Chapter 9: Molecular Geometry

Learning Outcomes
Student should be able to use Lewis structure to determine the electron domain geometry and the molecular shape of a compound.

Molecular Shapes
Lewis electron-dot structures: - give us the connectivity between atoms. - is drawn with atoms in the same plane. e.g. Lewis structure of CF4 shows 4F atoms bonded to a central C atom.
F F C F
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 The actual 3D arrangement of the atoms has F atoms at the corners of a tetrahedron. (4 corners, 4 faces, each which is an equilateral triangle) The overall shape of a molecule is determined by its bond angle. In CF4: all 6 C-F angles = 109.5o - characteristic of tetrahedron. 109.5o

The VSEPR Model

Valence Shell Electron Pair Repulsion Theory (think in 3D)

Developed by Ron Gillespie and Istvn Hargittai in 1957. Assumption: electron pairs repel, so the bonding pairs and lone pairs attached to a central atom are located as far apart from each other as possible.
Bonding pair of electron: a region/domain in which it is most likely to find electrons. Nonbonding pair/lone pair: an electron domain that is located principally on 1 atom.
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 e.g.

N H H H

Non bonding pair/lone pair electron

All the N-H bonds involve bonding electron pairs

Electron domain geometry: arrangement of electron pairs/domains around the central atom. Molecular geometry: arrangement of atoms around the central atom. When describing shapes of molecules - give the molecular geometry rather than electron domain geometry.
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The VSEPR Model 5 Basic Arrangements of Electron Pairs/Domain:

No. of electron domain 2 Electron-domain Geometry Bond angles

Linear

180o

3 Trigonal planar 120o

No. of electron domain 4

Electron-domain Geometry

Bond angles

Tetrahedral

109.5o

Trigonal 120o and 90o bipyramidal

Octahedral

90

The VSEPR Model

Trigonal bipyramid: the electron domains can point toward 2 distinct type of positions. 2 positions are called axial positions, remaining 3 120o equatorial positions. 120o

90o

The VSEPR Model

Axial (ax)

Equatorial (eq)

Axial (ax)
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Effects of Lone Pair Electrons on Bond Angle E.g. All 3 compounds below have tetrahedral electron-domain geometries, but their bond angles differ slightly. Why?
H H N H H H H 109.471o H 107.643o C H O

105.611o H

Note that the bond angle decreases as no. of lone pair electrons increases.
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Reasons: Lone pairs repel more than bonding pairs. Therefore, the lone pairs cause the bond angles to close up. Bonding pair of electrons is attracted by both nuclei of the bonded atoms whereas lone pair electron is attracted by only 1 nucleus. Because lone pair electrons experiences less nuclear attraction, its electron domain is spread out more in space/exert greater repulsion on adjacent electron domains (compress bond angles).
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Electron domain geometry: Trigonal Planar :

120o 115.4o

Molecular Geometry: :

Trigonal Planar
Eg: BF3
F B F F

Bent
Eg: NO2N O O

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Electron domain geometry: Tetrahedral :

109.5o

Molecular Geometry: Tetrahedral H : :

C H H H

Trigonal pyramidal:
N H H H

Bent
O H H

Molecules with Expanded Valence Shells When the central atom of a molecule is from the 3rd period and beyond of the periodic table, the atoms may have 4 electron pairs around it. Molecules with 5/6 electron domains display a variety of molecular geometries. E.g.: Trigonal bipyramidal: will lone pair electron domain occupy axial or equatorial positions? Repulsions between domain is greater if they are situated 90o from each other than when they are 120o. Hence equatorial domain experiences less repulsion than axial domain. Thus, lone pair electrons always occupy equatorial positions in a trigonal bipyramidal.
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The VSEPR Model

120o

120o
90o

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 Octahedron - solid object with 6 vertices and 8 faces, each of which is an equilateral triangle.

All angles are 90o, and all 6 positions are equivalent, thus lone pair electrons may occupy any of the 6 vertices.
However, if there are 2 lone pair electron domains, their repulsions are minimized by pointing them toward opposite sides of the octahedron.
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Steps to predict molecular geometries using VSEPR model

1. 2. Sketch Lewis structure of the molecule/ion. Count total no. of electron domains and arrange them in the way that minimizes repulsions among them. 3. Describe molecular geometry. 4. A double/triple bond is counted as 1 electron domain. Note: # of electron domains = (# of atoms bonded to the central atom) + (# of nonbonding pairs on the central atom)

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Example 1: Determine the molecular geometry in ammonia, NH3.

Valence Electrons:
N =5 3H = 3 1 = 3 Total = 8

H N H H

H N H

H N H H
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4 electron pairs around N:

Electron domain geometry is tetrahedral. 3 atoms around N with 1 lone pair:

Molecular geometry is trigonal pyramidal.

H H

N 107.6

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Example 2: Determine the molecular geometry and bond angles in the ammonium ion, NH4+.

Valence Electrons: N =5 4H = 4 1 = 4 Charge = -1 Total = 8

H H N H H

H H N H H

H H N H H
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4 pairs of electrons around N: Electron domain geometry is tetrahedral. 4 atoms around N: Molecular geometry is tetrahedral. No lone pairs: Bond angles are 109.5o.
H H N H H

109.5o N H H H
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Example 3:

Determine the molecular geometry and bond angles in water. Valence Electrons: O =6 2H = 2 1 = 2 Total = 8

H O H

H O H

H O H

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4 pairs of electrons around O: Electron domain geometry is tetrahedral. 2 atoms around O: Molecular geometry is bent. Two lone pairs: Bond angle is less than 109.5o.

H
H O H

105.6o H
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Example 4:

Determine the molecular geometry and bond angles in CO2. Valence Electrons: C =4 2O = 2 6 = 12 Total = 16

O C O

O C O

O C O

O C O

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In VSEPR, we count multiple bonds as a single electron domain. 2 pairs of electrons around C: Electron domain geometry is linear. 2 atoms around C: Molecular geometry is linear. No lone pairs on C: Bond angle is 180o.

O C O

180o O C O
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Example 5:

Determine the molecular geometry and approximate bond angles in XeOF4. Valence Electrons: Xe = 8 O=6 4F = 4 7 = 28 Total = 42

O F F Xe F F
F F

O Xe F F

O F Xe F F
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6 pairs of electrons around Xe: Electron domain geometry is octahedral. 5 atoms around Xe: Molecular geometry is square pyramidal. One lone pair on Xe: O-Xe-F bond angle is less than 90o.

O F F Xe F F

O F F Xe

F F
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Exercises: Determine the molecular geometry in each of the following:

(a)SF4

F S F F F
Seesaw Trigonal planar

(b)CH2O

O C

H
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End of Chapter 9

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The Lewis structure of phosphine, PH3 has

_____________ of electrons.

A. B. C. D.

four bonding pairs three bonding pairs and one lone pair one bonding pair and three lone pairs two bonding pairs and two lone pairs

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The Lewis structure of phosphine, PH3 has

_____________ of electrons.

A. B. C. D.

four bonding pairs three bonding pairs and one lone pair one bonding pair and three lone pairs two bonding pairs and two lone pairs

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Use Valence Shell Electron Pair Repulsion (VSEPR) theory to predict the molecular geometry of CO32 ion.

A.

Linear

B.
C.

Tetrahedral
Trigonal planar

D.

Trigonal pyramidal

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Use Valence Shell Electron Pair Repulsion (VSEPR) theory to predict the molecular geometry of CO32 ion.

A.

Linear

B.
C.

Tetrahedral
Trigonal planar

D.

Trigonal pyramidal

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