10-1
The Shapes of Molecules
10-2
Lewis Dot Structures
A bookkeeping way to keep track of valence
electrons and bonding in a molecule. Lines are used
to represent a pair of bonding electrons. Dots are
used to represent lone pair electrons.
10-3
The steps in converting a molecular formula into a Lewis structure.
Place atom
Molecular
Step 1 with lowest
formula
EN in center
Atom Add A-group
Step 2
placement numbers
Lewis
structure
10-4
Molecular
formula
For NF3
Atom
placement
5e-
:
N
: F: : F:
:
Sum of N F 7e- X 3 = 21e-
valence e-
Total 26e-
: F:
:
Remaining
valence e-
Lewis
structure
10-5
SAMPLE PROBLEM 10.1 Writing Lewis Structures for Molecules with
One Central Atom
PROBLEM: Write a Lewis structure for CCl2F2, one of the compounds
responsible for the depletion of stratospheric ozone.
SOLUTION: Cl
Step 1: Carbon has the lowest EN and is the central atom. Cl C F
The other atoms are placed around it.
F
Steps 2-4:
:
C has 4 valence e-, Cl and F each have 7. The : Cl :
sum is 4 + 4(7) = 32 valence e-.
:
:Cl C F:
Make bonds and fill in remaining valence
:
electrons placing 8e- around each atom. : F:
:
10-6
SAMPLE PROBLEM 10.2 Writing Lewis Structure for Molecules with
More than One Central Atom
PROBLEM: Write the Lewis structure for methanol (molecular formula
CH4O), an important industrial alcohol that is being used as a
gasoline alternative in car engines.
SOLUTION: Hydrogen can have only one bond so C and O must be next
to each other with H filling in the bonds.
There are 4(1) + 4 + 6 = 14 valence e-.
C has 4 bonds and O has 2. O has 2 pair of nonbonding e-.
H
:
H C O
: H
10-7
SAMPLE PROBLEM 10.3 Writing Lewis Structures for Molecules with
Multiple Bonds.
PROBLEM: Write Lewis structures for the following:
(a) Ethylene (C2H4), the most important reactant in the
manufacture of polymers
(b) Nitrogen (N2), the most abundant atmospheric gas
PLAN: For molecules with multiple bonds, there is an additional step which
follows the other steps in Lewis structure construction. If a central
atom does not have 8e-, an octet, then e- can be moved in to form a
multiple bond.
SOLUTION: (a) There are 2(4) + 4(1) = 12 valence e-. H can have only
one bond per atom.
H .. H H H
C C C C
H H H H
(b) N2 has 2(5) = 10 valence e-. Therefore a triple bond is required to make
the octet around each N.
.: :. : :
N N N N :
N N
:
. . . .
10-8
Resonance: Delocalized Electron-Pair Bonding
Ozone, O3 can be drawn in 2 ways
.. .. .. ..
: :
:
O O O
: O O O
.. .. .. ..
. .. .
: :
O O O
.. ..
10-9
10-10
Formal Charge: Selecting the Best Resonance Structure
An atom “owns” all of its nonbonding electrons and half of its bonding electrons.
# nonbonding e- = 2
# bonding e- = 6 X 1/2 = 3
Formal charge = +1
10-11
Resonance (continued)
10-12
Resonance (continued)
A B C
formal charges
-2 0 +1 -1 -1 0 0 0 0 -1 -1
-1
.. .. .. ..
:N
.. C O: :N C O: :N C O:
..
Forms B and C have negative formal charges on N and O; this makes them
more important than form A.
Form C has a negative charge on O which is the more electronegative
element, therefore C contributes the most to the resonance hybrid.
10-13
Lewis Structures - Exceptions to the Octet Rule
10-14
Using bond energies to calculate DH0rxn
DH0rxn = DH0reactant bonds broken + DH0product bonds formed
Enthalpy, H
DH0rxn
10-15
Using bond energies to calculate DH0rxn for combustion of methane
BOND BREAKAGE
4BE(C-H)= +1652kJ
2BE(O2)= + 996kJ
DH0(bond breaking) = +2648kJ
BOND FORMATION
2[-BE(C O)]= -1598kJ
Enthalpy,H
4[-BE(O-H)]= -1868kJ
DH0(bond forming) = -3466kJ
DH0rxn= -818kJ
10-16
SAMPLE PROBLEM 10.6 Calculating Enthalpy Changes from Bond
Energies
PROBLEM: Use average bond energies to calculate DH0rxn for the following
reaction:
CH4(g) + 3Cl2(g) CHCl3(g) + 3HCl(g)
PLAN: Write the Lewis structures for all reactants and products and
calculate the number of bonds broken and formed.
SOLUTION:
10-17
SAMPLE PROBLEM 10.6 Calculating Enthalpy Changes from Bond
Energies
continued
10-18
Valence-Shell Electron-Pair Repulsion Theory
(VSEPR)
10-19
Electron-group repulsions and the five basic
molecular shapes.
10-20
Looking at the Five Shapes in Detail
Examples:
CS2, HCN, BeF2
10-21
Factors Affecting Actual Bond Angles
Bond angles are consistent with theoretical angles when the atoms
attached to the central atom are the same and when all electrons are
bonding electrons of the same order.
Multiple bonds count just as one group but are larger than a single bond.
The result is some compression of the other bond angles.
10-22
The two molecular shapes of the trigonal planar electron-
group arrangement.
Class
Examples: Shape
10-23
The three molecular shapes of the tetrahedral electron-
group arrangement.
Examples:
CH4, SiCl4,
SO42-, ClO4-
NH3 H 2O
PF3 OF2
ClO3 SCl2
H 3 O+
10-24
The four molecular shapes of the trigonal bipyramidal
electron-group arrangement.
PF5 SF4
AsF5 XeO2F2
SOF4 IF4+
IO2F2-
ClF3 XeF2
BrF3 I3 -
IF2-
10-25
The three molecular shapes of the octahedral electron-
group arrangement.
SF6
IOF5
BrF5
XeF4
TeF5 -
ICl4-
XeOF4
10-26
The steps in determining a molecular shape.
Molecular
Step 1
formula
Molecular
shape
(AXmEn)
10-27
Lewis structures and molecular shapes
10-28
10-29
10-30
Molecular Shapes with More Than
One Central Atom
The tetrahedral
centers of ethane.
10-31
Molecular Shapes with More Than
One Central Atom
The tetrahedral
centers of ethanol.
10-32
SAMPLE PROBLEM 10.9 Predicting Molecular Shapes with More Than
One Central Atom
SOLUTION: tetrahedral
tetrahedral
trigonal planar
10-33
Molecular Polarity
10-34
SAMPLE PROBLEM 10.10 Predicting the Polarity of Molecules
PLAN: Draw the shape, find the EN values and combine the concepts to
determine the polarity.
10-35
SAMPLE PROBLEM 10.10 Predicting the Polarity of Molecules
10-36
End of Chapter 10
10-37