Writing Lewis Structures by Trial and Error

The Lewis structure of a compound can be generated by trial and error. We start by writing
symbols that contain the correct number of valence electrons for the atoms in the molecule. We
then combine electrons to form covalent bonds until we come up with a Lewis structure in
which all of the elements (with the exception of the hydrogen atoms) have an octet of valence
electrons.

Example: Let's apply the trial and error approach to generating the Lewis structure of carbon
dioxide, CO2. We start by determining the number of valence electrons on each atom from the
electron configurations of the elements. Carbon has four valence electrons, and oxygen has six.

C: [He] 2s2 2p2

O: [He] 2s2 2p4

We can symbolize this information as shown at the top of the figure below. We now combine
one electron from each atom to form covalent bonds between the atoms. When this is done,
each oxygen atom has a total of seven valence electrons and the carbon atom has a total of six
valence electrons. Because none of these atoms have an octet of valence electrons, we combine
another electron on each atom to form two more bonds. The result is a Lewis structure in which
each atom has an octet of valence electrons.

A Step-By-Step Approach To Writing Lewis Structures

The trial-and-error method for writing Lewis structures can be time consuming. For all but the
simplest molecules, the following step-by-step process is faster.

Step 1: Determine the total number of valence electrons.

Step 2: Write the skeleton structure of the molecule.

Step 3: Use two valence electrons to form each bond in the skeleton structure.

Step 4: Try to satisfy the octets of the atoms by distributing the remaining valence electrons as
nonbonding electrons.
The first step in this process involves calculating the number of valence electrons in the
molecule or ion. For a neutral molecule this is nothing more than the sum of the valence
electrons on each atom. If the molecule carries an electric charge, we add one electron for each
negative charge or subtract an electron for each positive charge.

Example: Let's determine the number of valence electrons in the chlorate (ClO3-) ion.

A chlorine atom (Group VIIA) has seven valence electrons and each oxygen atom (Group VIA)
has six valence electrons. Because the chlorate ion has a charge of -1, this ion contains one more
electron than a neutral ClO3 molecule. Thus, the ClO3- ion has a total of 26 valence electrons.

ClO3-: 7 + 3(6) + 1 = 26

The second step in this process involves deciding which atoms in the molecule are connected by
covalent bonds. The formula of the compound often provides a hint as to the skeleton structure.
The formula for the chlorate ion, for example, suggests the following skeleton structure.

The third step assumes that the skeleton structure of the molecule is held together by covalent
bonds. The valence electrons are therefore divided into two categories: bonding electrons and
nonbonding electrons. Because it takes two electrons to form a covalent bond, we can
calculate the number of nonbonding electrons in the molecule by subtracting two electrons
from the total number of valence electrons for each bond in the skeleton structure.

There are three covalent bonds in the most reasonable skeleton structure for the chlorate ion.
As a result, six of the 26 valence electrons must be used as bonding electrons. This leaves 20
nonbonding electrons in the valence shell.

26 valence electrons
- 6 bonding electrons
�������������������
20 nonbonding electrons

The nonbonding valence electrons are now used to satisfy the octets of the atoms in the
molecule. Each oxygen atom in the ClO3- ion already has two electrons the electrons in the
Cl-O covalent bond. Because each oxygen atom needs six nonbonding electrons to satisfy its
octet, it takes 18 nonbonding electrons to satisfy the three oxygen atoms. This leaves one pair of
nonbonding electrons, which can be used to fill the octet of the central atom.
 Drawing Skeleton Structures

The most difficult part of the four-step process in the previous section is writing the skeleton
structure of the molecule. As a general rule, the less electronegative element is at the center of
the molecule.

Example: The formulas of thionyl chloride (SOCl2) and sulfuryl chloride (SO2Cl2) can be
translated into the following skeleton structures.

It is also useful to recognize that the formulas for complex molecules are often written in a way
that hints at the skeleton structure of the molecule.

Example: Dimethyl ether is often written as CH3OCH3, which translates into the following
skeleton structure.

Finally, it is useful to recognize that many compounds that are acids contain O-H bonds.

Example: The formula of acetic acid is often written as CH3CO2H, because this molecule contains
the following skeleton structure.

Molecules that Contain Too Many or Not Enough Electrons

Too Few Electrons

Occasionally we encounter a molecule that doesn't seem to have enough valence electrons. If we
can't get a satisfactory Lewis structure by sharing a single pair of electrons, it may be possible to
achieve this goal by sharing two or even three pairs of electrons.

