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10 Lecture PPT

Uploaded by

Jerome Leo
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© © All Rights Reserved
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Chapter 10

The Shapes of Molecules

10-1

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

The Shapes of Molecules

10.1 Depicting Molecules and Ions with Lewis Structures

10.2 Valence-Shell Electron-Pair Repulsion (VSEPR) Theory and


Molecular Shape

10.3 Molecular Shape and Molecular Polarity

10-2

Figure 10.1

The steps in converting a molecular formula into a Lewis structure.

10-3

Sum of
valence e-

: F:

: F:

Atom
placement

For NF3

Molecular
formula

Remaining
valence eLewis
structure

10-4

: F:

N 5eF 7e- x 3 = 21eTotal

26e-

SAMPLE PROBLEM 10.1


PROBLEM:

Writing Lewis Structures for Molecules with


One Central Atom

Write a Lewis structure for CCl2F2, one of the compounds


responsible for the depletion of stratospheric ozone.

PLAN: Follow the steps outlined in Figure 10.1.


SOLUTION:

Cl

Step 1: Carbon has the lowest EN and is the central atom.


The
aree-placed
Steps 2-4:
C other
has 4atoms
valence
, Cl andaround
F eachit.have 7. The
sum is 4 + 4(7) = 32 valence e-.
Make bonds and fill in remaining valence electrons
placing 8e- around each atom.
:Cl :

: F:

10-5

: :

F:

F
Cl
Cl C

: :

:Cl

Cl C

SAMPLE PROBLEM 10.2


PROBLEM:

Writing Lewis Structure for Molecules with


More than One Central Atom

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-.

C
H

10-6

H
O

C
H

C
H

: :

SAMPLE PROBLEM 10.3


PROBLEM:

Writing Lewis Structures for Molecules with


Multiple Bonds

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 a Step 5 which follows the
other steps in Lewis structure construction. If a central atom does not
have 8e-, an octet, then two e- (either single or nonbonded pair) 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
C

(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
.
.
.
.

:.

.:

10-7

Resonance: Delocalized Electron-Pair Bonding


O3 can be drawn in 2 ways -

O
A

O
C

Neither structure depicts O3 accurately but can be drawn to represent a


structure which is a hybrid of the two - a resonance structure.
B

B
O

O
O
A

O
C

O
O

O
A

O
C

Resonance structures have the same relative atom placement but a


difference in the locations of bonding and nonbonding electron pairs.
is used to indicate that resonance occurs.

10-8

SAMPLE PROBLEM 10.4


PROBLEM:
PLAN:

Write resonance structures for the nitrate ion, NO3-.

After Steps 1-4, go to 5 and then see if other structures can be


drawn in which the electrons can be delocalized over more than
two atoms.

SOLUTION:

Writing Resonance Structures

Nitrate has 1(5) + 3(6) + 1 = 24 valence e-

10-9

N does not have an


octet; a pair of ewill move in to form
a double bond.

N
O

N
O

Formal Charge: Selecting the Best Resonance Structure


An atom owns all of its nonbonding electrons and half of its bonding electrons.
Formal charge is the charge an atom would have if the bonding electrons
were shared equally.
Formal charge of atom =

1
# of valence e (# of unshared electrons +
# of shared electrons)
2
B
For OC
O
For OA
# valence e- = 6
O
O
# valence e = 6
# nonbonding e- = 6
A
C
# nonbonding e = 4
1
For OB
1
#
bonding
e
=
2
x
=1
# bonding e- = 4 x
=2
2
2
# valence e = 6
Formal charge = -1
Formal charge = 0
# nonbonding e- = 2
1
# bonding e- = 6 x
=3
2
Formal charge = +1
-

10-10

Formal Charge: Selecting the Best Resonance Structure


(continued)
Three criteria for choosing the more important resonance structure:
Smaller formal charges (either positive or negative) are preferable
to larger charges.
Avoid like charges (+ + or - - ) on adjacent atoms.
A more negative formal charge should exist on a more
electronegative atom (an atom with a larger EN value).

10-11

Formal Charge: Selecting the Best Resonance Structure


(continued)
EXAMPLE: NCO- has 3 possible resonance forms:

N C

formal charges
-2
N

+1

-1

N C

0
O

0
N

0
C

-1
O

Forms B and C have negative formal charges on N and O; this makes them
more preferred 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.

10-12

SAMPLE PROBLEM 10.5


PROBLEM:

Writing Lewis Structures for Octet-Rule Exceptions

Write Lewis structures for (a) H3PO4 (pick the most likely
structure); (b) BFCl2.

PLAN: Draw the Lewis structures for the molecule and determine if there is
an element which can be an exception to the octet rule. Note that
(a) contains P which is a Period-3 element and can have an
expanded valence shell.
SOLUTION:
-1
0

0H O

O
0
H
0

10-13

(a) H3PO4 has two resonance forms and formal charges


indicate the more important form.
+1
O H 0
0

0
0 H O

0
O

O H 0

0
0 O
H more stable
0
lower formal charges

(b) BFCl2 will have only 1


Lewis structure.
F
Cl

Cl

VSEPR Valence-Shell Electron-Pair Repulsion Theory


Each group of valence electrons around a central atom is located as far
away as possible from the others in order to minimize repulsions.
These repulsions maximize the space that each object attached to the
central atom occupies.
The result is five electron-group arrangements of minimum energy seen
in a large majority of molecules and polyatomic ions.
The electron-groups are defining the object arrangement, but the
molecular shape is defined by the relative positions of the atomic nuclei.
Because valence electrons can be bonding or nonbonding, the same
electron-group arrangement can give rise to different molecular shapes.
A - central atom

X -surrounding atom

AXmEn
integers

10-14

E -nonbonding valence electron-group

Figure 10.2

Electron-group repulsions and the five basic molecular shapes.

