Chemical Bonding: For CHBrFCl, there are two distict structures with different

Shapes of Molecules or Molecular Geometries (Special Tutorial) properties. Isomers are molecules with same formula but
different structures and properties.
Lewis structures are useful. However, we need simple model for
predicting shapes of molecules.

Example
Consider the molecule chlorofluoromethane (CH2FCl) There are
two Lewis Dot Structure for this molecule

or
Notice that these can not be superimposed.
=> or
Flat representations produced in Lewis structures do not give a
If you're good at visualizing, you can see that two molecules complete picture. Molecules are not generally flat but exist in three
depicted are identical (Cl is red, F is green) and superimposible dimensions.

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Valence Shell Electron Pair Repulsion Theory (VSEPR)
This theory states that electron pairs in valence shell about an
atom repel one another and take up positions around atomic core
so that they are a maximum distance apart.
The positions of minimum energy for valence shell electron groups
centered around the nucleus are illustrated below, with each
balloon representing an electron group.

VESPR theory focuses not just on electron pairs but on electron

groups consisting of a bonded pair, lone pair, a single unpaired
electron or a double bond. Each is treated as one electron group
when determining shape.

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 Electron group geometry (electron group distribution)
APSC 131 – Chemical Bonding 4-04 –Shapes of Molecules : VSEPR theory
The following outlines various shapes molecules would exhibit
2 valence shell electron pairs (AX2 or 2,2,0)
BeCl2
This molecule is linear.
The Be does not fill its octet shell in this situation. To do so would
put large negative charge on it and a positive charge on chlorine
atoms. This is impossible because chlorine atoms are far more
electronegative than beryllium atoms.
APSC 131 – Chemical Bonding 4-04 –Shapes of Molecules : VSEPR theory
Each molecule can be represented by general formula AXnEy
x A represents central atom
x X represents atom bonded to A. Bond could be single, double
or triple bond. It makes no difference to the scheme.
x E represents non-bonded electron domain (lone pair).
Example
x Methane, CH4 ,is AX4 molecule- meaning that 4 H atoms are
bonded to the central C atom and there are no lone pairs
x Ammonia, NH3 ,is AX3E molecule- meaning that 3 H atoms
bonded to central N atom and there is a single lone pair of
electrons.
x Both of these molecules have four electron pair domains.
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3 valence shell electron pairs (AX3 or 3,3,0)
BF3 Trigonal Planar shape
LINEAR
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4 valence shell electron pairs Note

x In each of examples shown above, electron pair-domain

AX4 geometry is tetrahedral. However, the molecular shape is not
CH4 tetrahedral
(4,4,0) always so.

x In the case of CH4, the molecule is actually tetrahedral in

AX3E shape with a perfect tetrahedral angle of 109.5º.
NH3 trigonal pyramidal
(4,3,1)
x Next two examples have lone pairs which occupy a larger
AX2E2 domain volume (push more on the bonding pairs) and reduce
H2 O bent or angular the bond angle to less than 109.5º.
(4,2,2)

AX1E3 x The last case, HF, is simply a linear diatomic molecule. There
HF or just linear is no bond angle.
AXE3

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5 valence shell electron pairs x For five electron group molecules, electron-domain geometry
is always trigonal bipyramidal.
AX5
PCl5 trigonal bipyramidal
(5,5,0) x The first molecule, PCl5, has ideal angles of 90 and 120
degrees for axial and equatorial bonds, respectively.
x SF4 has one lone pair and four bonding pairs. Lone pair will
See Saw preferentially locate itself in an equatorial position since that
AX4E
SF4 or position has only two other pairs of electrons within 90
(5,4,1)
disphenoidal degrees while an axial position would have three. The
molecule has see-saw (disphenoidal) shape. Bond angles
less than ideal angles of 90 and 120 degrees.
AX3E2
ClF3 T-shaped x ClF3 has two lone pairs which locate themselves in equatorial
(5,3,2)
positionsThis molecule is T-shaped with bond angles of less
than 90 degrees.

