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 of neutral species A [=] atomic mass unit = amu = 1/12 mass of 12 C Atomic wt = wt of 6.022 x 1023 molecules or atoms 1 amu/atom = 1g/mol C H 12.011 1.008 etc.
Chapter 2 - 2

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

Chapter 2 - 3

Electronic Structure
Electrons have wavelike and particulate properties.
This means that 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 3p 3s 2p 2s 1s M-shell n = 3
Adapted from Fig. 2.4, Callister & Rethwisch 8e.

N-shell n = 4

L-shell n = 2 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 ... 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 & Rethwisch 8e.

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 3p 3s 2p 2s 1s M-shell n = 3
Adapted from Fig. 2.4, Callister & Rethwisch 8e.

3d 6 4s2

N-shell n = 4 valence electrons

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

give up 1egive up 2egive up 3e-

Li Be

accept 2eaccept 1einert gases

He O S F Ne Cl Ar
Adapted from Fig. 2.6, Callister & Rethwisch 8e.

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 - 9

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

Smaller electronegativity

Larger electronegativity
Chapter 2 - 10

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.

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 - 11

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 - 12

 Predominant bonding in Ceramics NaCl MgO CaF 2 CsCl

Examples: Ionic Bonding

Give up electrons

Acquire electrons
Chapter 2 - 13

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.

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.

CH 4
H

shared electrons from carbon atom

H shared electrons from hydrogen atoms

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

Chapter 2 - 14

Primary Bonding
Metallic Bond -- delocalized as electron cloud Ionic-Covalent Mixed Bonding
(X A X B )2 % ionic character = 4 1e x (100%) where XA & XB are Pauling electronegativities

Ex: MgO

XMg = 1.2 XO = 3.5

x (100%) = 73.4% ionic
Chapter 2 - 15

( 3.5 1.2 )2 4 % ionic character = 1 e

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 - 16

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 - 17

Properties From Bonding :

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

heated, T2

L = (T2 -T1) Lo

~ symmetric at ro Energy
unstretched length ro

Eo Eo

larger smaller

is larger if Eo is smaller.

Chapter 2 - 18

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 da r y bo n di n g

Directional Properties
Secondary bonding dominates small Tm small E large
Chapter 2 - 19

ANNOUNCEMENTS
Reading: Core Problems: Self-help Problems:

Chapter 2 - 20