periodintable e configurations valence e compounds ionic

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Lewis Structures Worksheet.doc Name:

Lewis Structures
2nonmetals
Objectives:
• ELITE Foreman compound
molecules
To learn how to use Lewis Structures of elements to predict formulas of simple binary molecular
compounds.
•
anonmetals
To learn the octet rule and how to apply it in drawing Lewis Structures for polyatomic ions and
molecules.
• To learn about charge distribution in chemical bonds in terms of electronegativity differences of
bonded atoms and formal charges.
• To learn how to use formal charges to predict the most stable Lewis Structure for a molecule or
polyatomic ion.
• To understand what is meant by the terms “resonance hybrid” and “resonance stabilization”.
• To learn about when the octet rule is violated and to be able to write Lewis Structures for such cases.
• To learn how to use the concepts of formal charges and expanded octets to explain experimentally
observed bond lengths.

tsthat dont
andenray
needoret
Pre-laboratory Reading:
Silberberg
eventsthat go beyond ottet
Chapter 9 sections 9.1, 9.3, 9.5
& Amateis Chapter 10, section 10.1

Background:
The properties of ionic, covalent (molecular) and metallic substances are remarkably different from each
other. Ionic compounds have high melting points, making them solids at room temperature. In contrast,
molecular compounds can be solids, liquids or gases at room temperature. Ionic compounds do not conduct
electricity in the solid state, whereas metallic substances do. These are just a couple of the many differences
between these three types of substances. The difference in their properties can be understood in terms of the
type of bonding that occurs in each: ionic bonding, covalent bonding and metallic bonding. We will focus our
attention mainly on covalent bonding in this exercise.

The chemical and physical properties of molecular substances depend upon which elements are bonded
together and how the atoms and valence electrons are arranged in the molecule. For example, the bond
between carbon and oxygen in CO requires more energy to break than the bond between carbon and oxygen
in CO2. Another example: CO2, a gas at room temperature, consists of linear molecules (the three nuclei lie in
a straight line), whereas H2O, a liquid at room temperature, consists of v-shaped molecules. These
differences can be explained by drawing the Lewis Structures of CO, CO2 and H2O. Chemists use Lewis
valence Structures as a simple way to depict the bonding in molecules. Based upon the Lewis Structure, chemists can
make reasonable predictions about the shape and properties of a molecule. A Lewis Structure shows the
netrule sequence in which the atoms are connected and the distribution of valence electrons around the atoms of a
inargemolecule or polyatomic ion. However, a Lewis Structure does not, by itself, depict the three dimensional
formal arrangement (the geometry) of the atoms. We will focus our attention in this exercise on drawing Lewis
Structures and will learn later how to use Lewis Structures to predict molecular geometries. It is important
that you become skilled at drawing Lewis Structures so that you can successfully predict molecular
geometries!

Exercise:
The questions in this worksheet up to the follow up questions should be completed with the guidance of your
lab instructor as a discussion during lab lecture. The follow-up questions are then to be completed by you
during the remainder of the lab time. As much of this exercise as possible should be completed during
lab.

Foothill College-Chemistry 1A, Larson, Daley page 1 Last Modified 9/14/14

iiiiii.fi Iiitii
1 18

Ei
1A 8A

1 maana 2
H 2 bonds re they are 13 14 15 16 17 He
Hydrogen 2A 3A 4A 5A 6A 7A Helium

1.008 covalent compounds 4.003

3 4 5 6 7 8 9 10
Li Be Ne 15Zs B C N O F Ne

yu.ge
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon

6.941 9.012 inoutermostshell stable 10.81 12.01 14.01 16.00 19.00 20.18
11 12 13 14 15 16 17 18
Na Mg 3 4 5 6 7 8 9 10 11 12 Al Si P S Cl Ar
Sodium Magnesium 3B 4B 5B 6B 7B 8B 8B 8B 1B 2B Aluminum Silicon Phosphorus Sulfur Chlorine Argon

