12/10/09

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
________
neutrons } ___________

•  atomic number = # of protons in nucleus of atom

= # of electrons of _______ species

•  A [=] atomic mass unit = ____ = 1/12 mass of 12C

Atomic wt = wt of ___________ molecules or atoms

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

Chapter 2 - 2

Atomic Structure

•  Valence electrons determine all of the

following properties
1)  Chemical
2)  ________
3)  Thermal
4)  ________

Chapter 2 - 3

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Electronic Structure
•  Electrons have wavelike and particulate
properties.
–  This means that electrons are in ______ defined by a
probability.
–  Each orbital at discrete ___________ determined by
quantum numbers.

Quantum # Designation
n = ________ (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 = __________ 1, 3, 5, 7 (-l to +l)
ms = spin ½, -½

Chapter 2 - 4

Electron Energy States

Electrons...
• have discrete energy states
• tend to occupy lowest available energy state.

4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s

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

SURVEY OF ELEMENTS
• Most elements: Electron configuration 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 2s 2
Boron 5 1s 2 2s 2 2p 1 Adapted from Table 2.2,
Callister & Rethwisch 8e.
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? Valence (outer) shell usually not filled completely.

Chapter 2 - 6

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Electron Configurations
•  Valence electrons – those in unfilled shells
•  ______________________
•  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 3d 6 4s2

4d
4p N-shell n = 4

3d
4s

Energy 3p M-shell n = 3
3s
Adapted from Fig. 2.4,
Callister & Rethwisch 8e.
2p L-shell n = 2
2s

1s K-shell n = 1

Chapter 2 - 8

The Periodic Table

• Columns: Similar Valence Structure
inert gases
give up 1e-
give up 2e-

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

H He
Li Be O F Ne
Adapted from
Na Mg S Cl Ar Fig. 2.6,
Callister &
K Ca Sc Se Br Kr
Rethwisch 8e.
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

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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 - 10

Ionic bond – metal + nonmetal

______ _______
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

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Ionic Bonding
•  Energy – ________ energy most stable
–  Energy balance of attractive and ________ terms
A B
EN = EA + ER = - +
r rn
Repulsive energy ER

Interatomic separation r

Net energy EN
Adapted from Fig. 2.8(b),
Callister & Rethwisch 8e.

Attractive energy EA
Chapter 2 - 13

Examples: Ionic Bonding

• Predominant bonding in _________
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 - 14

Covalent Bonding
•  similar ______________ ∴ share electrons
•  bonds determined by _______ – s & p _______
dominate bonding
•  Example: CH4
shared electrons
H from carbon atom
C: has 4 valence e-, CH 4
needs 4 more
H: has 1 valence e-, H C H
needs 1 more
shared electrons
__________________ H from hydrogen
are comparable. atoms

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

Chapter 2 - 15

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Primary Bonding
•  Metallic Bond -- delocalized as electron cloud

•  Ionic-Covalent Mixed Bonding

 (X A −X B )2 
 − 
4
% ionic character = 1− e  x (100%)
 
 
where XA & XB are _________electronegativities
Ex: MgO X€Mg = 1.2
XO = 3.5

Chapter 2 - 16

SECONDARY BONDING
Arises from interaction between _________
• Fluctuating _________
_________ electron ex: liquid H 2
clouds H2 H2

+ - + - H H H H
secondary secondary
bonding Adapted from Fig. 2.13,
bonding
Callister & Rethwisch 8e.

• Permanent dipoles-molecule induced

secondary
-general case: + - bonding
+ -
Adapted from Fig. 2.15,
Callister & Rethwisch 8e.
secondary
-ex: liquid HCl H Cl bonding H Cl

secon
-ex: polymer dary
bond secondary bonding
ing
Chapter 2 - 17

Summary: Bonding
Type Bond Energy Comments
Ionic Large! Nondirectional (_________)

Covalent Variable Directional

large-Diamond (_____________, _________
small-Bismuth polymer chains)

Metallic Variable
large-Tungsten Nondirectional (______)
small-Mercury
Secondary smallest Directional
inter-chain (________)
inter-molecular
Chapter 2 - 18

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Properties From Bonding: Tm

• Bond length, r • Melting Temperature, Tm
Energy
r

• ______ energy, Eo ro
r
Energy _________ Tm

____________ length
ro larger Tm
r
Eo = ____________if Eo is larger.
“bond energy”

Chapter 2 - 19

Properties From Bonding : α

• Coefficient of thermal expansion, α
length, L o coeff. _________ expansion
unheated, T1
ΔL ΔL
= α (T2 -T1)
heated, T2 Lo

• α ~ symmetric at ro
Energy
____________ length
ro
r _________ Eo is smaller.

Eo
________ α

Eo larger α
Chapter 2 - 20

Summary: Primary Bonds

Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
______ α

Metals Variable bond energy

(Metallic bonding): _________ Tm
_________ E
moderate α

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small Tm
secon
dary
bond
________ E
ing
large α

Chapter 2 - 21