10-15

Figure 10.3

The single molecular shape of the linear electron-group arrangement.

10-16

Figure 10.4
The two molecular shapes of
the trigonal planar electrongroup arrangement.

10-17

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.
H

Effect of Double Bonds


120

ideal

120o
C

greater
electron
density

real

Sn
Cl

Cl
95o

10-18

116o

Effect of Nonbonding (Lone) Pairs


Lone pairs repel bonding pairs
more strongly than bonding pairs
repel each other.

larger EN

122o
O

Figure 10.5

The three molecular shapes of


the tetrahedral electron-group
arrangement.

10-19

Figure 10.6

10-20

Lewis structures and molecular shapes.

Figure 10.7

The four molecular shapes of the


trigonal bipyramidal electrongroup arrangement.

10-21

Figure 10.8

The three molecular


shapes of the octahedral
electron-group
arrangement.

10-22

Figure 10.9

10-23

The steps in determining a molecular shape.

Predicting Molecular Shapes with Two, Three,


or Four Electron Groups

SAMPLE PROBLEM 10.6

PROBLEM:

Draw the molecular shape and predict the bond angles (relative
to the ideal angles) of (a) PF3 and (b) COCl2.

SOLUTION: (a) For PF3 - there are 26 valence electrons, 1 nonbonding pair
F

The shape is based upon the tetrahedral arrangement.

F
F

P
F

<109.5

The type of shape is

AX3E

10-24

The F-P-F bond angles should be <109.5o due


to the repulsion of the nonbonding electron
pair.
The final shape is trigonal pyramidal.

SAMPLE PROBLEM 10.6

Predicting Molecular Shapes with Two, Three,


or Four Electron Groups

continued

(b) For COCl2, C has the lowest EN and will be the center atom.
There are 24 valence e-, 3 atoms attached to the center atom.
Cl

Cl
O
C
Cl

10-25

Cl

C does not have an octet; a pair of nonbonding


electrons will move in from the O to make a
double bond.
The shape for a molecule with a central atom
having three attachments and no nonbonding
pairs is trigonal planar.
O
The Cl-C-Cl bond angle will
be less than 120o due to
the electron density of the
C=O.

124.5o

Cl
111o

Cl

Type AX3

Predicting Molecular Shapes with Five or Six


Electron Groups

SAMPLE PROBLEM 10.7


PROBLEM:
SOLUTION:

F
F

Sb
F

Determine the molecular shape and predict the bond angles


(relative to the ideal angles) of (a) SbF5 and (b) BrF5.
(a) SbF5 - 40 valence e-; all electrons around central
atom will be in bonding pairs; shape is AX5, trigonal
bipyramidal.
F
F

Sb
F

F
F

(b) BrF5 - 42 valence e-; 5 bonding pairs and 1 nonbonding pair on central
atom. Shape is AX5E, square pyramidal.
F
F
F

10-26

Br

F
F

SAMPLE PROBLEM 10.8

PROBLEM:

PLAN:

Predicting Molecular Shapes with More Than


One Central Atom

Determine the shape around each of the central atoms in


acetone, (CH3)2C=O.

Find the shape around one central atom at a time after writing
the Lewis structure.

SOLUTION:

tetrahedral

H
H C
H

O
C

H
C H
H

trigonal planar
O
H
C
H C

HH

10-27

tetrahedral

Figure 10.10

10-28

The tetrahedral centers of ethane and of ethanol.

ethane

ethanol

CH3CH3

CH3CH2OH

Figure 10.11

10-29

The orientation of polar molecules in an electric field.

SAMPLE PROBLEM 10.9


PROBLEM:

Predicting the Polarity of Molecules

From electronegativity (EN) values and their periodic trends


(see Figure 9.19), predict whether each of the following
molecules is polar and show the direction of bond dipoles and
the overall molecular dipole when applicable:
(a) Ammonia, NH3

(b) Boron trifluoride, BF3

(c) Carbonyl sulfide, COS (atom sequence SCO)


PLAN: Draw the shape, find the EN values and combine the concepts to
determine the polarity.
SOLUTION:

(a) NH3

The dipoles reinforce each


other, so the overall molecule
is definitely polar.

ENN = 3.0
H

ENH = 2.1

N
H

N
H

bond dipoles

10-30

N
H

molecular
dipole

SAMPLE PROBLEM 10.9

Predicting the Polarity of Molecules

continued
(b) BF3 has 24 valence e- and all electrons around the B will be involved in
bonds. The shape is AX3, trigonal planar.
F
B

120o

F (EN 4.0) is more electronegative


than B (EN 2.0) and all of the dipoles
will be directed from B to F. Because
all are at the same angle and of the
same magnitude, the molecule is
nonpolar.

(c) COS is linear. C and S have the same EN (2.0) but the C=O bond is
quite polar (EN) so the molecule is polar overall.
S

10-31

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