22.99 24.30 26.98 28.09 30.97 32.07 35.45 39.95

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
39.10 40.08 44.96 47.87 50.94 52.00 54.94 55.84 58.93 58.69 63.55 65.39 69.72 72.61 74.92 78.96 79.90 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
85.47 87.62 88.91 91.22 92.91 95.95 97.91 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3
55 56 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba Lu Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Cesium Barium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
132.9 137.3 175.0 178.5 180.9 183.8 186.2 190.2 192.2 195.1 197.0 200.6 204.4 207.2 209.0 209 210 222
87 88 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Lr Rf Db Sg Bh Hs Mt Ds Uuu Uub Uuq Uuh Uuo
Francium Radium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Unununium Ununbium Ununquadium Ununhexium Ununoctium
223 226 262 261 262 263 262 265 266 269 272 277 289 289 293

57 58 59 60 61 62 63 64 65 66 67 68 69 70
Lanthanides La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium
138.9 140.1 140.9 144.2 145 150.4 152.0 157.2 158.9 162.5 164.9 167.3 168.9 173.0
89 90 91 92 93 94 95 96 97 98 99 100 101 102
Actinides Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No
Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium
227 232.0 231.0 238.0 237 244 243 247 247 251 252 257 258 259 
 Lewis Structures madeupof

Part 1: Predicting formulas of binary molecular compounds

g anonmetals
For the representative (main group) elements, the number of valence electrons an atom of the element
possesses can be determined by its group number. (This is following the “A”, “B” numbering system where
the representative elements are in the eight columns labeled ”A”.) Atoms of these elements often lose, gain
or share electrons to achieve the same number of outer electrons as the noble gas closest to them. All noble
gases (except He) have eight valence electrons. These observations have resulted in the formulation of the
octet rule: atoms tend to lose, gain or share electrons until eight valence electrons surround them. We
understand this as only a rule, not a scientific law. Exceptions do occur. An octet of electrons corresponds to
a full valence shell (s and p subshells) in an atom. For hydrogen, its valence shell consists of only an s
subshell. Therefore, hydrogen can only accommodate two electrons in its valence shell and it follows its
own rule rigorously, the duet rule. We also see cases where the octet rule cannot be satisfied due to an
insufficient number of available valence electrons, cases where atoms acquire less than octet of valence
electrons and cases where atoms acquire more than an octet. Even with these exceptions, the octet rule
provides a useful framework for understanding many aspects of bonding.

When two atoms form a covalent bond, usually each atom provides one valence electron to share. (There are
cases where both of the shared electrons come from one atom. In such a case the bond is called a
Far bond.)
coordinate covalent y In either case, the shared electron pair is considered localized in the region
between the nuclei of the two atoms. The attractive forces that hold two covalently bonded atoms together
are thus electrostatic in nature; the positive nuclei of the two atoms are simultaneously attracted to the
shared electrons within the bond. Formation of the bond lowers the potential energy of the system, making it
an energetically favorable process.
ofvalencee for eachelement
We can predict formulas of binary molecular compounds by first considering the Lewis Symbol of the atoms
involved. In writing the Lewis Symbol for an atom, the chemical symbol for the element is used to represent
the core (the inner, non-valence electrons plus the nucleus) and the valence electrons are represented by
dots arranged around the core. The dots are placed arbitrarily, one at a time, around the symbol. If there are
more than four valence electrons, we continue around the symbol, pairing the dots until all the valence
electrons are represented by dots.

The Lewis Symbol for hydrogen is: H•

H ive
The Lewis Symbol for sulfur is:
bve

Since hydrogen needs one more electron to satisfy its duet rule and sulfur needs two more electrons to
satisfy the octet rule, we can predict that the formula for a binary compound containing hydrogen and sulfur
will be H2S, sulfur forming two bonds and hydrogen forming one bond. In writing the Lewis Structure for the
molecule, the valence electrons are arranged to satisfy the octet and duet rules as shown below:

sue
dihydrogen sulfe 00
name
ig'sifiEIiiEiy
In this structure, the line (—) between each hydrogen atom and the sulfur atom represents a shared pair of
electrons (a bonding pair) and the unshared (non-bonding or lone pair) electrons on the sulfur are
represented by dots. Note that the hydrogen atoms have attained a duet of electrons and the sulfur has
attained an octet by sharing of electrons.

Practice:
1. Write the Lewis Symbols for all of the elements in the second period of the periodic table.

hi B N rat
2.
Be
Based on the Lewis Symbols for nitrogen and fluorine, predict the formula of a stable binary compound of
nitrogen and fluorine and draw its Lewis Structure. Also, give the name of this compound.

