Helpful Hints

Ionic Bonding
Lattice energy associated with a compound can give insight to the physical properties such
as melting point, hardness, solubility, etc. A method for approximating lattice energy, based on
Coulomb's law, relates the ionic charges (q1 and q2) to the internuclear distance (r) with a
constant (k):
=

=
4

A higher product of charges for a compound indicates a higher lattice energy; when the product
of the charges is the same between two different compounds then the internuclear distance must
be compared based on the general trend for atomic radius with a larger "r" value indicating lower
lattice energy.
Another method for determining lattice involves an application of Hess's law whereby known
enthalpy values are used to determine the final lattice energy, called the Born-Fajans-Haber
Cycle. The general idea is to take the energy of all theoretical steps involved along with the
reaction enthalpy and use them to find the lattice energy. Using NaCl as an example, the general
steps involved would include:
1.) Sublimation of 1 mol of Na(s):
2.) 1st ionization energy of 1 mol Na(g):
3.) Dissociation of 1 mol Cl2(g):
4.) Electron affinity of 1 mol Cl(g):
5.) Lattice Energy of 1 mol NaCl(s):

Na(s)
Na(g)
Na(g)
Na+(g) + e Cl2(g)
Cl(g)
Cl(g) + e-
Cl-(g)
Na+(g) + Cl-(g)
NaCl(s)

These values add up to give the reaction enthalpy for the overall reaction:
Na(s) + Cl2(g)
NaCl(s)

H4 = -411 kJ

Hrxn = H1 + H2 + H3 + H4 + H5
H5 = Elattice NaCl = -787 kJ

H1 = +107 kJ
H2 = +496 kJ
H3 = +122 kJ
H4 = -349 kJ
H5 = unknown

Lewis Structures Octet Rule

Lewis structures are a basic representation of how atoms interact to form compounds based on
bond formation by the outermost, or valence electrons. A simple representation of an atom or
ion is the Lewis dot symbol where valence electrons are placed one per side prior to pairing them
similar to how the lugs are put back on when changing a tire. A correct Lewis dot symbol for
phosphorus would appear as:

Often, non-metals will often follow the octet rule when sharing or gaining electrons, so based on
the Lewis symbol for phosphorus it should be observed that for it to have an octet it will either
need to share its three unpaired electrons when acting covalently, or gain three electrons when
acting ionically. The phosphide ion alone, or in an ionic compound such as Na3P would appear
as:

For Lewis structures of covalent compounds the following 3 steps should be followed:
1.) The least electronegative element will generally be the central atom with more
electronegative elements as terminal atoms. In PF3, P will be the central atom with the fluorines
as terminal atoms.

2.) Non-bonding valence electrons are first placed around the most electronegative elements to
give them octets, in this case fluorine; if any more are left they will go around the central atom.

3.) Finally, the formal charge for each atom is determined allowing adjustments to electron
locations to be made if necessary. The sum of the formal charges must be the total charge.
FC = # of valence electrons (# of bonds + # of nonbonding electrons)
FCF = 0; FCP = = 0
A low range of formal charges is the best, with all elements having formal charges of zero
(when possible) being the best, therefore the correct Lewis structure for PF3 is:

Expanded Lewis
Many compounds do not follow the octet rule either due to a deficiency or excess amount of
electrons; only the elements C, N, O, F, and Ne must follow the octet rule except cases where
not enough electrons are available. It is important to realize that the central atom should be the
only one to violate the octet rule due to an expanded octet, terminal atoms will still attempt to
follow the octet rule.
Determining the correct Lewis structure for expanded valence molecules is effectively the same
as for those that follow the octet rule. Using SF4 as an example:

1.) Least electronegative element is the central atom, more electronegative elements are terminal
atoms.

2.) Valence electrons are first put on the most electronegative elements to give octets, with any
extra electrons are put on the central atom.

3.) Formal charges are determined with lowest range being the best; FCs agree with the above
structure.

The most appropriate Lewis structure has sulfur surrounded by more than 8 electrons with
terminal atoms following the octet rule. Only elements in the third energy level or higher can
exceed an octet, and only as a central atom.
In cases where an odd number of electrons exist it will be impossible for each atom to have an
octet, this is called a radical. The method stays exactly the same as for any other except that the
single extra electron will go to the most electropositive element, other atoms will still try to form
octets. An example molecule which is a radical is NO2 which appears as the following; note that
nitrogen, the most electropositive element is the location of the radical.

Resonance
Oftentimes multiple valid Lewis structures can be drawn for the same molecule, these are called
resonance structures. In order to be a resonance structure the Lewis structures must have the
same atomic arrangement, number of electrons, and number of bonds, but with different electron
arrangements. The carbonate ion is a resonance structure due to the delocalized nature of the
double bond.

Realize that the molecule is not being rotated; the electrons are moving to create a double bond
from the carbon central atom to different oxygen atoms.
Resonance structures are necessary because in reality none of these Lewis structures are
completely accurate as the electrons are not actually forming a double bond from the carbon to
any of the oxygen atoms. In would be more accurate to say that the extra bonding electrons are

shared equally to all the oxygen atoms giving something closer to a 1 bond between the carbon
and each oxygen.
Sometimes a compound/ion can have resonance, but while each structure would be valid, not all
would be equally accurate. For example, the cyanate ion (OCN- ) has three valid resonance
structures:

The middle structure would be the most unfavorable due to the higher range of formal charges;
the first and last Lewis structures have the same range. Since the ranges between the first and
last are identical it's time to compare the locations of the formal charges relative to the
electronegativity of each atom; negative FCs should be on the most electronegative atom.
Oxygen is the most electronegative atom in this molecule so the most valid resonance structure
will be the last one where the formal charge of -1 is located on the oxygen: