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Ch.

9 Chemical Bonding and


Molecular Structure
Brady & Senese, 5th Ed
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Index
9.1. Molecules are three-dimensional with shapes that are bui
lt from five basic arrangements
9.2. Molecular shapes are predicted using the VS!" model
9.#. Molecular s$mmetr$ affects the polarit$ of molecules
9.%. Valence bond theor$ explains bondi
ng as an overlap of orbitals
9.&. '$brid orbitals are used to explain experimental molecul
ar geometries
9.(. '$brid orbitals can be used to explain multiple bonds
9.). Molecular orbital theor$ explains bon
ding as constructive interference of atomic orbitals
9.*. Molecular orbital theor$ uses delocali+ed orbitals to des
cribe molecules with resonance structure
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9.1 Molecules are three-dimensional with shapes that are built from five basic
arrangements
#
,he -ive .asic lectron /rrangements
lectron
0omains
Shape lectron !air
1eometr$
2 linear
# trigonal planar
% tetrahedral
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9.1 Molecules are three-dimensional with shapes that are built from five basic
arrangements
%
,he -ive .asic lectron /rrangements 23ont.4
lectron 0omains Shape lectron !air 1eometr$
& trigonal bip$ramidal
has e5uatorial and axial
positions.
( octahedral
has e5uatorial and axial
positions
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9.1 Molecules are three-dimensional with shapes that are built from five basic
arrangements
&
6earning 3hec78
Identif$ ,he lectron !air 1eometr$ -or ach 3enter
tetrahedral tetrahedral
,rigonal
bip$ramidal
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9.1 Molecules are three-dimensional with shapes that are built from five basic
arrangements
(
9our ,urn:
;hat is the electron pair geometr$ for 3 in 3<
2
=
/. linear
.. planar triangular
3. tetrahedral
0. trigonal bip$ramidal
. octahedral
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9.2 Molecular shapes are predicted using the VS!" model )
.onding 0omains /nd >on-bonding 0omains
?
Bonding domains are shared
between nuclei
?
Non-bonding domains are not
shared between nuclei-the$ exert a
greater electrical field
?
"epulsion leads non-bonding
domains to occup$ larger space
?
,he basic shapes are distorted b$
non-bonding domains to create the
molecular geometry
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9.2 Molecular shapes are predicted using the VS!" model *
,rigonal !lanar Molecular 1eometries
.onding 0omains >on-bonding
0omains
Molecular
1eometr$
# @ trigonal planar
2 1 bent
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9.2 Molecular shapes are predicted using the VS!" model 9
,etrahedral Molecular geometries
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9.2 Molecular shapes are predicted using the VS!" model 1@
,rigonal .ip$ramidal
?
Equatorial 2e4
positions are
substituted first
?
,his is because
the eAe bond
angles are 12@BA
while aAe bond
angles are onl$
9@B
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9.2 Molecular shapes are predicted using the VS!" model 11
<ctahedral 1eometries
?
/ll bond angles
are 9@B
?
Axial positions
are substituted
first
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9.2 Molecular shapes are predicted using the VS!" model 12
6earning 3hec78
Identif$ the molecular geometr$ for each center
,rigonal
p$ramidal
>on-linearA
bent
6inear
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9.2 Molecular shapes are predicted using the VS!" model 1#
9our ,urn:
;hich re5uire more space=
/. bond pairs
.. lone pairs
3. both are the same
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9.2 Molecular shapes are predicted using the VS!" model 1%
9our ,urn:
;hich bond angles are closer in a trigonal
bip$ramidal structure 2aC axialD eCe5uatorial4=
/. a-a
.. a-e
3. e-e
0. the$ are all the same
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9.2 Molecular shapes are predicted using the VS!" model 1&