XeF2 AX2E3 Linear

(5,2,3)

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6 valence shell electron pairs x In above examples, the electron-domain geometry is
octahedral and in the case of SF6, so is the shape.

SF6
AX6
Octahedral x Molecule ClF5 has one lone pair and five bonding pairs but
(6,6,0) since all positions in the octahedral geometry are equivalent, it
doesn't matter which position the lone pair takes. The
molecule is square pyramidal.
AX5E
ClF5 Square Pyramidal
(6,5,1) x In the case of XeF4, the two lone pairs will locate themselves
on opposite sides of the square planar molecule.
AX4E2
XeF4 Square Planar
(6,4,2)

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Dipole Moments and Predicting the Polarity of Molecules
x Electronegativity values used to determine bonding type
(covalent, ionic or polar covalent)
x In molecule HF, electron density shifts towards the more
electronegative F atom making F end of molecule more
electron rich and slightly negative (red) while H end of
molecule becomes electron poor and slightly positive (blue).
x Quantitatively, polarity of a bond (extent if charge
displacement) is measured using dipole moment (μ, mu),
where for polar bond between atoms A and B
A+ --- B-
μ=QxR
where
Q =the fraction of charge on an electron ( of 1.6 x 10-19 C)
that has shifted towards B, the more electronegative atom
R =bond length (m)
Dipole moment unit in debyes, D, where 1 D=3.336 x 10-30C.m

e.g. Suppose that in molecule of H–Cl, Q = 2.70 x 10-20 C,

experimentally determined by finding μ and R, which is 17%
charge on an electron. Means that shift of electron cloud density
towards Cl has given Cl an equivalent additional charge of 17%
of charge on electron. Bond is 17% ionic.

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 x Molecules having a dipole moment are said to be polar Consider the molecule NH3
molecules while those that don’t are called non polar
molecules.

x To be able to determine if a molecule is polar, both the

shape of the molecule and electronegativity values must be
known.

x The dipole moment of entire molecule is made up of bond

moments (the individual dipole moments in the bonds)
Each bond moment is a vector quantity and the vector sum
of all of the bond moments gives the dipole moment of
the entire molecule.
x Electron density shifts towards nitrogen (higher
electronegativity) and away from hydrogen
x Electron density of lone pair produces dipole
x Vector sum shows resultant molecular dipole
x This molecule is polar with N end of molecule, negative, and
hydrogen end of molecule, positive.

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Consider the substance NF3 Example

Predict whether each of the following molecules has a dipole

moment: (a) IBr, (b) BF3, (c) CH2Cl2

x Electron density shifts towards fluorine (higher

electronegativity) and away from nitrogen
x Electron density of lone pair produces dipole upwards
x Vector sum shows resultant molecular dipole is down
indicating that the three N – F bond moments acting down
offset the contribution of the lone pair acting up
x This molecule is polar with N end of molecule, positive, and
fluorine end of molecule, negative.

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Suggested Homework
Read Petrucci 395 -406
Study examples 10-10 and 10-11
Problems Chapter 10: 53, 55, 59, 61, 63, 69

Draw a Lewis structure and give the shape of each of the

following. Is the molecule polar or non polar?
x F2O (angular, polar) SCl4 (seesaw, polar)
x NF3 (trigonal pyramid, polar) XeCl2 (linear, non polar)
x CH4 (tetrahedral, non polar) ClI3 (T-shape, polar)
x BF3 (trigonal planar, non polar) TeCl4 (seesaw, polar)
x BeH2 (linear, non polar) H2 S (angular, polar)
x XeI4 (square planar, non polar) AsCl5 (trigonal bipyram)
x PI5 (trigonal bipyramid, non polar)
x SbCl5 (trigonal bipyramidal, non polar)
x BrF5 (square base pyramid, polar)

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