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General Chemistry

Principles and Modern Applications


Petrucci Harwood Herring
8th Edition

Chapter 11: Chemical Bonding I:


Basic Concepts
Philip Dutton
University of Windsor, Canada
N9B 3P4
Prentice-Hall 2002

Contents
11-1
11-2
11-3
11-4
11-5
11-6
11-7
11-8
11-9

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Lewis Theory: An Overview


Covalent Bonding: An Introduction
Polar Covalent Bonds
Writing Lewis Structures
Resonance
Exceptions to the Octet Rule
The Shapes of Molecules
Bond Order and Bond Lengths
Bond Energies
Focus on Polymers
Macromolecular Substances
General Chemistry: Chapter 11

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General Chemistry: Chapter 11

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11-1 Lewis Theory: An Overview


Valence e- play a
fundamental role in
chemical bonding.
e- transfer leads to ionic
bonds.
Sharing of e- leads to
covalent bonds.
e- are transferred of
shared to give each atom
a noble gas configuration
the octet.
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Lewis Symbols
A chemical symbol represents the nucleus
and the core e-.
Dots around the symbol represent valence e-.

Si

Al

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As

Se

Bi

Sb

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Ar

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Lewis Structures for Ionic Compounds


O

2+

Ba

Ba

BaO

Cl

Mg

2 Cl

Cl

2+

Mg

MgCl2

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11-2 Covalent Bonding

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Coordinate Covalent Bonds

Cl

H N H

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Cl

H N

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Multiple Covalent Bonds

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O C O

O C O

O C O

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Multiple Covalent Bonds

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N N

N N

N N

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Writing Lewis Structures


All the valence e- of atoms must appear.
Usually, the e- are paired.
Usually, each atom requires an octet.
H only requires 2 e-.

Multiple bonds may be needed.


Readily formed by C, N, O, S, and P.

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Skeletal Structure
Identify central and terminal atoms.
H
H C
H

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H
C O H
H

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Skeletal Structure
Hydrogen atoms are always terminal atoms.
Central atoms are generally those with the lowest
electronegativity.
Carbon atoms are always central atoms.
Generally structures are compact and symmetrical.

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Strategy for
Writing Lewis
Structures

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Formal Charge

FC = #valence e- - #lone pair e- -

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1
2

#bond pair e-

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Example 11-6
Writing a lewis Structure for a Polyatomic Ion.
Write the Lewis structure for the nitronium ion, NO2+.
Step 1:

Total valence e- = 5 + 6 + 6 1 = 16 e-

Step 2:

Plausible structure:

Step 3:

Add e to terminal atoms:

Step 4:

Determine e- left over:

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ONO

ONO

16 4 12 = 0
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Example 11-6
Step 5:

Use multiple bonds to satisfy octets.

O=N=O

Step 6:

ONO

Determine formal charges:


1
FC(O) = 6 - 4
(4) = 0
2
FC(N) = 5 - 0

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1
(8) = +1
2

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Alternative Lewis Structure


+

O N O

ONO

1
FC(O) = 6 - 2
(6) = +1
2
FC(N) = 5 - 0

1
(8) = +1
2

FC(O) = 6 - 6

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1
(2) = -1
2

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Alternative Lewis Structures


Sum of FC is the overall charge.
FC should be as small as possible.
Negative FC usually on most electronegative elements.
FC of same sign on adjacent atoms is unlikely.
+

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ONO

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Example 11-7
Using the Formal Charge Concept in Writing Lewis Structures.
Write the most plausible Lewis structure of nitrosyl chloride,
NOCl, one of the oxidizing agents present in aqua regia.

2+

2-

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2+

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11-5 Resonance

+ -

O
O O

O
O O

+ -

O
O O

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11-6 Exceptions to the Octet Rule


Odd e- species.

N=O

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OH

HCH

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Exceptions to the Octet Rule


Incomplete octets.

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Exceptions to the Octet Rule


Expanded octets.

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F
F

Cl

Cl

Cl

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Cl

Cl

Cl

P
Cl

Cl

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Expanded Valence Shell

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VBT
Bond is cosequence of overlapping of two atomic
orbitals
Orbital with unpaired e can only overlape
Combination of two atomic orbital will form one
moecular orbital
M.O. can be of two type i and ii
i = e density is max. along inter nuclear axis
i = e density is max. above and below
inter nuclear axis
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Potential Energy Diagram

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12-2 Introduction to the Valence-Bond


Method
Atomic orbital overlap describes covalent
bonding.
Area of overlap of orbitals is in phase.
A localized model of bonding.

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Valence shell electron pair repulsion


(VSEPR) theory
(VSEPR) theory is a model in chemistry used to
predict the shape of individual molecules
It is based upon the extent of electron-pair
electrostatic repulsion.
The premise of VSEPR is that the valence electron
pairs surrounding an atom mutually repel each
other, and will therefore adopt an arrangement that
minimizes this repulsion,

The number of electron pairs surrounding an atom,


both bonding and nonbonding, is called its steric
number.
The AXE method of electron counting is
commonly used when applying the VSEPR theory.
The X represents the number of sigma bonds
between the central atoms and outside atoms
Multiple covalent bonds (double, triple, etc) count
as one X.

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The E represents the number of lone electron pairs surrounding the


central atom.
The sum of X and E, known as the steric number, is also associated
with the total number of hybridized orbitals used by valence bond
theory.
Based on the steric number and distribution of Xs and Es, VSEPR
theory makes the predictions in the following tables.
Note that the geometries are named according to the atomic positions
only and not the electron arrangement.
For example the description of AX2E1 as bent means that AX2 is a
bent molecule without reference to the lone pair, although the lone
pair helps to determine the geometry.

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Parent shapes for EXn molecules n= steric number

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Steric No -2 linear

AX2

Steric number =3 , trigonal planer

AX3

3= 3+0

AX2E1
3= 2+1

Bent

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Steric number =4 , tetrahedral


AX4

AX3E1

AX2E2
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Steric number =5, trigonal bi pyramidal


AX4E1
AX5

See saw

T shaped
Linear

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Steric number =6 , Octahedral

AX6
AX5L

AX4L2

Square planer

Square pyramid

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Steric number =7 , pentagonal bipyramidal

AX7

Applying VSEPR Theory


Find steric number by S.N.= HO= M+V/2
Determine the number of identify them as bond or
lone pairs.
BONDS.= Number of all surrounding atoms
LONE PAIRS = all Surrounding atoms - BONDS
Multiple bonds count as one group of electrons.
More than one central atom can be handled
individually.

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11-7 The Shapes of Molecules


H

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Terminology
Bond length distance between nuclei.
Bond angle angle between adjacent bonds.
VSEPR Theory
Electron pairs repel each other whether they are in
chemical bonds (bond pairs) or unshared (lone pairs).
Electron pairs assume orientations about an atom to
minimize repulsions.

Electron group geometry distribution of e- pairs.


Molecular geometry distribution of nuclei.
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Methane, Ammonia and Water

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Table 11.1 Molecular Geometry as a


Function of Electron Group Geometry

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Polar Molecules
Molecules with ends

50

Polar Molecules

Molecules with a partially positive end

and a partially negative end


Requires two things to be true
The molecule must contain polar bonds
This can be determined from
differences in electronegativity.
Symmetry can not cancel out the effects
of the polar bonds.
Must determine geometry first.
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5.5 Properties of
covalent bonds
Dipole moments depend on bond polarities

They also depend on molecular shape

Dipole moments
Polar bonds
Polar bonds can result in polar
molecules, depending on
the molecules geometry
A polar molecule will align
itself in an electric field
The extent to which the
molecules align in a field is
referred to as the dipole
moment and has the Greek
symbol mu,
9.5 Properties of Covalent Bonds

Hydrogen Halides

9.5 Properties of Covalent Bonds

11-3 Polar Covalent Bonds

Cl

POLAR COVALENT BONDS


1. Electronegativity (EN) is the ability of an element to attract
electrons that it is
sharing in a covalent bond.
1) When two atoms of different EN forms a covalent bond, the
electrons are not shared equally between them.
2) The chlorine atom pulls the bonding electrons closer to it and becomes
somewhat electron rich bears a partial negative charge ().
3) The hydrogen atom becomes somewhat electron deficient bears a
partial charge (+).

Electronegativity

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Dipole moment of HF

Dipole Moments
Dipole Moments

Debye [unit of dipole moment]


Dipole Moment : the product of charge on pole and distance of
separation (bond length)
Let charge on any one end to be e and distance Between ends
to be d then
Dipole moment of this bond will be

Dipole moment = charge (in esu) x distance (in cm)


=exd
( 1debye = 1 x 1018 esu cm)
The charges are typically on the order of 10 10 esu; the
8

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Dipole Moments

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Properties of bond

Four important properties of bonds


Bond length the nuclear separation distance
where the molecule is most stable.
Bond energy the stability of a chemical bond
Bond polarityBond angles
9.5 Properties of Covalent Bonds

Table 9 1: Average Bond Lengths

9.5 Properties of Covalent Bonds

What affects bond length?


1.

The smaller the principle quantum numbers of the


valence orbitals, the shorter the bond.

2.

The higher the bond multiplicity, the shorter the bond.

3.

The higher the effective nuclear charge of the bonded


atoms, the shorter the bond.

4.

The larger the electronegativity difference, the shorter


the bond.

9.5 Properties of Covalent Bonds

Bond Energy
1.

Bond strength increases as more electrons are shared


between the atoms

2.

Bond strength increases as the electronegativity


difference () between bonded atoms increases.

3.

Bond strength decreases as bonds become longer.

9.5 Properties of Covalent Bonds

Table 9 3 Features of Molecular Geometries

9.5 Properties of Covalent Bonds

Percent Ionic Character

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Bond Order and Bond Length


Bond Order
Single bond, order = 1
Double bond, order = 2

Bond Length
Distance between two nuclei

Higher bond order


Shorter bond
Stronger bond
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Bond Length

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Bond Energies

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Bond Energies

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Bond Energies and Enthalpy of Reaction

Hrxn = H(product bonds) - H(reactant bonds)


= H bonds formed - H bonds broken
= -770 kJ/mol (657 kJ/mol) = -114 kJ/mol
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Focus on Polymers Macromolecular


Substances

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Chapter 11 Questions

1, 4, 6, 8, 10, 11, 15, 27, 33, 37,


53, 57, 65 (also calculate formal charges),
71, 86, 94

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