Foothill College-Chemistry 1A, Larson, Daley page 2 Last Modified 9/14/14

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Lewis Structures lath element want oleet
Part 2: Simple Lewis Structures
The following steps outline general guidelines for writing SIMPLE Lewis Structures
(Octet and Duet Rules Obeyed):
Step 1. Determine the total number of valence electrons available. This exact number of electrons must
be included in the Lewis Structure.
a) Add up the valence electrons of all the atoms present. thisintocomes fromPT
b) Add extra electrons for (–) ions, subtract electrons for (+) ions.
Step 2. Decide the sequence of atoms, i.e. the skeleton arrangement of the atoms.
a) For some compounds, the formula gives the order in which the atoms are attached in the
molecule. Two examples are HCN and condensed structural formulas such as CH3OCH3.
b) When there is a central atom surrounded by other atoms bonded to it, the central atom is usually
written first in the formula. For example, nitrogen is the central atom in NO3—.
c) The central atom is usually the least electronegative atom.
d) Oxygen is rarely the central atom.
e) Hydrogen is NEVER the central atom.
f) Exceptions to (b) (c) and (d) do exist. For example, in H2O and NH3 where the highly
electronegative O and N are the central atoms. Note, however, that in these two examples
guideline (e) is followed.
Step 3. Draw a single bond (a line) between each atom in the skeleton arrangement. usedinbonds
a) All atoms must have at least one bond.
b) Subtract two electrons for each bond from the total available electrons.
Step 4. Distribute the remaining electrons in pairs so each atom acquires eight electrons (two for H).
omer
a) Place lone pairs on the surrounding (terminal) atoms first to complete an octet on each.
Fitehunused b) If any electrons remain add them as lone pairs on the central atom(s).
Step 5. If, after step 4, a central atom still does not have an octet, change a lone pair from one of the
dist
gets terminal atoms into a bonding pair to the central atom to make a multiple bond. In this way,
sufficient multiple bonds should be made in order to complete an octet for the central atom(s).
outer
amit When forming bonds follow these general guidelines:
a) H atoms ALWAYS make only one bond.
b) O atoms usually make a total of either one or two bonds: When an oxygen atom makes only one
bond, it is a coordinate covalent bond with the other atom providing both electrons for the bond.
In the case of two bonds, oxygen can make either two single bonds or one double bond.
c) C atoms usually make a total of four bonds: four single, two double, a double with two single or a
triple with one single.
d) For oxyacids, the acidic hydrogen atoms are bonded to oxygen atoms, which in turn are bonded
to the central atom. For example, in H2CO3 the carbon is the central atom, the oxygen atoms are
all bonded to the carbon atom and the hydrogen atoms are bonded to two separate oxygen
atoms.

A common exception to (b) and (c) that we will explore later in this exercise is found with carbon
monoxide.
Practice (Lewis Structures containing only single bonds):
1) Draw Lewis structures for the following molecules or polyatomic ions.
a) H2O c) OH— 6 1 1sue 8 z eve

4 n 1 45
b) NH3 d) HF 1 7 Sue
H HH H H F
H

Foothill College-Chemistry 1A, Larson, Daley page 3 Last Modified 9/14/14

 a o

yourstruture should
havesue
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4 H
sue starting
45

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Lewis Structures

e) SOCl2 g) CH3CH2OH
(S is the central atom, O and Cl are both
bonded to S)

O H
H

4 a

f) CH3OCH3 h) NH4+

I
4 o

II
Molecules with Multiple Bonds multiplebonds arenecessarywhen centralatomdoes nothaveoctet
If, after step 4, the structure does not satisfy the octet rule for all atoms, excluding hydrogen, Step 5 is
needed: make one or more multiple bonds (double or triple bonds). A single bond is defined as the sharing
of two electrons (one pair). A double bond is the sharing of four electrons (two pairs) and a triple bond the
sharing of six electrons (three pairs). Many atoms do make multiple bonds to complete their octet. In these
cases, the multiple bond(s) is/are often formed to a central atom.

