Chemistry: A Molecular

Approach, 1st Ed.

Nivaldo Tro

Roy Kennedy
Massachusetts Bay Community College
Wellesley Hills, MA

2008, Prentice Hall

Structure Determines
Properties!
properties of molecular substances depend on
the structure of the molecule
the structure includes many factors, including:
the skeletal arrangement of the atoms
the kind of bonding between the atoms
 ionic, polar covalent, or covalent
the shape of the molecule
bonding theory should allow you to predict the
shapes of molecules

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Molecular Geometry
Molecules are 3-dimensional objects
We often describe the shape of a molecule
with terms that relate to geometric figures
These geometric figures have characteristic
“corners” that indicate the positions of the
surrounding atoms around a central atom in
the center of the geometric figure
The geometric figures also have
characteristic angles that we call bond
angles

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Using Lewis Theory to Predict
Molecular Shapes
Lewis theory predicts there are regions of
electrons in an atom based on placing shared
pairs of valence electrons between bonding
nuclei and unshared valence electrons
located on single nuclei
this idea can then be extended to predict the
shapes of molecules by realizing these
regions are all negatively charged and should
repel

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VSEPR Theory
electron groups around the central atom will
be most stable when they are as far apart as
possible – we call this valence shell electron
pair repulsion theory
since electrons are negatively charged, they
should be most stable when they are separated
as much as possible
the resulting geometric arrangement will allow
us to predict the shapes and bond angles in the
molecule

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Electron Groups
the Lewis structure predicts the
arrangement of valence electrons around the
central atom(s)
each lone pair of electrons constitutes one
electron group on a central atom
each bond constitutes one electron group on
a central atom
regardless of whether it is single, double, or triple
•• •• •• there are 3 electron groups on N
1 lone pair
•O N O ••1 single bond
• •• 1 double bond
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Molecular Geometries
there are 5 basic arrangements of electron
groups around a central atom
based on a maximum of 6 bonding electron groups
 though there may be more than 6 on very large atoms, it is
very rare
each of these 5 basic arrangements results in 5
different basic molecular shapes
in order for the molecular shape and bond angles to
be a “perfect” geometric figure, all the electron
groups must be bonds and all the bonds must be
equivalent
for molecules that exhibit resonance, it doesn’t
matter which resonance form you use – the
molecular geometry will be the same
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Linear Geometry
 when there are 2 electron groups around the
central atom, they will occupy positions opposite
each other around the central atom
this results in the molecule taking a linear
geometry
the bond
 angle is 180°

   
Cl Be Cl 
 O C O 

 
 

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Trigonal Geometry
when there are 3 electron groups around the
central atom, they will occupy positions in the
shape of a triangle around the central atom
this results in the molecule taking a trigonal
planar geometry
the bond angle is 120°
 
 
 F B F 
 

 F 



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Because the bonds are
not identical, the
observed angles are
slightly different from
ideal.

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Tetrahedral Geometry
when there are 4 electron groups around the
central atom, they will occupy positions in the
shape of a tetrahedron around the central atom
this results in the molecule taking a
tetrahedral geometry
the bond angle is 109.5°


 F 

 

 F C F 

 

 F 



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 ••
•• • Cl•
• Cl • • •• •
• •• Cl •
P ••
•• ••
• Cl
• •• Cl ••
••

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 ••
•• •F • ••
•F
• ••
• • F ••
••
•• S •• •
•F F•
• •• ••
• F•
• •• •

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 The Effect of Lone Pairs
lone pair groups “occupy more space” on the
central atom
because their electron density is exclusively on the
central atom rather than shared like bonding
electron groups
relative sizes of repulsive force interactions is:
Lone Pair – Lone Pair > Lone Pair – Bonding Pair > Bonding
Pair – Bonding Pair
this effects the bond angles, making them smaller
than expected

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The nonbonding
bonding electrons
electrons
are are
shared
localized
by twoonatoms,
the so
some ofatom,
central the negative
so area charge
of negative
is removed
charge from
takesthe
central
more space.
atom.

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Derivative of Trigonal Geometry
when there are 3 electron groups around
the central atom, and 1 of them is a lone
pair, the resulting shape of the molecule is
called a trigonal planar - bent shape
the bond angle is < 120°
        
     
 O S O   O S O   O S O 

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 1
    
 


O  Cl  O 

      

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Predicting the Shapes
Around Central Atoms
1) Draw the Lewis Structure
2) Determine the Number of Electron Groups
around the Central Atom
3) Classify Each Electron Group as Bonding or
Lone pair, and Count each type
 remember, multiple bonds count as 1 group
4) Use Table 10.1 to Determine the Shape and
Bond Angles

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Representing 3-Dimensional Shapes on
a 2-Dimensional Surface
one of the problems with drawing molecules is
trying to show their dimensionality
by convention, the central atom is put in the
plane of the paper
put as many other atoms as possible in the
same plane and indicate with a straight line
for atoms in front of the plane, use a solid
wedge
for atoms behind the plane, use a hashed
wedge
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 Multiple Central Atoms
many molecules have larger structures with
many interior atoms
we can think of them as having multiple
central atoms
when this occurs, we describe the shape
around each central atom in sequence


hape around left C is tetrahedral H O 

| ||  
hape around center C is trigonal planar
HCCOH
| 
hape around right O is tetrahedral-bent
H

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 Polarity of Molecules
 in order for a molecule to be polar it must
1) have polar bonds
 electronegativity difference - theory

 bond dipole moments - measured

2) have an unsymmetrical shape

 vector addition

 polarity affects the intermolecular forces of

attraction
 therefore boiling points and solubilities
 like dissolves like

 nonbonding pairs affect molecular polarity,

strong pull in its direction
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The H-Cl bond is polar. The bonding electrons
are pulled toward the Cl end of the molecule.
The net result is a polar molecule.

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The O-C bond is polar. The bonding electrons
are pulled equally toward both O ends of the
molecule. The net result is a nonpolar molecule.

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The H-O bond is polar. The both sets of
bonding electrons are pulled toward the O
end of the molecule. The net result is a polar
molecule.

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The H-N bond is polar. All the sets of bonding
electrons are pulled toward the N end of the
molecule. The net result is a polar molecule.

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Molecular Polarity Affects
Solubility in Water
polar molecules are attracted
to other polar molecules
since water is a polar
molecule, other polar
molecules dissolve well in
water
and ionic compounds as well
some molecules have both
polar and nonpolar parts

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Problems with Lewis Theory
Lewis theory gives good first approximations
of the bond angles in molecules, but usually
cannot be used to get the actual angle
Lewis theory cannot write one correct
structure for many molecules where resonance
is important
Lewis theory often does not predict the correct
magnetic behavior of molecules
e.g., O2 is paramagnetic, though the Lewis
structure predicts it is diamagnetic

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