9our ,urn:
;hich bond angles are closer in a trigonal
bip$ramidal structure 2aC axialD eCe5uatorial4=
/. a-a
.. a-e
3. e-e
0. the$ are all the same
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9.2 Molecular shapes are predicted using the VS!" model 1(
9our ,urn:
;hat is the molecular geometr$ of 3 in 3'
%
=
/. 6inear
.. S5uare planar
3. S5uare p$ramidal
0. ,etrahedral
. >one of these
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9.# Molecular s$mmetr$ affects the polarit$ of molecules 1)
!olar Molecules /re /s$mmetric
?
,o determine the polarit$A draw the structure using
the proper molecular geometr$
?
0raw the bond dipoles
?
If the$ cancelA the molecule is non-polar
?
If the molecule has uneven dipole distributionA it is
polar
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9.# Molecular s$mmetr$ affects the polarit$ of molecules 1*
6earning 3hec78
!olar or non-polar=
polar >on-polar polar
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9.# Molecular s$mmetr$ affects the polarit$ of molecules 19
9our ,urn:
3'
2
3l3'
2
3l 2freon-1&@4 is li7el$ to be8
/. !olar
.. non-polar
3. cannot tell
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9.# Molecular s$mmetr$ affects the polarit$ of molecules 2@
9our ,urn:
.en+o$l peroxide 2used in common acne
medications4 is li7el$ to be8
/. polar
.. non-polar
3. cannot tell
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9.% Valence bond theor$ explains bonding as an overlap of atomic orbitals 21
Valence .ond ,heor$
? '
2
bonds form because atomic valence orbitals
overlap
?
'- involves overlaps between the s orbital on '
and the 2p orbital of -
1s 1s
1s 2s 2p
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9.% Valence bond theor$ explains bonding as an overlap of atomic orbitals 22
V. ,heor$ /nd '
2
S
?
/ssume that the
unpaired e
-
in S and '
are free to form a
paired bond
?
;e ma$ assume that
the '-S bond forms
between an s and a p
orbital
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9.% Valence bond theor$ explains bonding as an overlap of atomic orbitals 2#
9our turn:
/ccording to V. ,heor$8
;hich t$pe of overlap does not occur in .'
#
=
/. s-s
.. s-p
3. p-p
0. none of these
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9.% Valence bond theor$ explains bonding as an overlap of atomic orbitals 2%
9our turn:
/ccording to V. ,heor$8
;hich orbitals overlap in the formation of >'
#
=
/. s-s
.. s-p
3. p-p
0. none of these
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9.% Valence bond theor$ explains bonding as an overlap of atomic orbitals 2&
0ifficulties ;ith V. ,heor$ So -ar8
?
Most experimental bond angles do not support
those predicted b$ mere atomic orbital overlap
?
-or example8 3 1s
2
2s
2
2p
2
and ' 1s
1
?
xperimental bond angles in methane are 1@9.&B
and all are the same
?
p orbitals are 9@B apartA and not all valence e
-
in 3
are in the p orbitals
?
'ow can multiple bonds form=
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9.& '$brid orbitals are used to explain experimental molecular geometries 2(
'$bridi+ation
?
,he mixing of atomic orbitals to allow formation
of bonds that have realistic bond angles
?
,he new shapes that result are called Eh$brid
orbitalsF
?
,he number of h$brid orbitals re5uired C the
number of bonding domains G the number of
non-bonding domains on the atom
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9.& '$brid orbitals are used to explain experimental molecular geometries 2)
;hat Shall ;e 3all ,hese >ew <rbitals=
?
Since we have annexed the spaces previousl$
defined b$ atomic orbitalsA we name the h$brid as
a combination of the orbitals used to form the new
h$brid
?
<ne atomic orbital is used for ever$ h$brid formed
2orbitals are conserved4
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9.& '$brid orbitals are used to explain experimental molecular geometries 2*
'$brids -rom s H p /tomic <rbitals ta7e
VS!" 1eometr$
'$brid /tomic
<rbitals
Ised
lectron
1eometr$
sp
#
s G p
x
G p
$

