CHAPTER 2: BONDING AND PROPERTIES

ISSUES TO ADDRESS...
What promotes bonding? What types of bonds are there? What properties are inferred from bonding?

Chapter 2 - 1

IMPORTANCE OF BONDING

In some cases the type of bond explains materials properties Geckos have very sticky feet that cling to any surface! There are a large number of microscopic hairs on their toe-pads. Which are self cleaning! Weak intermolecular forces are established between the hairs and any surface; resulting in adhesion. Self cleaning reversible adhesives!
Chapter 2 - 2

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 of neutral species A [=] atomic mass unit = amu = 1/12 mass of 12C Atomic wt = wt of 6.023 x 1023 molecules or atoms 1 amu/atom = 1g/mol C H 12.011 1.008 etc.
Chapter 2 - 3

Atomic Structure
Valence electrons determine all of the following properties
1) 2) 3) 4) Chemical Electrical Thermal Optical

Chapter 2 - 4

Electronic Structure
Electrons have wavelike and particulate properties.
This means that electrons in orbitals are defined by a probability. Each orbital at discrete energy level determined by quantum numbers. Quantum #
n = principal (energy level-shell) l = subsidiary (orbitals) ml = magnetic ms = spin

Designation
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) , -
Chapter 2 - 5

Electron Energy States

Electrons...
have discrete energy states tend to occupy lowest available energy state.
4d 4p 3d 4s Energy 3p 3s 2p 2s 1s M-shell n = 3
Adapted from Fig. 2.4, Callister 7e.

N-shell n = 4

L-shell n = 2 K-shell n = 1
Chapter 2 - 6

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 ... Argon ... Krypton 18 ... 36
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 ... 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 ... 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)

Adapted from Table 2.2, Callister 7e.

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

Chapter 2 - 7

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 - 8

Electronic Configurations
ex: Fe - atomic # = 26 1s2 2s2 2p6 3s2 3p6
4d 4p 3d 4s Energy 3p 3s 2p 2s 1s M-shell n = 3
Adapted from Fig. 2.4, Callister 7e.

3d 6 4s2

N-shell n = 4 valence electrons

L-shell n = 2 K-shell n = 1
Chapter 2 - 9

give up 1e give up 2e give up 3e

Li Be

accept 2e accept 1e inert gases

He O S F Ne Cl Ar
Adapted from Fig. 2.6, Callister 7e.

Columns: Similar Valence Structure

The Periodic Table

Na Mg

K Ca Sc Rb Sr Cs Ba Fr Ra Y

Se Br Kr Te I Xe

Po At Rn

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

Electronegative elements: Readily acquire electrons to become - ions.

Chapter 2 - 10

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

Smaller electronegativity

Larger electronegativity
Chapter 2 - 11

Adapted from Fig. 2.7, Callister 7e. (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.

Ionic bond metal

donates electrons

nonmetal
accepts electrons

Dissimilar electronegativities
ex: MgO Mg 1s2 2s2 2p6 3s2 [Ne] 3s2 O 1s2 2s2 2p4

Mg2+ 1s2 2s2 2p6 [Ne]

O2- 1s2 2s2 2p6 [Ne]

Chapter 2 - 12

Occurs between + and - ions. Requires electron transfer. Large difference in electronegativity required. Example: NaCl Na (metal) unstable electron Na (cation) stable Cl (nonmetal) unstable

Ionic Bonding

Coulombic Attraction

Cl (anion) stable

Chapter 2 - 13

Ionic Bonding
Energy minimum energy most stable
Energy balance of attractive and repulsive terms

EN = EA + ER =
Repulsive energy ER

A r

B rn

Interatomic separation r Net energy EN

Adapted from Fig. 2.8(b), Callister 7e.

Attractive energy EA
Chapter 2 - 14

 Predominant bonding in Ceramics NaCl MgO CaF 2 CsCl

Examples: Ionic Bonding

Give up electrons

Acquire electrons
Chapter 2 - 15

Adapted from Fig. 2.7, Callister 7e. (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.

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. Bonding is directional.

CH 4
H

shared electrons from carbon atom

H shared electrons from hydrogen atoms

Adapted from Fig. 2.10, Callister 7e.

Chapter 2 - 16

Metallic Bonding
Metallic Bond -- delocalized as electron cloud

Chapter 2 - 17

Mixed Bonding
Ionic-Covalent Mixed Bonding % ionic character =

(X A X B )2 4 1e x (100%)

where XA & XB are Pauling electronegativities Ex: MgO XMg = 1.3 XO = 3.5
x (100%) = 70.2% ionic
Chapter 2 - 18

(3.5 1.3 )2 4 % ionic character = 1 e

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

ex: liquid H 2 H2 H2 H H
secondary bonding

secondary bonding

H H

Adapted from Fig. 2.13, Callister 7e.

Permanent dipoles-molecule induced

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

secondary bonding secondary bonding

Adapted from Fig. 2.14, Callister 7e.

H Cl
secon da

H Cl
secondary bonding
Chapter 2 - 19

r y bo n di n g

Chapter 2 - 20

Chapter 2 - 21

Summary: Bonding
Type
Ionic Covalent

Bond Energy
Large! Variable large-Diamond small-Bismuth Variable large-Tungsten small-Mercury smallest

Comments
Nondirectional (ceramics) Directional (semiconductors, ceramics polymer chains) Nondirectional (metals) Directional inter-chain (polymer) inter-molecular
Chapter 2 - 22

Metallic

Secondary

Properties From Bonding: Tm

Bond length, r r Bond energy, Eo Energy
unstretched length ro

Melting Temperature, Tm Energy

ro smaller Tm r larger Tm

Eo = bond energy

Tm is larger if Eo is larger.

Chapter 2 - 23

Properties From Bonding :

Coefficient of thermal expansion, length, L o coeff. thermal expansion
unheated, T1 heated, T2

L = (T2 -T1) Lo

~ symmetry at ro Energy
unstretched length ro

is larger if Eo is smaller.

Eo Eo

larger smaller
Chapter 2 - 24

Summary: Primary Bonds

Ceramics
(Ionic & covalent bonding):

Large bond energy

large Tm large E small

Metals
(Metallic bonding):

Variable bond energy

moderate Tm moderate E moderate

Polymers
(Covalent & Secondary):
secon d ar y b o n d in g

Directional Properties
Secondary bonding dominates small Tm small E large
Chapter 2 - 25

Chapter 2 - 26

Chapter 2 - 27

Chapter 2 - 28