
Valence electrons those occupy the outmost shell.
Many physical and chemical properties of solids are
based on these valence electrons.
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 - 11

The Periodic Table


give up 1egive up 2egive up 3e-

accept 2eaccept 1einert gases

Columns: Similar Valence Structure

K Ca Sc

Se Br Kr

He

Li Be

F Ne

Na Mg

Cl Ar

Rb Sr

Cs Ba

Te

Adapted from
Fig. 2.8,
Callister &
Rethwisch 9e.

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 - 12

Electronegativity
Ranges from 0.9 to 4.1,
Large values: tendency to acquire electrons.

Smaller electronegativity

Larger electronegativity

Chapter 2 - 13

Ionic bond metal

donates
electrons

nonmetal
accepts
electrons

Dissimilar electronegativities
ex: MgO

Mg

1s2 2s2 2p6 3s2


[Ne] 3s2

Mg2+ 1s2 2s2 2p6


[Ne]

1s2 2s2 2p4

O2- 1s2 2s2 2p6


[Ne]

Chapter 2 - 14

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 - 15

Chapter 2 - 16

Examples: Ionic Bonding


Predominant bonding in Ceramics
NaCl
MgO
CaF 2
CsCl

Give up electrons

Acquire electrons

Chapter 2 - 17

Covalent Bonding
similar electronegativity: share electrons
bonds determined by valence s & p orbitals
dominate bonding
Directional
H2
Example: H2
Each H: has 1 valence e-,
needs 1 more
Electronegativities
are the same.

shared 1s electron
from 1st hydrogen
atom

shared 1s electron
from 2nd hydrogen
atom

Fig. 2.12, Callister & Rethwisch 9e.


Chapter 2 - 18

Bond Hybridization
Carbon can form sp3 hybrid
orbitals
Tetrahedron

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.


Chapter 2 - 19

Covalent Bonding: Carbon sp3


Example: methane 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.)

Chapter 2 - 20

Methane sp3
C-H bonds

Diamond - sp3

C-C bonds
Extremely strong
High melting T
Very hard material
Chapter 2 - 21

Covalent Bonding: Carbon sp2

Fig_2-16

Chapter 2 - 22

C-C covalent bonds


6 sp2 triangles form
a hexagon
Chapter 2 - 23

What does diamond have in common


with your lead pencil?

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Chapter 2 - 24

Methane sp3

Graphite sp2

Diamond, sp3

www2.warwick.ac.uk
Chapter 2 - 25

Metallic Bonding
Metallic Bonding -- delocalized as electron cloud
electrons not bound to any particular atom

or
electron cloud

free electrons shield positively charged ion cores


from the mutually repulsive electrostatic forces
nondirectional
metals are good conductors of heat and electricity
Chapter 2 - 26

Bonding
Primary Bonding
types: ??

Chapter 2 - 27

Bonding
Primary Bonding
types: ??
Secondary Bonding
weak compared to primary bonds
van der Waals bonds: from interaction between dipoles
hydrogen bonding

Chapter 2 - 28

Density of ice vs. water?

Chapter 2 - 29

Bonding
unusual, most substances experience an increase in
density upon transforming from liquid to solid
ice formation => expansion of approximately 9 pct
4 hydrogen bonds form per H2O molecule
open structure => lower density
upon melting
structure partially destroyed
molecules closer packed

Chapter 2 - 30

Mixed Bonding
For many real materials, the atomic bonds are mixtures
bonding tetrahedron

Covalent-Ionic Mixed Bonding: percent ionic character (%IC)

electronegativity

Chapter 2 - 31

Mixed Bonding
Covalent-Ionic Mixed Bonding: percent ionic character (%IC)

Ex: MgO

XMg = 1.3
XO = 3.5

Chapter 2 - 32

Read Chapter 2

Chapter 2 - 33