G p
+
,etrahedralA
bond angles
1@9.&J
sp
2
s G p
x
G p
$
,rigonal
planarA bond
angles 12@ J
sp s G p
x
6inearA
bond angles
1*@ J
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9.& '$brid orbitals are used to explain experimental molecular geometries 29
6earning 3hec78
Identif$ ,he '$brid <rbitals In ,he -ollowingA .ased
<n ,heir VS!" 1eometr$
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9.& '$brid orbitals are used to explain experimental molecular geometries #@
0etermining h$bridi+ation8
1. expand all valence electrons within the valence
energ$ level. -or 3A for example this means8
?
2sKL 2p K M K MMM N'eO2s
2
2p
1

?
.ecomes8
?
2sK 2p K M K M K MM
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9.& '$brid orbitals are used to explain experimental molecular geometries #1
'$bridi+ation
?
2. >ow anal$+e the bonding and lone pair needs.
9ou will need to use one h$brid orbital for ever$
bonding domain and one for ever$ non-bonding
domain.
? -or 3 in 3'
%
we see that there are % attached
atoms and no lone pairs on 3. ,hus we will need %
h$brid orbitals.
H
H
H
H
C
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9.& '$brid orbitals are used to explain experimental molecular geometries #2
'$bridi+ation 2sp
#
4
?
#. >ow anal$+e the atomic orbital needs. 9ou will need
to use one atomic orbital for ever$ h$brid orbital .
? -or 3 in 3'
%
we will need % h$brid orbitals.
?
2sK 2p K M K KM
?
,husA we will need to use all valence level atomic
orbitals available to us.
?
22sK 2p K M K M K4
?
S G p G p G p P % new e5uivalent Esp
#
F orbitals.
H
H
H
H
C
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9.& '$brid orbitals are used to explain experimental molecular geometries ##
.onding in 3'
%

?
,he % h$brid orbitals are
evenl$ distributed around
the 3
?
,he ' s-orbitals overlap
the sp
#
h$brid orbitals to
form the bonds.
H
H H
H
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9.& '$brid orbitals are used to explain experimental molecular geometries #%
s H p h$brid shapes
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9.& '$brid orbitals are used to explain experimental molecular geometries #&
9our ,urn:
In the compound 3'
#
<'A what is the expected
h$bridi+ation on <=
/. sp
.. sp
2
3. sp
#
0. < does not h$bridi+e
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9.& '$brid orbitals are used to explain experimental molecular geometries #(
xpanded <ctet '$bridi+ation
?
3an be predicted from the geometr$ as well
?
In these situationsA d orbitals are be needed to
provide room for the extra electrons
?
<ne d orbital is added for each pair of electrons in
excess of the standard octet
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9.& '$brid orbitals are used to explain experimental molecular geometries #)
xpanded <ctet h$bridi+ation
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9.( '$brid orbitals can be used to describe multiple bonds #*
.onding ,$pes
?
,wo t$pes of bonds result from
orbital overlap8
?
sigma bonds

from head-on overlap

lie along the bond axis

account for the first bond


?
pi bonds

from lateral overlap b$ adQacent p or


d orbitals

pi bonds are perpendicular to bond


axis

account for the second and third


bonds in a multiple bond
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9.( '$brid orbitals can be used to describe multiple bonds #9
'$bridi+ation of 3 in 3'
2
<
<
' '
3
1. xpand all valence electrons within the same energ$
level. -or 3A for example this means8
?
2sKL 2p K M K MMM N'eO2s
2
2p
1

?
.ecomes8
?
2sK 2p K M K M K MM
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9.( '$brid orbitals can be used to describe multiple bonds %@
'$bridi+ation of 3 in 3'
2
<
<
' '
3
?
2. >ow anal$+e the bonding and lone pair needs.
9ou will need to use one h$brid orbital for
ever$ attached atom and one for ever$ lone pair.
-or 3 in 3'
2
< we see that there are # attached atoms
and no lone pairs on 3. ,hus we will need # h$brid
orbitals.
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9.( '$brid orbitals can be used to describe multiple bonds %1
sp
2
'$bridi+ation
?
#. >ow anal$+e the atomic orbital needs. 9ou will
need to use one atomic orbital for ever$ h$brid
orbital.
-or 3 in 3'
2
< we will need # h$brid orbitals.

