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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 H 12.011 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 #
n = ________ (energy level-shell) l = subsidiary (orbitals) ml = __________ 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 - 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 Hydrogen Helium Lithium Beryllium Boron Carbon ... Neon Sodium Magnesium Aluminum ... Argon ... Krypton Atomic # 1 2 3 4 5 6 10 11 12 13 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) ... 2 2 6 2 6 10 2 1s 2s 2p 3s 3p 3d 4s 4p 6 (stable)

Adapted from Table 2.2, Callister & Rethwisch 8e.

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 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 - 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

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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


______ electrons

nonmetal
_______ 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 _______________. Large difference in ________________________ Example: NaCl Na (metal) unstable electron Na (cation) stable Cl (nonmetal) unstable

Ionic Bonding

Coulombic Attraction

Cl (anion) stable

Chapter 2 - 12

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Ionic Bonding
! Energy ________ energy most stable
! Energy balance of attractive and ________ terms

EN = EA + ER =
Repulsive energy ER

A r

B rn

Interatomic separation r Net energy EN


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

Attractive energy EA
Chapter 2 - 13

Predominant bonding in _________ NaCl MgO CaF 2 CsCl

Examples: Ionic Bonding

Give up electrons!

Acquire electrons
Chapter 2 - 14

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 ______________ ! share electrons ! bonds determined by _______ s & p _______ dominate bonding ! Example: CH4
C: has 4 valence e-, needs 4 more H: has 1 valence e-, needs 1 more __________________ 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 - 15

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Primary Bonding
! Metallic Bond -- delocalized as electron cloud ! Ionic-Covalent Mixed Bonding % ionic character =
# ( X A " X B )2 & " % ( 4 %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 _________ ex: liquid H 2 _________ electron H2 H2 clouds

secondary bonding

H H

H H
secondary bonding

Adapted from Fig. 2.13, Callister & Rethwisch 8e.

Permanent dipoles-molecule induced


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

secondary bonding secondary bonding


bond

Adapted from Fig. 2.15, Callister & Rethwisch 8e.

H Cl
secon dary

H Cl
secondary bonding
Chapter 2 - 17

ing

Summary: Bonding
Type!
Ionic! Covalent!

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

Comments!
Nondirectional (_________) Directional (_____________, _________ polymer chains) Nondirectional (______) Directional inter-chain (________) inter-molecular
Chapter 2 - 18

Metallic!

Secondary! smallest!

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Properties From Bonding: Tm


Bond length, r r ______ energy, Eo Energy ro
____________ length

Melting Temperature, Tm Energy

ro

r _________ Tm

r Eo = bond energy

larger Tm ____________if Eo is larger.

Chapter 2 - 19

Properties From Bonding : "#


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

$L = " (T2 -T1) Lo

" ~ symmetric at ro Energy ro


Eo Eo
____________ length

r ________ " larger "

_________ Eo is smaller.

Chapter 2 - 20

Summary: Primary Bonds


Ceramics
(Ionic & covalent bonding):!

Large bond energy


large Tm large E ______ "!

Metals
(Metallic bonding):!

Variable bond energy


_________ Tm _________ E moderate "!

Polymers
(Covalent & Secondary):!
secon dary bond ing

Directional Properties
Secondary bonding dominates small Tm ________ E large "!

Chapter 2 - 21