GEOMETRY AND SHAPE OF MOLECULES

A. Molecular Shapes

The Lewis structure helps us understand the composition of molecules and they form bonds. However,
the Lewis structure has limitations and only represents the bonding of electrons but not the shape of the
molecule. Therefore, we need to introduce another theory to define the shape of molecules.

The shape of a molecule is determined by its bond angles, the angles made by the lines joining the nuclei
of the atoms in the molecule. The bond angles of a molecule, together with the bond lengths define the
shape and size of the molecule.

Figure 1: There are five basic molecular shapes.

NOTE: Molecular geometry gives information about the general shape of the molecule as well as bond
lengths, bond angles, torsional angles and any other geometrical parameters that determine the position of
each atom.

In covalent molecules the bonds are of directional nature because the shared pairs of electrons remain
localized in a definite space between the nuclei of the participating atoms. The space model obtained by
joining the points which represent the different bonds in a covalent molecule accounts for its shape.
 VESPR MODEL
The VSEPR model or Valence Shell Electron Pair Repulsion is used to predict the molecular geometry
of a molecule when both bonding and nonbonding pairs are present in the molecule. The arrangement of
electron domains about the central atom of a molecule or ion is called its electron-domain geometry.

Imagine tying two identical balloons together at their ends. NOTE: The VSEPR model can predict
The two balloons naturally orient themselves to point away from the structure of nearly any molecule
each other; that is, they try to “get out of each other’s way” as or polyatomic ion in which the central
much as possible. If we add a third balloon, the balloons orient atom is a nonmetal, as well as the
themselves toward the vertices of an equilateral triangle, and if we structures of many molecules
add a fourth balloon, they adopt a tetrahedral shape. We see that an and polyatomic ions with a central
optimum geometry exists for each number of balloons. In some metal atom. The premise of the
ways, the electrons in molecules behave like these balloons. We VSEPR theory is that electron pairs
have seen that a single covalent bond is formed between two located in bonds and lone pairs repel
atoms when a pair of electrons occupies the space between the each other and will therefore adopt the
atoms. geometry that places electron pairs as
far apart from each other as possible.
We can use the VSEPR model to predict the geometry of most This theory is very simplistic and does
polyatomic molecules and ions by focusing only on the number of not account for the subtleties of orbital
electron pairs around the central atom, ignoring all other valence interactions that influence molecular
electrons present. According to this model, valence electrons shapes; however, the simple VSEPR
in the Lewis structure form groups, which may consist of a single counting procedure accurately predicts
bond, a double bond, a triple bond, a lone pair of electrons, or even the three-dimensional structures of a
a single unpaired electron, which in the VSEPR model is counted large number of compounds, which
as a lone pair. Because electrons repel each other electrostatically, cannot be predicted using the Lewis
the most stable arrangement of electron groups (i.e., the one with electron-pair approach.
the lowest energy) is the one that minimizes repulsions. Groups
are positioned around the central atom in a way that produces the
molecular structure with the lowest energy.

A bonding pair of electrons thus defines a region in which the electrons are most likely to be found. We
will refer to such a region as an electron domain. Likewise, a nonbonding pair (or lone pair) of electrons.

There are two types of electron domains:

1) A bonded atom

2) A non-bonding pair of electrons

 Each multiple bond in a
molecule also constitutes a
single electron domain. Each
nonbonding pair, single bond,
or multiple bond produces a
single electron domain around
the central atom in a molecule.

Using the VSEPR model, the

molecular geometry can be
determined when there is
nonbonding electron present in
the central atom. For example,
in Figure 11, NO has 3
2
-

electron domains. Therefore,

the electron domain geometry
is trigonal planar, and the
molecular geometry is bent.

Figure 12: electron-domain geometry and the functions of the number of electron domain geometry.

MOLECULAR SHAPE AND MOLECULAR POLARITY

SHORT RECAP: FORCES OF ATTRACTION

1. Intramolecular Forces of Attraction – Within/inside the molecule.

- Ionic Bonding: Transfer of Electron

- Covalent Bonding: Sharing of Electrons

Polar Covalent – electron shared unequally

Non-polar Covalent – electron shared equally.

