VSEPR Theory

 Types of e- Pairs
– Bonding pairs - form bonds
– Lone pairs - nonbonding electrons

Lone pairs repel

more strongly than
bonding pairs!!!
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 VSEPR Theory
 Lone pairs reduce the bond angle between
atoms.

Bond Angle
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Determining Molecular Shape
 Draw the Lewis Diagram.
 Tally up e- pairs on central atom.
– double/triple bonds = ONE pair
 Shape is determined by the # of bonding pairs and lone pairs.

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 Common Molecular Shapes

2 total
2 bond
0 lone

LINEAR
B A B

BeH2 180°
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 Common Molecular Shapes

3 total B

A
3 bond B B

0 lone

BF3
TRIGONAL PLANAR
120°
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 Common Molecular Shapes

3 total
2 bond
1 lone

SO2 BENT
<120°
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 Common Molecular Shapes
B

4 total A
B
4 bond B
B

0 lone

CH4 TETRAHEDRAL
109.5°
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 Common Molecular Shapes

4 total
3 bond
1 lone

NH3
TRIGONAL PYRAMIDAL
107°
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 Common Molecular Shapes

4 total
2 bond
2 lone

H2O BENT
104.5°
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 Examples
 PF3

4 total F P F
3 bond
1 lone F
TRIGONAL
PYRAMIDAL
107°

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 Examples
 CO2

2 total O C O
2 bond
0 lone
LINEAR
180°

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 H
H
109.5o
CH4 H C H C
H H

H H

molecular structural molecular

formula formula shape

C
H
H
H
tetrahedral tetrahedron ball-and-stick
shape of model
methane
 Methane & Carbon Tetrachloride
molecular structural molecular ball-and-stick
formula formula shape model

H H

CH4 H C H 109.5o
C
H H
H H

Cl

CCl4 Cl C Cl

Cl
space-filling model
 Molecular Geometry
180o
H
109.5o
109.5o
C
H
H
Linear Trigonal planar H

Tetrahedral

104.5o
107.3o
Bent
Trigonal pyramidal
H2O CH4 AsCl3 AsF5 BeH2 BF3 CO2
 H .. ..

C N O
H H H H H

..
109.5o 107o 104.5o

H H H
CH4, methane NH3, ammonia H2O, water

lone pair ..
electrons

O
O
O O
O O
O3, ozone
 Molecular Shapes
Three atoms (AB2) Four atoms (AB3) B
•Linear (180o) •Trigonal planar (120o)
•Bent •Trigonal pyramidal A
•T-shaped B B
B A B
linear trigonal planar

B
Five atoms (AB4)
•Tetrahedral (109.47o) tetrahedral
A
•Square planar
B
•Seesaw B

Bailar, Moeller, Kleinberg, Guss, Castellion, Metz, Chemistry, 1984, page 313.
 Bonding and Shape of Molecules
Number Number of Covalent
of Bonds Unshared Pairs Structure Shape Examples

2 0 -Be- Linear BeCl2

B
3 0 Trigonal planar BF3

4 0 C Tetrahedral CH4, SiCl4

:

3 1 N Pyramidal NH3, PCl3

:

2 2 O: Bent
H2O, H2S, SCl2
 AB2
Linear Molecular Shapes

AB3 AB3E
Trigonal planar Angular or Bent AB4 AB3E AB3E2
Tetrahedral Trigonal Angular
pyramidal or Bent

AB5 AB4E AB3E2 AB2E3

Trigonal bipyramidal Irregular tetrahedral T-shaped Linear
(see saw)

AB6 AB6E AB5E2

Octahedral Square pyramidal Square planar
 The VSEPR Model
The Shapes of Some Simple ABn Molecules

Linear Bent Trigonal Trigonal

planar pyramidal
O C O
O SF6
..
S
O O N F
.. .. SO2 F
F
S
O O

Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 305
 Molecular Shapes

AB2
Linear
AB3
Trigonal planar

AB2E
Angular or Bent
AB4
AB3E
Tetrahedral
Trigonal
AB2E2
pyramidal
Angular
or Bent
 Geometry of Covalent Molecules ABn, and ABnEm
Shared Unshared
Type Electron Electron Ideal Observed
Formula Pairs Pairs Geometry Molecular Shape Examples

AB2 2 0 Linear Linear CdBr2

AB2E 2 1 Trigonal planar Angular, or bent SnCl2, PbI2
AB2E2 2 2 Tetrahedral Angular, or bent OH2, OF2, SCl2, TeI2
2 3 Trigonal bipyramidal Linear XeF2
AB2E3
3 0 Trigonal planar Trigonal planar
AB3 BCl3, BF3, GaI3
3 1 Tetrahedral Triangular pyramidal
AB3E NH3, NF3, PCl3, AsBr3
3 2 Triangular bipyramidal T-shaped
AB3E2 4 0 Tetrahedral Tetrahedral ClF3, BrF3
AB4 CH4, SiCl4, SnBr4, ZrI4
4 1 Triangular bipyramidal Irregular tetrahedral
AB4E (or “see-saw”) SF4, SeCl4, TeBr4
4 2 Octahedral Square planar
AB4E2 5 0 Triangular bipyramidal Triangular bipyramidal XeF4
AB5 PF5, PCl5(g), SbF5
5 1 Octahedral Square pyramidal
6 0 Octahedral Octahedral
AB5E ClF3, BrF3, IF5
AB6 SF6, SeF6, Te(OH)6,
MoF6
Bailar, Moeller, Kleinberg, Guss, Castellion, Metz, Chemistry, 1984, page 317.
 Electron-Domain Geometries
Number of Arrangement of Electron-Domain Predicted
Electron Domains Electron Domains Geometry Bond Angles

B A B Linear 180o
2
B

A
3 Trigonal 120o
B B planar
B

4 Tetrahedral 109.5o
A
B
B

B
 Acetic Acid, CH3COOH

H O

H C C O H

Number of electron domains 4 3 4

Trigonal
Electron-domain geometry Tetrahedral Tetrahedral
planar

Predicted bond angles 109.5o 120o 109.5o

Hybridization of central atom sp3 sp2 none

Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 314
 First, the formation of BeH2 using pure s and p orbitals.
Be = 1s22s2
H

Be BeH2
H
s p No overlap = no bond!
atomic orbitals atomic orbitals

The formation of BeH2 using hybridized orbitals.

atomic orbitals

Be H
H Be H
s p
hybrid orbitals
H Be
BeH2
Be
s p sp p
All hybridized bonds have equal strength and have orbitals with identical energies.
 Hybrid Orbitals
Ground-state Be atom

1s 2s 2p

Be atom with one electron “promoted”

1s 2s 2p

hybrid orbitals
Energy

px py pz
n=2 1s sp 2p
sp
s Be atom of BeH2 orbital diagram
n=1
hybridize
H Be H
s orbital p orbital
two sp hybrid orbitals sp hybrid orbitals shown together
(large lobes only)
 Hybrid Orbitals
Ground-state B atom

2s 2p

B atom with one electron “promoted”

2s 2p

hybrid orbitals
Energy

px py pz
sp2 2p
sp2 B atom of BH3 orbital diagram
s
H
hybridize

s orbital B
H H
sp hybrid orbitals shown together
2
p orbitals three sps hybrid orbitals (large lobes only)
 Carbon 1s22s22p2

Carbon could only make two bonds

if no hybridization occurs. However,
carbon can make four equivalent bonds.

A
B
B

hybrid orbitals B
Energy

px py pz
sp3
sp3
s C atom of CH4 orbital diagram

Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 321
 Hybridization Involving d Orbitals

promote

3s 3p 3d 3s 3p 3d
unhybridized P atom vacant d orbitals
P = [Ne]3s23p3 hybridize

Ba
F
F Be five sp3d orbitals 3d
P F A Be

F
Be degenerate
F orbitals

Ba (all EQUAL)

Trigonal bipyramidal
 Multiple Bonds
promote hybridize

2s 2p 2s 2p sp2 2p

C2H4, ethene
H H
C C
H H
one  bond and one  bond

H H
  H H
C  C
C C
 
H H
H H
Two lobes of
one  bond
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 325-326
 C C
Multiple Bonds
promote hybridize

2s 2p 2s 2p sp2 2p

C2H4, ethene
HH HH
p p

sp 2
sp 2

C sp2
sp2 C
sp2 sp2
H HH
H p p

one  bond and one  bond

H H
  H H
C  C
C C
 
H H
H H
Two lobes of
one  bond
Brown, LeMay, Bursten, Chemistry The Central Science, 2000, page 325-326
 bond

Internuclear axis

p p