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CH 02

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CH 02

ch02

Uploaded by

Ela Macabante
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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?

Chapter 2 - 1

Atomic Structure (Freshman Chem.)


atom

electrons 9.11 x 10-31 kg


protons
1.67 x 10-27 kg
neutrons

atomic number = # of protons in nucleus of atom


= # of electrons in 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 = 1 g/mol
C
H

12.011
1.008 etc.
Chapter 2 - 2

Atomic Structure
Some of the following properties
1)
2)
3)
4)

Chemical
Electrical
Thermal
Optical

are determined by electronic structure

Chapter 2 - 3

Electronic Structure
Electrons have wavelike and particulate properties.
Two of the wavelike characteristics are
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)


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

, -
Chapter 2 - 4

Electron Energy States


Electrons...

have discrete energy states


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

Energy

N-shell n = 4
Adapted from Fig. 2.6, Callister &
Rethwisch 9e.
(From K. M. Ralls, T. H. Courtney, and J. Wulff,
Introduction to Materials Science and
Engineering, p. 22. Copyright 1976 by John
Wiley & Sons, New York. Reprinted by
permission of John Wiley & Sons, Inc.)

3p
3s

M-shell n = 3

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 2 - 5

SURVEY OF ELEMENTS
Most elements: Electron configuration not stable.
Element
Atomic #
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 - 6

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 - 7

Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6
4d
4p
3d
4s
Energy

3d 6 4s2

valence
N-shell n = 4
electrons
Adapted from Fig. 2.6, Callister &
Rethwisch 9e.
(From K. M. Ralls, T. H. Courtney, and J.
Wulff, Introduction to Materials Science and
Engineering, p. 22. Copyright 1976 by John
Wiley & Sons, New York. Reprinted by
permission of John Wiley & Sons, Inc.)

3p
3s

M-shell n = 3

2p
2s

L-shell n = 2

1s

K-shell n = 1
Chapter 2 - 8

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 - 9

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

Smaller electronegativity

Larger electronegativity

Chapter 2 - 10

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 - 11

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 - 12

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
Chapter 2 - 13

Examples: Ionic Bonding

Predominant bonding in Ceramics


NaCl
MgO
CaF 2
CsCl

Give up electrons

Acquire electrons

Chapter 2 - 14

Covalent Bonding
similar electronegativity share electrons
bonds determined by valence s & p orbitals
dominate bonding
Example: H2
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 - 15

Bond Hybrization
Carbon can form sp3 hybrid
orbitals

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 - 16

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.)

Chapter 2 - 17

Primary Bonding
Metallic Bond -- delocalized as electron cloud
Ionic-Covalent Mixed Bonding
% ionic character =

x (100%)

where XA & XB are Pauling electronegativities

Ex: MgO

XMg = 1.3
XO = 3.5

Chapter 2 - 18

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. 2.20,


Callister & Rethwisch 9e.

Permanent dipoles-molecule induced


-general case:

secondary
bonding

secondary
bonding

H Cl

-ex: liquid HCl

H Cl

-ex: polymer

secon
dary b
ondin
g

Adapted from Fig. 2.22,


Callister & Rethwisch 9e.

secondary bonding
Chapter 2 - 19

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 - 20

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 - 21

Properties From Bonding:


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

L
= (T2 -T1)
Lo

heated, T2

~ symmetric at ro
Energy
unstretched length
ro

Eo
Eo

is larger if Eo is smaller.

larger
smaller
Chapter 2 - 22

Summary: Primary Bonds


Ceramics

Large bond energy

(Ionic & covalent bonding):

Metals

Variable bond energy

(Metallic bonding):

Polymers

moderate Tm
moderate E
moderate

Directional Properties

(Covalent & Secondary):


secon
dary b

large Tm
large E
small

ondin
g

Secondary bonding dominates


small Tm
small E
large

Chapter 2 - 23

ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:

Chapter 2 - 24

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