Examples of Lewis Structures with multiple bonds:

O2 HCN

A single bond is described as having a bond order of 1, a double bond as having a bond order of 2 and a
triple bond as having a bond order of 3. Bond order has an effect on bond length and bond energy. Bond
length is defined as the distance between the centers (nuclei) of two bonded atoms. Bond energy is defined as
the enthalpy change (∆H) required to break the bond that holds two adjacent atoms together in a molecule
when the substance is in the gas phase. Bond breaking is always an endothermic process (positive ∆H values)
and bond energies are usually expressed on a per mole basis (the energy needed to break one mole of the
specified bonds). Greater bond energy indicates a stronger bond. In your text you will find tables that list the
average bond energies and average bond lengths for some common single, double and triple bonds. The table
below gives the average bond lengths and bond energies for carbon–carbon single, double and triple bonds as
an example.
Bond Bond Order Average Bond Length Average Bond Energy*
(Å) (kJ/mol)
C—C 1 1.54 348
C=C 2 1.34 614
C≡C 3 1.20 839
* Referred to as Bond Enthalpy in our textbook.
Questions and Practice: qq.gg T.ITa B.E
1. In general, what happens to bond length and bond energy as bond order increases between two atoms?

As B o increases length decreases everay increases

Foothill College-Chemistry 1A, Larson, Daley page 4 Last Modified 9/14/14

 Lewis Structures

2. Draw Lewis structures for the following molecules or polyatomic ions:

a. N2 e. CO2

b. CH3COOH (acetic acid) f. N 2H 2

(Be sure to use the correct skeletal arrangement
for the –COOH group. It is NOT C–O–O–H.)

H N N H
H I O H

g. O3 (Structure is not a ring, it is a chain.)

c. HNO3 (nitric acid)

o o o
o H

h. HCCH (acetylene)

d. H2C2O4 (oxalic acid)

H C C H
c
a

3. Draw Lewis Structures for formaldehyde (H2CO) and methanol (CH3OH).

H
E H
4
ÉO H

a) Which one of the above, H2CO or CH3OH, has the shortest carbon-oxygen bond length?

b) Which one of the above, H2CO or CH3OH, has the weakest carbon-oxygen bond?

Foothill College-Chemistry 1A, Larson, Daley page 5 Last Modified 9/14/14

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 Lewis Structures

Part 3: Advanced Lewis Structures

3.A Resonance Structures ifthemultiplebondcan one from equivalentmeaning
For molecules and polyatomic ions with multiple bonds adjacent to single bonds it is often possible to write
more than one Lewis structure for the same sequence of atoms that satisfies the octet rule and general
rules of bonding. Consider the following Lewis structures for ozone, O3.

off ↔ a
net miasma
Notice how the double bond can be written in two different positions. We call these structures resonance
forms of each other. Which of the above two resonance forms is the correct representation of bonding in the
O3 molecule? The answer is neither of them! Resonance structures are not real bonding descriptions:
the bonding arrangement does not shift back and forth between the different forms. The correct
representation of bonding in O3 is a combination of the two resonance forms to create a resonance hybrid, a
blend of the two structures. To describe the bonding in O3 properly, we write both resonance hybrids and use
a double-arrow to indicate that the real molecule is a blend of the two. Be careful not to misinterpret the
double arrow as meaning that the molecule flips back and forth between two forms; it does NOT! In terms of
bond length and bond energy, the O3 molecule has two equivalent oxygen–oxygen bonds with bond lengths
and energies between those of a single and double bond. The bond order for both of the oxygen–oxygen
bonds in ozone is described as being “one-and-one-half” (one bond plus half of the second bond). In other
words, one of the bonds is spread out (delocalized) over all three atoms.

It is important to remember that resonance forms of the same molecule differ in only the location of the
bonding and lone pair electrons, but not in the sequence of atoms. Resonance forms are common in many
molecules and polyatomic ions; in these cases some of the bonding electrons are delocalized, that is they are
shared between more than two atoms. This results in greater stability (lower overall energy) of the molecule
or ion and we say that the structure is resonance stabilized.

In Summary: Resonance is the blending of two or more Lewis Structures with the same arrangement of
atoms but different arrangements of electrons. It spreads multiple bond character out over three or
more atoms giving a more stable (lower energy) structure (resonance stabilization).

Questions:

1. Draw all possible resonance structures for the nitrate ion, NO3—. 5 3167 1 24ve

1 1 I

if
a) Do you expect the nitrogen–oxygen bonds in the nitrate ion to be equivalent to each other?

do we have 1 double 2single of 3 its bonds

b) What is the nitrogen-oxygen bond order in the nitrate ion?

B 0 4bonds 3oxygen bondorder

c) The average bond length and energy for a nitrogen–oxygen single bond are 1.36 Å and 201 kJ/mol.
For a nitrogen–oxygen double bond they are 1.22 Å and 607 kJ/mol. Compared to these, what would
you predict for the length and energy of the nitrogen–oxygen bonds in the nitrate ion?
bw doubleand
Bond length shorterthan 1.36A longerthan 1.225
single bond
Bond eneral greaterthan 201k but lessthan607kt

Foothill College-Chemistry 1A, Larson, Daley page 6 Last Modified 9/14/14

 Lewis Structures
fectronegativity
3.B Charge Distribution in Molecules and Ions: Formal Charge and Polar Bonds.
Close analysis of molecules reveals that the valence electrons are not always distributed as evenly as Lewis
Structures may suggest. Some atoms might have a slight positive charge and others a slight negative charge.
We will discuss the charge distribution in molecules in terms of electronegativity differences and formal
charges.

Bond Polarity and Electronegativity:

When two identical atoms bond, as in H2 or Cl2, the electron pairs are shared equally since both atoms
exert the same force of attraction for electrons. When electrons are shared equally, the bond is described
as being nonpolar covalent. In contrast, for ionic compounds, such as KCl, there is essentially no
sharing of electrons. Instead, electrons are viewed as being transferred from one atom to another
resulting in the formation of oppositely charged ions that are held together by strong electrostatic forces
of attraction. In between these two extremes, as is the case for bonding in the HCl molecule, there exists
polar covalent bonds where the electrons are not equally shared between the two atoms. These
differences in bonding arise due to differences in electronegativities of the bonded atoms.
Electronegativity is defined as the ability of an atom in a molecule to attract electrons to itself. (A
common misconception students tend to have is that molecules have electronegativity values. This is not
true; electronegativity is a property of atoms, not molecules.) Electronegativity values are listed in your
much
How textbook. Electronegativily is not a measured property, the values are calculated and you will find that
they vary slightly depending on the reference source. Generally, electronegativity increases from bottom
doatoms to top within a group of the periodic table and from left to right across a period. Thus, fluorine (in the
pull on upper right-hand corner of the periodic table) has the greatest electronegativity and cesium (in the lower
left-hand corner) has the lowest electronegativity. A chlorine atom has a greater electronegativity
sharede compared to a hydrogen atom, therefore in HCl the electron distribution is uneven; the hydrogen atom
inbond having a partial positive charge and the chlorine a partial negative charge. We can illustrate the charge
distribution in a polar covalent bond like that in HCl in one of two ways as illustrated below:

δ+ δ- +—>

L δ+aandI δ- symbols
H—Cl or H—Cl
YET The 30
as.fi moee.name
indicate the partial positive and partial negative charges on the H and Cl
atoms. The arrow is used to show the shift in electron density from H towards Cl.
A separation of charge between two bonded atoms is called a bond dipole. The greater the difference in
electronegativity values between two bonded atoms the more polar the bond, and the greater the
magnitude of the bond dipole. When the difference becomes large enough, electron transfer occurs
instead of sharing, and an ionic compound results. There thus exists a graduation in bond types.
Generally, if the difference in electronegativities between two bonded atoms is about 0.3 or less the bond
is considered to be nonpolar. If the difference is between 0.3 and 0.5, the bond is slightly polar. If the
anion difference is between about 0.5 and 2.0 the bond is considered to be polar covalent. For electronegativity
differences of 2.0 or greater the bond is considered to be ionic.

howextronegatie aneventis

cos theevent

Foothill College-Chemistry 1A, Larson, Daley page 7 Last Modified 9/14/14

Lewis Structures

Example Electron Density Distributions and Bond Types: In the following figures1 regions of
relatively low electron density (net positive charge) appear blue, those of relatively high electron density (net
negative charge) appear red, and regions that are close to electrically neutral appear green.

