CHEM 108

Lab Activity: Background information for

L.D. structures, geometrical structures, polarities, etc.

Lewis Dot Structure:

A Lewis Dot Structure is used to show covalent molecule’s (or polyatomic ion’s) structures with the valence electrons
shown distributed about the bonded atoms. The electrons are either shared electron pairs (bonded pairs) or unshared
electron pairs (lone pairs). Lines are drawn between atoms that are bonded to one another (sometimes pairs of dots are
used instead of lines). Double bonds share two pairs of electrons and are represented by two short lines. Triple bonds
consist of three pairs of electrons and are represented by three short lines. Non-bonding valance electrons are
represented as dots, and are placed next to the atoms.

Steps in drawing Lewis Dot Structures:

Example: sulfite (SO32-) ion.

1) Draw the skeletal structure of the compound. The least electronegative atom is usually the central atom.

2) Count the total number of valence electrons present; add electrons for
negative charges and subtract electrons for positive charges.

Valence e- :
1xS=6
+ 3 x O = 3 x 6 = 18
+ Negative charge = 2
---------------------------------
TOTAL = 26 e- (or 13 pairs)

3) For each bond in the skeletal structure, subtract two electrons from
the total valence electrons.

4) Use the remaining electrons to complete octets of the terminal atoms.

Complete the octets of the more electronegative atoms first.
5) Place any remaining electrons on the central atom (resulting in the extended octet).

6) In the case there are not enough electrons to allocate eight electrons on the central atom, complete the octet by
forming multiple bonds.

7) In case of ions, place the structure in a bracket and write the charge outside of the bracket.

Example: sulfur trioxide, SO3.

(1) Draw a skeletal structure with a central S atom.
(2) Calculate the total number of valence electrons.
Valence e- :
1xS=6
+ 3 x O = 3 x 6 = 18
---------------------------------
TOTAL = 24 e- (or 12 pairs)

(3) Deduct a pair of electrons for each of the single bonds drawn in Step #1. Use the remaining pairs to complete octets
for each of the other atoms.
24 e - 6 e (bonding) = 18 e – to be allocated to give octet to all atoms.

(4) If there are not enough electrons to provide an octet for each atom, move a nonbonding (unshared) electron pair
between two atoms that already share an electron pair.

Resonance: Sometimes, more than one Lewis structure can be correct. For these molecules, a resonance arrow  is
drawn between the possible structures. There are three possible resonance structures for the Lewis dot structure of SO3 .

There are also three possible resonance structures for the Lewis dot structure of CO32- ion and many other molecules with
multiple bonds.

Formal Charge: a formal charge (F.C.) is the charge assigned to an atom in a molecule, assuming that electrons in all
chemical bonds are shared equally between atoms, regardless of relative electronegativity.

FC = valence electrons – associated electrons

associated electrons = [ # lone pair electrons + (# bonding electrons / 2) ]

Example: Isocyanate ion: CNO-

Valence e- 4 5 6
Associated e- 5 4 7
Formal Charge -1 +1 -1

Radicals:
A radical Molecule is molecule that contains at least one unpaired electron.

Hydroxyl ion

Hydroxyl radical (unpaired electron)

Three-dimensional shapes of molecules (geometry).

Electron Group Geometry

Electron Group Geometry shows the arrangement of bonding and nonbonding electrons around the
central atom. Bonding and nonbonding electrons are considered equivalent. For example, the three
molecules below all contain four electron groups (pairs) – there is no distinction made between
bonding and nonbonding electron groups in describing their electron group geometry. All three
molecules have tetrahedral electron pair geometry

Molecular Geometry

Three-dimensional molecular shape is called molecular geometry. The shape of the molecule depends on how
many of the electron groups around the central atom are bonded to atoms and how many are unshared. Bond
angle is defined as the angle formed by any two atoms bonded to a central atom. The no bonded electron
pairs create a larger cloud of electrons and create a greater repulsion than do the bonded electron
groups. The effect of no bonded pairs is to decrease the bond angle. The effect is well illustrated by the
following examples:

Bond angles and geometry of different molecules are listed in the following table.
Polarity

Polar bonds are a type of covalent bond in which the electrons that are shared are drawn more
closely to one of the atoms than the other. The unequal sharing of electrons results from differences
in electronegativity of the bonded atoms. Electronegativity (En) is a numerical value that describes
the ability of an atom to attract electrons in a chemical bond. The general trends in electronegativity
are apparent in the periodic table. Electronegativity increases across the period left to right -
nonmetals have high En, metals have low En. Electronegativity decreases down a group - small atoms
have high En, than larger atoms.

Bond polarity can be calculated by taking the difference in En between the two atoms involved in the
bond.

If ∆ En is =0, the bond is nonpolar (the electrons are shared equally)

If ∆En is 0< and <2, the bond is polar (the electrons are shared but unequally)
If ∆En is > 2.0, the bond is considered to be ionic (the electrons are completely transferred from
one atom to the other)
For example: H-Cl H = 2.1 & Cl = 3.0. The difference in En = 3.0 - 2.1 = 0.9. Therefore, the bond
between H and Cl is polar and the electron pair is attracted more towards the Cl than the H, because
Cl has a higher electronegativity. This makes the Cl partially negative and the H partially positive.

The delta notation () for polar bonds shows this partially charged situation by using - to indicate the
negative region and + to indicate the positive region.

+ H - Cl -

Polar and non-Polar molecules

Polar Molecules are molecules with polar bonds that add together to form a net dipole moment.

The following guidelines are helpful in determining if a molecule is polar of non-polar.

- A molecule that contains only nonpolar bonds tends to be a nonpolar molecule (example: CH4)
- A binary molecule (2 atoms) will be nonpolar if the bond is nonpolar (example: Br 2) or polar if the
bond is polar (example: HBrl)
- For molecules that contain 3 or more atoms and contain polar bonds, the molecular geometry of the
molecule must be considered.

Molecular shapes that are symmetric (have no lone pairs on the central atom), tend to be
nonpolar. All atoms bonded to the central atom must be the same (example: CCl4, CO2, BF3)

Molecular shapes that are asymmetric (have one or more lone pairs on the central atom) tend
to be polar.
Molecules that have different atoms bonded to the central atom (example: CH3Cl, CH2Cl2,
CHCl3, NF3, H2O) are usually polar regardless if they contain lone pair electrons or not.

The following table and examples can be used to predict if the molecule is polar or not.

Asymmetric
Symmetric
Shape
Shape
(the central atom
(no lone pairs on
has at least one
the central atom)
lone pair)
Contains
only Nonpolar
Weakly Polar
nonpolar Molecule
bonds
Nonpolar – if all
bonds are the
Contains at
same
least one Polar
polar bond
Polar – if bonds
are different