Example: Consider formaldehyde (H2CO) which contains 12 valence electrons.

H2CO: 2(1) + 4 + 6 = 12

The formula of this molecule suggests the following skeleton structure.

We therefore assume that the carbon and oxygen atoms share two pairs of electrons. There are
now four bonds in the skeleton structure, which leaves only four nonbonding electrons. This is
enough, however, to satisfy the octets of the carbon and oxygen atoms.

Every once in a while, we encounter a molecule for which it is impossible to write a satisfactory
Lewis structure.

Example: Consider boron trifluoride (BF3) which contains 24 valence electrons.

BF3: 3 + 3(7) = 24

There are three covalent bonds in the most reasonable skeleton structure for the molecule.
Because it takes six electrons to form the skeleton structure, there are 18 nonbonding valence
electrons. Each fluorine atom needs six nonbonding electrons to satisfy its octet. Thus, all of the
nonbonding electrons are consumed by the three fluorine atoms. As a result, we run out of
electrons while the boron atom has only six valence electrons.

The elements that form strong double or triple bonds are C, N, O, P, and S. Because neither
boron nor fluorine falls in this category, we have to stop with what appears to be an
unsatisfactory Lewis structure.

Too Many Electrons

It is also possible to encounter a molecule that seems to have too many valence electrons. When
that happens, we expand the valence shell of the central atom.

Example: Consider the Lewis structure for sulfur tetrafluoride (SF4) which contains 34 valence
electrons.

SF4: 6 + 4(7) = 34

There are four covalent bonds in the skeleton structure for SF4. Because this requires using
eight valence electrons to form the covalent bonds that hold the molecule together, there are 26
nonbonding valence electrons.
Each fluorine atom needs six nonbonding electrons to satisfy its octet. Because there are four of
these atoms, so we need 24 nonbonding electrons for this purpose. But there are 26 nonbonding
electrons in this molecule. We have already satisfied the octets for all five atoms, and we still
have one more pair of valence electrons. We therefore expand the valence shell of the sulfur
atom to hold more than eight electrons.

This raises an interesting question: How does the sulfur atom in SF4 hold 10 electrons in its
valence shell? The electron configuration for a neutral sulfur atom seems to suggest that it takes
eight electrons to fill the 3s and 3p orbitals in the valence shell of this atom. But let's look, once
again, at the selection rules for atomic orbitals. According to these rules, the n = 3 shell of
orbitals contains 3s, 3p, and 3d orbitals. Because the 3d orbitals on a neutral sulfur atom are all
empty, one of these orbitals can be used to hold the extra pair of electrons on the sulfur atom in
SF4.

S: [Ne] 3s2 3p4 3d0

Practice Problem 3:

Write the Lewis structure for xenon tetrafluoride (XeF4).

Click here to check your answer to Practice Problem 3

Resonance Hybrids

Two Lewis structures can be written for sulfur dioxide.

The only difference between these Lewis structures is the identity of the oxygen atom to which
the double bond is formed. As a result, they must be equally satisfactory representations of the
molecule.

Interestingly enough, neither of these structures is correct. The two Lewis structures suggest
that one of the sulfur-oxygen bonds is stronger than the other. There is no difference between
the length of the two bonds in SO2, however, which suggests that the two sulfur-oxygen bonds
are equally strong.
When we can write more than one satisfactory Lewis structure, the molecule is an average, or
resonance hybrid, of these structures. The meaning of the term resonance can be best
understood by an analogy. In music, the notes in a chord are often said to resonate they mix
to give something that is more than the sum of its parts. In a similar sense, the two Lewis
structures for the SO2 molecule are in resonance. They mix to give a hybrid that is more than the
sum of its components. The fact that SO2 is a resonance hybrid of two Lewis structures is
indicated by writing a double-headed arrow between these Lewis structures, as shown in the
figure above.

Practice Problem 4:

Write the Lewis structures for the acetate ion, CH3CO2-.

Click here to check your answer to Practice Problem 4

Formal Charge

It is sometimes useful to calculate the formal charge on each atom in a Lewis structure. The
first step in this calculation involves dividing the electrons in each covalent bond between the
atoms that form the bond. The number of valence electrons formally assigned to each atom is
then compared with the number of valence electrons on a neutral atom of the element. If the
atom has more valence electrons than a neutral atom, it is assumed to carry a formal negative
charge. If it has fewer valence electrons it is assigned a formal positive charge.