F F
EN o no 3otionics
4.0 DEN 2
My
DEN
4 4 the e density inbindshiftsto
Calculated electron-density distribution showing the degree of charge separation in F2, HF and LiF.
The bonding in the F2 molecule is nonpolar, the HF molecule is polar covalent and LiF is ionic. 1Tarm

Calculated electron-density distribution showing the degree of charge separation in the hydrogen
halides. In HF the strongly electronegative F atom pulls much of the electron density away from
the H atom. In HI the I atom, being much less electronegative than an F atom, does not attract
electrons as strongly, and consequently there is far less polarization of the bond.

CO2 and H2O are molecules that contain polar bonds. However, CO2 is a nonpolar molecule. This
is because the overall polarity of the molecule results from the sum of its bond dipoles. In the CO2
molecule the bond dipoles are equal in magnitude, but exactly oppose each other resulting in a
nonpolar molecule. In H2O the bond dipoles are also equal in magnitude, but do not exactly
oppose each other resulting in a polar molecule.

1
Brown, T.L., LeMay, H.E., Bursten, B.E. and Murphy, C.J. Chemistry The Central Science, 11th ed. ; Prentice Hall: New
Jersey, 2009.

Foothill College-Chemistry 1A, Larson, Daley page 8 Last Modified 9/14/14

 Lewis Structures

Summary of general rules for bond types and electronegativity difference (∆EN):
Bond Type $∆EN$
Nonpolar ≤ 0.3
Weakly Polar Between 0.3 to 0.5
Polar Between 0.5 to 2
Ionic ≥2

Practice:
1) Use electronegativity values to determine if each of the following bonds are nonpolar, weakly polar, polar,
or ionic.
0 25 a) C-H
DEN 2 5 d) H-O g) K-Cl

1 21 b) C-O

c) O=O
21 man e) C-S

f) H-Cl
if
Formal Charge: determine the best lewisstruiture
In the ozone example previously discussed, there are two equivalent resonance forms and each
one contributes equally to the overall resonance hybrid. However, cases exist where resonance
forms of the same molecule or polyatomic ion are not equivalent. In cases with nonequivalent
resonance forms, the concept of formal charge can be used to determine which resonance
structure has the lowest potential energy and is therefore the most stable form. The most stable
form is the best representation of the correct bonding within the molecule or ion and contributes
the most to the overall resonance hybrid. Structures with lower formal charges on the atoms tend
to be lower in potential energy. The formal charge on an atom in a molecule or polyatomic ion is
the hypothetical charge the atom would have if each bonding electron pair were shared equally
between its two atoms and each lone pair belonged completely to the atom it is attached to in the
Lewis Structure. Formal charges should not be considered to be actual charges, but they are
useful for determining the most stable resonance form. They can also be used to determine the
most favorable sequence of attachment for the atoms when this is in question.

Formal charge is calculated for each atom (FCatom) in a molecule/ion in the following manner:

–
FCatom = # valence e– – { # shared
2
e
+ # unshared e– } = # valence e– – (dots +
lines)
FC of
valence e bonds of non
mange
Remember: Each “dot” represents an unshared electron on the atom and each “line”
represents a shared pair of electrons on the atom.

The sum of formal charges for all the atoms equals the overall charge of the
molecule/ion.

As an example, calculate the formal charges for each atom in the three resonance structures of

ii –
the cyanate ion, OCN . Two of the resonance structures are shown below, you should draw the
third in the space to the right:

s it have.cat
2
I ↔Y is
iak Fc
To select the most stable resonance form we use the following guidelines:
1. Small formal charges (positive or negative) are preferable to larger ones. minimize
2. Negative formal charges should reside on the more electronegative atom(s). ftp.istsibe
3. Positive formal charges should reside on the least electronegative atom(s).
4. Formal charges with the same sign should not reside on adjacent atoms.
Using these guidelines, choose the resonance form that is the most stable and, therefore,
–
contributes the most to the overall resonance hybrid for OCN .

Foothill College-Chemistry 1A, Larson, Daley page 9 Last Modified 9/14/14

 Better structure
O 5 2 4
62 4 4 4 0O

532 O
4 40O 616 1
 Lewis Structures

Practice and Questions: 1 5 316 24ve

1. There are three resonance structures for HNO3 (nitric acid). Draw the three structures and predict
which structure(s) is (are) the major contributor(s) to the resonance hybrid.