2sK 2p K M K KM

,husA we will need to use # valence level atomic


orbitals available to usA and one of the p orbitals will
remain.

22sK 2p K M K 4 M K

s G p G p P # new Esp
2
F orbitals.

;e are left with one unh$bridi+ed orbital.


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9.( '$brid orbitals can be used to describe multiple bonds %2
>ow anal$+e the <8
?
N'eO 2s
2
2p
2
22sKL 2p K LM K 4 M K
?
,he < is has one bonding domain and 2 non-
bonding domainsA hence it will re5uire three
h$brid orbitals.
?
>o expansion neededA as one unpaired e
-
is
available to bond. Ise # atomic orbitals to ma7e
the new h$bridsA sp
2
. 22sKL 2p K LM K 4 M K
?
/gain we are left with one unh$bridi+ed p
orbital
<
' '
3
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9.( '$brid orbitals can be used to describe multiple bonds %#
!i .onding
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9.( '$brid orbitals can be used to describe multiple bonds %%
'R3S3 R'
?
ach 3 has a
triple bond
and a single
bond
?
"e5uires 2
h$brid
orbitalsA sp
?
unh$bridi+ed
p orbitals
used to form
the pi bond
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9.( '$brid orbitals can be used to describe multiple bonds %&
9our ,urn:
3onsider a molecule of 3'
#
3<
2
'8
'ow man$ pi bonds are there in the molecule=
/. 1
.. 2
3. #
0. %
. ,here are none
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9.) Molecular orbital theor$ explains bonding as constructive interference of atomic
orbitals
%(
Molecular <rbital ,heor$
?
Modification of V. theor$ that considers that the orbitals
ma$ exhibit interference.
?
;aves ma$ interfere constructivel$ or destructivel$
?
.onding orbitals stabili+eA antibonding destabili+e.
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9.) Molecular orbital theor$ explains bonding as constructive interference of atomic
orbitals
%)
M< diagrams
?
Show atomic energ$ level diagram for each atom
?
Show molecular orbitals 2bonding and
antibondingT4
?
1 M< for each /tomic orbital.
?
Show electron occupanc$ of the orbitals.
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9.) Molecular orbital theor$ explains bonding as constructive interference of atomic
orbitals
%*
-illing M< diagrams
1. lectrons fill the lowest-energ$ orbitals that are
available.
2. >o more than two electronsA with spins pairedA
can occup$ an$ orbital.
#. lectrons spread out as much as possibleA with
spins unpairedA over orbitals that have the same
energ$.
%. .ond order C e
-
in bonding orbital-e
-
in
nonbonding orbitals.
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9.) Molecular orbital theor$ explains bonding as constructive interference of atomic
orbitals
%9
0iatomic M< diagrams differ b$ group
?
/4 I - V .4 VI-VIII/
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9.) Molecular orbital theor$ explains bonding as constructive interference of atomic
orbitals
&@
M< diagrams
0raw the expected M< diagram for8
? <
2
?
.'
? 'e
2
;hich are not li7el$ to existA and wh$=
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9.* Molecular orbital theor$ uses delocali+ed orbitals to describe molecules with
resonance structures
&1
0elocali+ed lectrons
?
6ewis structures use resonance to explain that the
actual molecule appears to have several e5uivalent
bondsA rather than different possible structures
?
M< theor$ shows the electrons being delocalized
in the structure
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9.* Molecular orbital theor$ uses delocali+ed orbitals to describe molecules with
resonance structures
&2
3<
#
2-
'$bridi+ation
?
3arbonate has three e5uivalent resonance
structures. ;hat are the$A and which electrons are
delocali+ed=
?
0raw the h$brid molecule to indicate the
delocali+ation of these electrons.
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