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Chapter 1
Chapter 1
The Basics
Bonding and Molecular
Structure
Created by
Professor William Tam & Dr. Phillis Chang
Copyright © 2014 by John Wiley & Sons, Inc. All rights reserved.
About The Authors
These Powerpoint Lecture Slides were created and prepared by Professor
William Tam and his wife Dr. Phillis Chang.
Professor William Tam received his B.Sc. at the University of Hong Kong in
1990 and his Ph.D. at the University of Toronto (Canada) in 1995. He was an
NSERC postdoctoral fellow at the Imperial College (UK) and at Harvard
University (USA). He joined the Department of Chemistry at the University of
Guelph (Ontario, Canada) in 1998 and is currently a Full Professor and
Associate Chair in the department. Professor Tam has received several awards
in research and teaching, and according to Essential Science Indicators, he is
currently ranked as the Top 1% most cited Chemists worldwide. He has
published four books and over 80 scientific papers in top international journals
such as J. Am. Chem. Soc., Angew. Chem., Org. Lett., and J. Org. Chem.
Dr. Phillis Chang received her B.Sc. at New York University (USA) in 1994, her
M.Sc. and Ph.D. in 1997 and 2001 at the University of Guelph (Canada). She
lives in Guelph with her husband, William, and their son, Matthew.
(2) 1H 2H 3H
ionic bonding
+ –
Na Cl
1s2 2s2 2p6 1s2 2s2 2p6 3s2 3p6
8 8
© 2014 by John Wiley & Sons, Inc. All rights reserved.
3B. Covalent Bonds & Lewis
Structures
Covalent bonds form by sharing of
electrons between atoms of similar
electronegativities to achieve the
configuration of a noble gas
:Cl. . Cl:
: :
: :
[Ne] 3s2 3p5 [Ne] 3s2 3p5
: : covalent bonding
: :
:Cl—Cl:
© 2014 by John Wiley & Sons, Inc. All rights reserved.
Ions, themselves, may contain covalent
bonds. Consider, as an example, the
ammonium ion
H
H+ N
N H H
H H
H H
(ammonia) (ammonium cation)
(3 bonds on N) (4 bonds on N with
a positive charge on N)
C H Br
4 + 1 x 3 + 7 = 14
● H
: :
H C Br:
8 H remaining
valence 6 valence
electrons electrons
© 2014 by John Wiley & Sons, Inc. All rights reserved.
(2) Lewis structure of methylamine
(CH5N)
C H N
4 + 1 x 5 + 5 = 14
:
H C N H
12 valence H H
electrons
© 2014 by John Wiley & Sons, Inc. All rights reserved.
4A. Exceptions to the Octet Rule
(SiF62-)
© 2014 by John Wiley & Sons, Inc. All rights reserved.
Some highly reactive molecules or ions
have atoms with fewer than eight
electrons in their outer shell
F
B
F F
or F = Z - S /2 - U
where F is the formal charge, Z is the
group number of the element, S equals the
number of shared electrons, and U is the
number of unshared electrons
© 2014 by John Wiley & Sons, Inc. All rights reserved.
Examples
(1) The Ammonium ion (NH4+)
H
H NH Recall: F = Z - S /2 - U
H
Formal charge of H:
= 1 – 2/2 – 0 = 0
group number number of
number of shared unshared
of H electrons electrons
© 2014 by John Wiley & Sons, Inc. All rights reserved.
Formal charge of N:
= 5 – 8/2 – 0 = +1
group number number of
number of shared unshared
of N electrons electrons
Charge on ion = 4 x 0 +1 = +1
The arithmetic sum of all the formal
charges in a molecule or ion will equal
the overall charge on the molecule or ion
© 2014 by John Wiley & Sons, Inc. All rights reserved.
-
(2) The Nitrate ion (NO3 )
O
N Recall: F = Z - S /2 - U
O O
Formal charge of O:
= 6 – 2/2 – 6 = -1
group number number of
number of shared unshared
of O electrons electrons
© 2014 by John Wiley & Sons, Inc. All rights reserved.
Formal charge of O:
= 6 – 4/2 – 4 = 0
group number number of
number of shared unshared
of O electrons electrons
Formal charge of N:
= 5 – 8/2 – 0 = +1
group number number of
number of shared unshared
of N electrons electrons
Charge on ion = 2 x (-1) + 0 +1 = -1
© 2014 by John Wiley & Sons, Inc. All rights reserved.
(3) Water (H2O)
The sum of the formal charges on
each atom making up a molecule
must be zero
Charge on molecule = 0 + 2 x 0 = 0
© 2014 by John Wiley & Sons, Inc. All rights reserved.
5A. A Summary of Formal Charges
C4H10 and
Butane 2-Methylpropane
Cl
C3H7Cl Cl
and
1-Chloropropane 2-Chloropropane
© 2014 by John Wiley & Sons, Inc. All rights reserved.
Examples
Molecular Constitutional
Formula Isomers
O
OCH3
OH and
C4H8O2
O
Butanoic acid Methyl propanoate
© 2014 by John Wiley & Sons, Inc. All rights reserved.
7. How to Write and Interpret
Structural Formulas
H H Br
C OR C OR C etc.
H H H
Br Br H
H H H
Bromomethane
© 2014 by John Wiley & Sons, Inc. All rights reserved.
Br
H
H OH Cl
H
Examples of bond-line formulas that include
three-dimensional representations
H NH
2 Br H
HO
O O O
C C C
O O O O O O
1 2 3
O O O
C C C
O O O O O O
HO H NOT HO H
NOT
-O -O
N N
H H
H C H C
H H
O O
O
H3C O H+ OH H3C O +H H
© 2014 by John Wiley & Sons, Inc. All rights reserved.
Examples
(1) Benzene
R O
(3) Ozone (O3)
O
O O
© 2014 by John Wiley & Sons, Inc. All rights reserved.
8C. How to Decide When One
Resonance Structure Contributes
More to the Hybrid
The more covalent bonds a structure
has, the more stable it is
Charge separation decreases stability
Resonance structures for formaldehyde
Four O O Three
covalent covalent
C C
bonds H H H H bonds
more stable less stable
© 2014 by John Wiley & Sons, Inc. All rights reserved.
Structures in which all the atoms have
a complete valence shell of electrons
(i.e., the noble gas structure) are more
stable
C
1s 2s 2px 2py 2pz
109o H Tetrahedral
structure
C H
H H
Carbon with
(3-D stucture) 4 bonds
© 2014 by John Wiley & Sons, Inc. All rights reserved.
12A. The Structure of Methane
p-bond
(p-orbitals overlap)
H H
C C
H H
Planar structure
Carbon with (3 + 1p) bonds
© 2014 by John Wiley & Sons, Inc. All rights reserved.
© 2014 by John Wiley & Sons, Inc. All rights reserved.
© 2014 by John Wiley & Sons, Inc. All rights reserved.
An sp2-hybridized carbon atom
H H
i
H3C identical to Pr
H H
i
Pr CH3
vs. H
H H
trans -3-Hexene cis -3-Hexene
(3)
Br
Br Br vs. Br
trans -1,3- cis -1,3-
Dibromopropene Dibromopropene
Linear structure
Carbon with (2 + 2 p) bonds
sp2 orbital
● 33% s character, 66% p character
sp3 orbital
● 25% s character, 75% p character