6
o tot
az
doesn't 5 4 041

Yet 11 11
21010 c
p 6 2

4 i i o O
a) Do you expect all three nitrogen–oxygen bonds in the HNO3 to be equivalent to each other? If
not, describe in what ways they will differ from each other.
of 1 1 do it 1 1 10
no one N o bondwillhave B of 5
minimmedto

B0
second N o bond will
have B of
f
2. Use formal charges to determine whether the atom sequence for dinitrogen oxide is most likely
NNO or NON.

More Practice: Electronegativity Differences vs. Formal Charge:

1) Draw the Lewis Structure for carbon monoxide. Indicate by using δ+ and δ- symbols which atom
is partially positive and which is partially negative according to the relative electronegativities of
carbon and oxygen. Redraw the structure and use an arrow to indicate the polarity of the bond.

2) Calculate the formal charges on carbon and oxygen in carbon monoxide. Do the signs of the
formal charges on the atoms agree with the electron distribution predicted by electronegativity
differences?

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Lewis Structures

Carbon monoxide serves as an example that we may have to consider both electronegativity and
formal charges to understand the behavior of some molecules. In fact, the bonding in carbon
monoxide leads to the extremely unusual condition of carbon and oxygen forming three bonds and the
carbon atom having a lone pair. One could argue that carbon monoxide behaves as if the carbon, not
the oxygen, side of the molecule is partially negative. For example, when bonding to the Fe2+ ion in
hemoglobin the carbon atom, not the oxygen, is attracted to and forms the bond with the iron.
Carbon monoxide uses its lone pair on the carbon atom to form this bond. Carbon monoxide
poisoning is the result of CO bonding to the Fe2+ ion in hemoglobin, preventing an O2 molecule from
attaching to the iron. This results in suffocation.

3.C Exceptions to the Octet Rule

The octet rule is very simple and useful for determining the structures of many molecules and
polyatomic ions of the main group elements. Carbon, nitrogen, oxygen, and fluorine obey the octet
rule rigorously, provided that there are enough electrons. However, in some cases there are
insufficient electrons to form a complete octet to all atoms. In addition, a number of atoms of the
main group elements do not always follow the octet rule, either acquiring less than or more than an
octet of valence electrons. The three exceptions to the octet rule are discussed in more detail below.
1. Odd number of electrons: A few molecules have an odd number of total valence electrons. They
cannot possible have all their electrons in pairs. These molecules contain a lone (unpaired)
electron and are called free radicals. Free radicals tend to be reactive. Two examples of single
atom free radicals are H and Cl. When drawing Lewis Structures for free radicals, one atom will
have less than an octet. Formal charges can be used to determine the most stable arrangement of
the electrons.

Example: Draw all possible resonance structures for NO and predict which is (are) the major
contributor(s) to the resonance hybrid.
6 he
6 2 4,05

j.N.gg IN É Beststructure
5 1 3 41 512 3 major contributor
p
2. Less than an octet of valence electrons: This situation is relatively rare, Be and B tend to be
the most common elements to form structures with an incomplete octet.

Example: Draw two Lewis Structures for BCl3. One where the boron atom has an incomplete octet
of only six electrons and one where the octet rule is satisfied for all atoms in the structure.

Bol 3 317 240 H Ibmd

B nothaveoctet be 2bmd
but its FCiso B 3band
stance

Calculate the formal charges on the atoms for the two structures that you drew for BCl3. Choose
the structure (circle it) that is the most stable based upon formal charges.

The Lewis Structure in which the boron atom has a complete octet forces the highly
electronegative chlorine atom to carry a positive formal charge, an unfavorable situation. Thus,

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 Lewis Structures

this structure is considered to be less stable than the Lewis structure where the boron atom has
an incomplete octet. The chemical behavior of boron trichloride is consistent with an electron
deficient boron atom, as predicted by the structure where boron has an incomplete octet. The
other boron trihalides exhibit similar behavior.