2. Intermolecular Forces of Attraction – Between molecules.

- Hydrogen Bond

- Ion Dipole

- Ion-induced dipole

- Van der Waals

* London Dispersion

* Debye

* Keesom
 INTERMOLECULAR FORCES

HYDROGEN BOND

- Attraction of Hydrogen Atom to a highly electronegative atoms (F, O, N).

- is an intermolecular force (IMF) that forms a special type of dipole-dipole attraction when a hydrogen
atom bonded to a strongly electronegative atom exists in the vicinity of another electronegative atom with
a lone pair of electrons.

ION-DIPOLE NOTE:
- An ion-dipole interaction is the intermolecular force of attraction
Ion – contains unequal number of
between a charge ion (cation or anion) and a molecule. It is found
commonly in the solution where ionic compounds dissolve in polar protons and electrons.
solvents.
Dipole – contains 2 charges, where
one side is positive (+), and the other
is negative (-)
ION-INDUCED DIPOLE

- When an ion is placed next to a non-polar molecule, the ion forced it to be dipole.
- The dipole is TEMPORARY
- An ion-induced dipole force is a weak attraction that results when an ion interacts with a nonpolar
molecule The ion disturbs the arrangement of electrons in the nonpolar molecule, causing it to form a
temporary dipole.

VAN DER WAALS

LONDON DISPERSION

- Force of attraction between a non-polar, and non-polar molecule.

- Weakest force
- aka: Induced-Dipole – Induced-Dipole Interaction
DEBYE

-is defined as the attraction between a polar molecule and a nonpolar molecule, which governs many
self-assembling processes in materials.
- always attractive; does not vanish with higher temperature
- permanent (dipole – induced dipole)
- aka: Dipole-induced dipole interaction

KEESOM

-attrraction between a polar and a polar molecule.

- are the electrostatic forces between two permanent polar molecules. Generally, the positive end of one
molecule is attracted to the negative end of another molecule. As a result, the two molecules come closer,
adding to the stability of the substance. This interaction is different from a regular ionic or covalent bond
since there is no transfer or sharing of electrons.
- aka: Dipole-Dipole Interaction

- nothing follows -
 MOLECULAR POLARITY: BOND POLARITY

Bond Polarity - a measure of how equally the electrons in a bond are shared between the atoms of the
bond.

The polarity of a bond—the extent to which it is polar—is determined largely by the relative
electronegativities of the bonded atoms. Electronegativity (χ) was defined as the ability of an atom in a
molecule or an ion to attract electrons to itself. Thus there is a direct correlation between electronegativity
and bond polarity. A bond is nonpolar if the bonded atoms have equal electronegativities. If the
electronegativities of the bonded atoms are not equal, however, the bond is polarized toward the more
electronegative atom.

Bond Polarity related to electronegativity, and now it is related to the molecular geometry of a molecule.
For a molecule consisting of more than two atoms, the dipole moment depends on both the polarities of the
individual bonds and the geometry of the molecule. For each bond in the molecule, we consider the bond
dipole, which is the dipole moment due only to the two atoms in that bond.

Bond dipoles and dipole

moments are vector quantities; that is,
they have both a magnitude and a
direction. The dipole moment of a
polyatomic molecule is the vector sum of
its bond dipoles. Both the magnitudes
and the directions of the bond dipoles
must be considered when summing
vectors
For example in Figure 13, CO2 molecule is consisting of two C-O bonds. The molecular geometry of the
molecule is linear. So, the dipole moment of two C-O bond are cancelled out. Since dipole moment is a
vector quantity, means, it has direction. Therefore, the overall dipole moment of the molecule is the
vector sum of its bond dipoles and is equal to zero. The geometry of the molecule dictates that the overall
dipole moment be zero, making CO2 a nonpolar molecule.

The molecular geometry of water tells that the molecule is polar due to the fact that it has a bent shape, as
shown in Figure 14. This shape indicates that the electronegative central atom contains more electron
density, making the molecule more polar.