Practice Problem 5:

The formula of the amino acid known as glycine is often written as H3N+CH2CO2-. Use the
concept of formal charge to explain the meaning of the positive and negative signs in the
following Lewis structure.

Click here to check your answer to Practice Problem 5

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 General rules for drawing Lewis structure

The following is a list of rules that can be used to determine the Lewis structure of a molecule:

1.
Count up the total number of valence electrons. First add up the group numbers of all
atoms in the molecule. If the molecule is an anion, add one electron for each unit of
charge on the anion. If it is a cation, subtract one electron for each unit of charge on the
cation.

2.
Calculate the total number of electrons that would be needed for each atom to have an
octet (or doublet for H).

3.
Subtract the result of step 1 from the result of step 2. This is the total number of shared
or bonding electrons.

4.
Assign two bonding electrons to each bond.

5.
If bonding electrons remain, assign them in pairs making some of the bonds double or
triple bonds. (Usually, only C,N,O, and S can form double bonds, and only C and N can
form triple bonds). There may be more than one way to do this. Keep all possible
structures that result.

6.
Assign remaining electrons as lone pairs, giving octets to all atoms except H.

7.
Determine the formal charges and put them next to the appropriate atoms. (A formal
charge of 0 need not be written explicitly). Check that the formal charges add up to the
total charge on the molecule/ion. Do this for all structures obtained in step 5. The
 structure with the smallest formal charges should be considered as the preferred
structure.

Example: Ethylene (C H ).

Step 1: Total valence electrons = 2 4 + 4 = 12

Step 2: Total electrons needed for octets/doublets = 2 8+4 2 = 24

Step 3: Total shared/bonding electrons = 24 - 12 = 12. Total electrons in lone pairs = 12 - 12 = 0.

Step 4:

Figure 2:

Note that, in order to use up all of the bonding electrons, the C=C double bond is necessary. For
this case, all of the formal charges work out to be 0, which is shown straightforwardly.

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How to draw Lewis Diagrams

An outline of how to detemine the "best" Lewis structure for an example, NO3- is given below:

1. Determine the total number of valence electrons in a molecule

2. Draw a skeleton for the molecule which connects all atoms using only single bonds. In simple
molecules, the atom with the most available sites for bondng is usually placed central. The
number of bonding sites is detemined by considering the number of valence electrons and the
ability of an atom to expand it's octet. As you become better, you will be able to recognise that
certain groups of atoms prefer to bond together in a certain way.

3. Of the 24 valence electrons in NO3-, 6 were required to make the skeleton. Consider the
remaining 18 electrons and place them so as to fill the ocets of as many atoms as possible (start
with the most electronegative atoms first then proceed to the more electropositive atoms).

4. Are the octets of all the atoms filled? If not then fill the remaining octets by making multiple
bonds (make a lone pair of electrons, located on a more electronegative atom, into a bonding
pair of electrons that is shared with the atom that is electron defficient).

5. Check that you have the lowest FORMAL CHARGES possible for all the atoms, without
violating the octet rule; (valence e-) - (1/2 bonding e-) - (lone electrons).

IMPORTANT : no Lewis diagram is complete without formal charges. Lewis diagrams are
drawn to examine mechanisms so knowing which parts of a molecule are electron defficient (+)
and which are electron rich (-) is vital.
It is best to have a formal charge of 0 for as many of the atoms in a structure as possible.
If a formal charge of 1- is located next to a formal charge of 1+, the formal charges can usually be
minimized by having a lone pair of electrons, located on the atom with the 1- charge become a
bonding pair of electrons that is shared with the atom that has the 1+ formal charge (this can be
visualised in the same way as the formation of multiple bonds were above).
CAUTION : octets can be expanded to minimise formal charges but only for atoms in the second
row of the periodic table (where n=3 or greater). For instance in our example, N cannot
expand its octet so keeps a formal charge of 1+ and both singly bonded oxygens a formal charge
of 1-. If our molecule were SO3 , however, it would be possible to minimize all formal charges by
having the sulfur expand its octet.

6. You may find that the best Lewis diagram (the one with the lowest formal charges and all
octets satisfied) is given in a number of different ways. For NO3-, three different diagrams are
given below. From left to right they start with the most complete Lewis diagram to the most
simplified.

Why so many different ways? Depends on the need of the chemist. For instance, complete
structures are more useful for the novice organic chemist learning to appreciate the mechanism
of a reaction while simplified versions may be preferred by inorganic chemists.

Now you should be ready to try some questions.

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