Example: Draw the most stable Lewis Structure, based upon formal charges rather that the octet
rule, for BeCl2. Similar to the boron example, this structure is considered to be the one that is
consistent with the known properties of BeCl2.

to me
3. More than an octet of valence electrons: Many molecules and polyatomic ions exist where the
II
central atom has acquired more than eight valence electrons; we call this an “expanded octet”.
Atoms that exceed an octet do so by using empty valence d orbitals for bonding in addition
to valence s and p orbitals. Thus, only atoms from period 3 or higher are capable of
expanding beyond an octet. (Remember that the valence shell must have a principle quantum
number of 3 or higher for it to contain a d subshell.) The “extra” electrons in an expanded valence
shell may be present as lone pairs, usually on the central atom, or they may be the result of the
central atom forming multiple bonds. The minimization of formal charges to form a more stable
structure is considered to be a factor in cases where an octet is exceeded due to the formation of
multiple bonds. Beginning with silicon, Group 4A and 5A atoms will usually expand to 10
electrons, group 6A atoms to 10 or 12 electrons and group 7A atoms to 10, 12 or 14
electrons.
When do you expand an octet? There is much controversy about this in the literature, but we
will follow the rule to expand ONLY WHEN NEEDED! That is we expand only when an atom
must expand to accommodate its bonding and lone pair electrons or when needed to explain
observed (stated) chemical reactivity and/or bond lengths and strengths.

Practice:

1. Draw expanded octet Lewis Structures for the following:

a) SF4 b) H2PO4– (This is phosphoric acid with one H+
removed. Draw the most stable Lewis structure
e 4 28 according to formal charges in this case.)

28 634ve

i
E É 0 O H

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Lewis Structures

2. Draw an expanded octet Lewis Structure for sulfur trioxide that exceeds the octet for sulfur and
also results in zero formal charge on all atoms.

a) Based upon the structure you drew, what is the predicted S–O bond order for sulfur trioxide?

(Note: The observed S–O bond lengths and strengths for sulfur trioxide are consistent with
this prediction!)

l.p. is abbreviation for “lone pair”

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Lewis Structures Name:
Lab Section: MW or TTH

Follow-up questions:
1. Complete the following table for compounds formed by the indicated elements by doing the following:
(1) Draw the Lewis Symbol for the atoms of each element.
(2) Predict if the bonds between the atoms of the given elements are ionic, polar covalent or nonpolar
covalent.
(3) If the compound formed is ionic, give the formula of the ions formed. If the compound is molecular,
predict the bonding ratio between the elements and draw the Lewis Structure for the simplest
possible compound formed by the given elements.
(4) Predict the formula for the compound formed.
(5) Give the name of the compound formed.

Is the bonding If Ionic give

Lewis Predicted
ionic, polar formula of ions
Symbol of chemical Name of
Element covalent or If molecular draw
each formula of compound.
nonpolar predicted Lewis
atom compound.
covalent? Structure

carbon

hydrogen

oxygen

fluorine

barium

fluorine

2. Draw a suitable Lewis structure for:

a) ClO2– c) PCl5

b) BClF2 (Recall how B tends to behave!) d) SO2

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Lewis Structures Name:
Lab Section: MW or TTH

e) HPO42– f) IO3—

3. There are three possible resonance structures for carbonic acid, H2CO3. Draw the three resonance
structures, calculate the formal charges for each atom in each structure and select the resonance
structure(s) that is (are) predicted to be the major contributor(s) to the resonance hybrid.

a) Do you expect the three carbon–oxygen bonds in the H2CO3 molecule to be equivalent to each other?
If not, describe in what ways they will differ from each other.

4. In H2SO4, the sulfur-oxygen bonds are not all the same length; two of them are 157 pm long and two are
142 pm long. Draw the Lewis Structure for H2SO4 that is predicted to be most stable in terms of formal
charges. (Recall that sulfur atoms can accommodate an expanded octet.) Is the structure you drew
consistent with the observed sulfur-oxygen bond lengths?

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Lewis Structures Name:
Lab Section: MW or TTH

a) In the sulfate ion the S–O bond lengths are all identical; they are all shorter than a single S–O bond,
but longer than a double S–O bond. Justify this observation using a Lewis Structure along with a brief
written explanation.

5. A compound has the empirical formula HO and a molar mass of 34.02 g/mol. Determine the most likely
Lewis Structure for this compound.

6. Although I3— exists, F3— does not. Use Lewis structures to help you explain these facts. (Think about
where in the periodic table I and F are located.)

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