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Chapter 2: Atomic Structure & Interatomic Bonding

Chapter 2: Atomic Structure &


Interatomic Bonding

ISSUES TO ADDRESS...
What characteristics of atoms/molecules
promote interatomic/intermolecular bonding?
What types of interatomic/intermolecular
bonds exist ?
What properties of materials depend on the
magnitude of interatomic/intermolecular bonds ?

Chapter 2 - 1

Atomic Structure (Freshman Chem.)


atom electrons 9.11 x 10-31 kg
_______
}
neutrons ____________
atomic number = # of protons in nucleus of atom
= # of electrons in ______ species

atomic mass unit = ___ = 1/12 mass of 12C

A = Atomic wt = wt of __________ molecules or atoms


1 amu/atom = 1 g/mol
C 12.011
H 1.008
etc.
Chapter 2 - 2

Atomic Structure (cont.)


Some of the following properties are
determined by an atom's electronic structure:
1) Chemical
2) ________
3) Thermal
4) ________

Chapter 2 - 3

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Chapter 2: Atomic Structure & Interatomic Bonding

Electronic Structure
Electrons have wave-like and particle-like
characteristics.
Two wave-like characteristics are
Electron position in terms of _____________________
shape, size, ____________ of probability density
determined by quantum numbers

Quantum # Designation/Values
n = ________ (shell) K, L, M, N, O (1, 2, 3, 4, etc.)
= azimuthal (subshell) s, p, d, f (0, 1, 2, 3,, n-1)
m = ____________________ 1, 3, 5, 7 (- to +)
ms = spin , -

Chapter 2 - 4

Electron Energy States


Electrons...
have discrete energy values
tend to occupy lowest available energy states

4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s

2p L-shell n = 2
2s

1s K-shell n = 1
Chapter 2 - 5

SURVEY OF ELEMENTS
Most elements: Electron configurations 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 2s2
Boron 5 1s 2 2s 2 2p 1
Carbon 6 1s 2 2s 2 2p 2
... ...
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 2s 2p 3s 3p 3d 4s 4p 6 (stable)
2 2 6 2 6 10 2

Why not stable? Valence (outer) shell usually not


completely filled.
Chapter 2 - 6

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Chapter 2: Atomic Structure & Interatomic Bonding

Electron Configurations
Valence electrons those in outer unfilled shells
_________________________ require more
energy to gain or lose electrons
Valence electrons available for bonding and
tend to determine an atoms chemical properties

example: C (atomic number = 6)

1s2 2s2 2p2

valence electrons

Chapter 2 - 7

Electronic Configurations (cont.)


ex: Fe (atomic # = 26)
Electron configuration 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

2p L-shell n = 2
2s

1s K-shell n = 1
Chapter 2 - 8

The Periodic Table


Elements in each column: Similar valence electron structure
inert gases
give up 1e-
give up 2e-

accept 2e-
accept 1e-
give up 3e-

H He
Li Be O F Ne
Na Mg S Cl Ar
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. Chapter 2 - 9

3
Chapter 2: Atomic Structure & Interatomic Bonding

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

Smaller electronegativity Larger electronegativity

Chapter 2 - 10

Ionization Process
metal atom + nonmetal atom

_______ _______
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]

Chapter 2 - 11

Ionic Bonding
Occurs between + and - ions.
Requires _______________.
Large difference in __________________________.
Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction

Chapter 2 - 12

4
Chapter 2: Atomic Structure & Interatomic Bonding

Ionic Bonding (cont.)


Energy ___________ energy most stable
Net energy = sum of attractive and __________ energies
Equilibrium separation when net energy is a minimum

EN = EA + ER = - A + Bn
r r
Repulsive energy ER

Interatomic separation r

Net energy EN
Fig. 2.10(b), Callister &
Rethwisch 10e.

Attractive energy EA

Chapter 2 - 13

Ionic Bonding (cont.)


Predominant bonding in ____________
NaCl
Examples:
MgO
CaF 2
CsCl

Give up electrons Acquire electrons

Chapter 2 - 14

Covalent Bonding
Similar _________________ share electrons
Bonds involve _______________ normally s and p
orbitals are involved
Example: H2
H2

Each H: has 1 valence e-,


needs 1 more
H H
_______________
are the same.
shared 1s electron shared 1s electron
from 1st hydrogen from 2nd hydrogen
atom atom

Fig. 2.12, Calliser & Rethwisch 10e.

Chapter 2 - 15

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Chapter 2: Atomic Structure & Interatomic Bonding

Covalent Bonding: Bond Hybrization


Carbon can form sp3 _____
orbitals

sp3

109.5
sp3
C
sp3

sp3

Fig. 2.14, Callister & Rethwisch 10e.


(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 10e.


Chapter 2 - 16

Covalent Bonding (cont.)


Hybrid sp3 bonding involving carbon
Example: CH4
H
C: each has 4 valence electrons, 1s
needs 4 more sp3
sp3
H: each has 1 valence electron,
needs 1 more sp3
H C
1s
H
1s
H sp3
Electronegativities of C and H 1s
are similar so __________ are Region of overlap
shared in sp3 hybrid covalent Fig. 2.15, Callister & Rethwisch 10e.
bonds. (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

Metallic Bonding
Electrons ____________ to form an electron cloud

Fig. 2.19b, Callister & Rethwisch 10e.

Chapter 2 - 18

6
Chapter 2: Atomic Structure & Interatomic Bonding

Mixed Bonding
Most common mixed bonding type is Covalent-Ionic
mixed bonding
"
( X A XB )2 %
% ionic character = $$1 e 4 ' x (100%)
'
# &
where XA & XB are _____________________ of the two
elements participating in the bond
Ex: MgO XMg = 1.2
XO = 3.5


(3.51.2)2
% ionic character = 1 e 4 x (100%) = 73.3%

Chapter 2 - 19

Secondary Bonding
Arises from attractive forces between __________
Fluctuating __________
___________ electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding bonding

Permanent dipoles
secondary
-general case: + - bonding
+ -

secondary
-ex: liquid HCl H Cl bonding H Cl

second
-ex: polymer ary bo
nding linear polymer molecule
Chapter 2 - 20

Properties Related to Bonding I:


Melting Temperature (Tm)
Bond length, r Melting Temperature, Tm
Energy
r

________ energy, Eo ro
r
Energy smaller Tm

unstretched length
ro larger Tm
r
Eo = ________ Eo, the higher Tm
bond energy
Chapter 2 - 21

7
Chapter 2: Atomic Structure & Interatomic Bonding

Properties Related to Bonding II:


Coefficient of Thermal Expansion (l)
Coefficient of thermal expansion, l
length, L o L
= l (T2 -T1)
unheated, T1 Lo
L
heated, T2

The ______ Eo, the larger l.

___________ length Increase in bond length is due to


Energy

ro asymmetry of the E vs. r curve. This


r results in an increase in l.
Eo
______ l As E0 increases this asymmetry
decreases.
Eo smaller l
Chapter 2 - 22

Summary: Properties Related to


Bonding Type and Bonding Energy
Ceramics Large bond energy
(Ionic & covalent bonding): high Tm
large E
_________ l

Metals Variable bond energy


(Metallic bonding): __________ Tm
__________ E
moderate l

Polymers Weak bond energy (between chains)


(Covalent & Secondary): Secondary bonding responsible for
most physical properties
second low Tm
ary bo
nding
_________ E
large l
Chapter 2 - 23

SUMMARY
A materials chemical, electrical, thermal, and optical
properties are determined by electronic configuration.
Valence electrons occupy the outermost unfilled
electron shell.
Primary bonding types include covalent, ionic, and
metallic bonding.
Secondary or van der Waals bonds are weaker than
the primary bonding types.
The percent ionic character of a covalent-ionic mixed
bond between two elements depends on their
electronegativities.

Chapter 2 - 24