ChemActivity 12

Lewis Structures (I)

(What Makes a Molecule?)

WARM-UP
Molecules are created when atoms are combined together. The properties of
molecules vary greatly – even for molecules that may seem very similar at first. For
example, it takes more energy to separate an oxygen atom from a carbon atom in a
molecule of carbon monoxide, CO, than it does to separate an oxygen atom from a
carbon atom in a molecule of carbon dioxide, CO2. Also, the three nuclei in CO2 lie
in a straight line, but the three nuclei in H2O do not.
Chemists have developed a method for predicting these types of properties by
making diagrams of molecules, called Lewis structures. Lewis structures are based on
the number of valence electrons present in each of the constituent atoms of the
molecule. The purpose of Lewis structures is to provide a method for making
reasonable predictions about the structure and properties of actual molecules. We
begin our development of the Lewis structure model with a consideration of the
representation of atoms.
Model 1: Common Methods to Designate Atoms.
Figure 1. Two methods to designate atoms

F atom H atom

+7 or F +1 or H

A fluorine atom has a core charge of +7 and seven valence electrons. A

hydrogen atom has a core charge of +1 and one valence electron. Core charge
models for these two atoms are shown in Figure 1. Alternatively, we could represent
each atom with the appropriate atomic symbol and a dot for each valence electron,
also shown in Figure 1. These types of representations with the atomic symbol and
valence electrons shown are the basis for Lewis structures of molecules; the core
charge is not explicit, and it is the responsibility of the reader to keep the core
charges in mind.
76 ChemActiivity 12 ewis Structurres (I)
Le

Below
w are Lewiss structure representatio
r ons for atom
ms in the indicated groups.
1 2 13 14 155 16 17 18

Mod
del 2: Lew ctures forr Moleculles.
wis Struc
The
T covalen he sharing of
nt bond—th o two elec trons in th
he valence sshell of botth
atom
ms:

Or, more simply,

s

for a covalent b
bond

Addiitional exam
mples:

O + 2 H = O H or O + 2 H = O H
H H

H
N + 3 H = H N H
 ChemActivity 12 Lewis Structures (I) 77

Critical Thinking Questions

1. For each of the following neutral atoms give the core charge.
a) b) c)

2. Draw the Lewis representation for each of the following atoms.

a) iodine b) sulfur c) phosphorus

3. Complete the first three columns of the following table based on the
information in Models 1 and 2. Complete the last columns based on your
knowledge of valence electrons in atoms.
# of # of total # of total # of
electrons electrons total # of valence valence
surrounding surrounding electrons electrons from electrons from
each H atom other atom shown in H atoms the other atom
in the in the Lewis in the in the
molecule molecule structure molecule molecule
HF 8
H2O 2
NH3 2 5

Information
Here are two rules for Lewis structures:
• Hydrogen must share two electrons—a bonding pair.
• The sum of the shared (bonding) electrons and the lone pair electrons for
carbon, nitrogen, oxygen, and fluorine atoms must be eight. That is, the total
number of electrons surrounding these atoms much be 8. This requirement is
known as the octet rule. Usually, the other elements in groups 14, 15, 16, and
17 also follow the octet rule.

Critical Thinking Questions

4. Confirm that your answers to CTQ 3 are consistent with the Information
above.

END OF WARM-UP
78 ChemActivity 12 Lewis Structures (I)

5. Given the shell model of the atom, suggest a possible reason that Lewis
proposed a maximum of two electrons for hydrogen and a maximum of eight
for carbon, nitrogen, oxygen, and fluorine atoms.

6. Based on the Lewis structure model for atoms and the Information above,
construct a Lewis structure for a molecule composed of hydrogen atoms and
one sulfur atom. Explicitly describe how you used the Lewis structure model
for atoms and the Information.

7. Calculate the total number of valence electrons in each of these molecules by

summing up the number of valence electrons present in each constituent atom.
In each case, explicitly show how you reached your final answer.
a) H2CO

b) N2

c) Cl2
 ChemActivity 12 Lewis Structures (I) 79

Model 3: Lewis Structures of Some Molecules.

H2CO N2 Cl2

Critical Thinking Questions

8. a) How many electrons are shared by the two Cl atoms of Cl2 in Model 3?

b) How many electrons are shared by the two N atoms of N2 in Model 3?

c) How many electrons are shared by the C atom and the O atom of H2CO
in Model 3?

9. a) For each atom in each molecule, draw a single circle that encompasses
all of the lone pair electrons and bonds that are considered to be around
the atom, and then indicate the number of electrons that have been
circled.

b) Using your answers to part a, confirm that the numbers of electrons

around each atom is consistent with the Lewis structure rules given in
the Information section.

10. Indicate the total number of electrons in the Lewis structure in Model 3 for
each molecule below.
a) H2CO

b) N2

c) Cl2

11. Explain why your answer for each molecule in CTQ 10 is not equal to the sum
of the circled electrons for each of the atoms in the molecule from CTQ 9.
80 ChemActivity 12 Lewis Structures (I)

12. Compare your answers to CTQs 7 and 10. Based on these answers and the
entries in the three right-most columns in the table in CTQ 3, provide a
description of how to determine the total number of electrons that should be
used to generate a Lewis structure.

13. Create a checklist that can be used to determine if a Lewis structure for a
molecule is correct. Two items from the Information section are included below
as a start.
• H must be surrounded by two electrons – a single bond.
• C, N, O, and F must be surrounded by eight electrons (the octet rule).

14. Use your checklist to determine whether or not the following is a valid
structure for CO2:

For each item in your checklist, describe how you determined whether or not it
was met. Then indicate whether or not the above structure is valid.
 ChemActivity 12 Lewis Structures (I) 81

Exercises
1. How many valence electrons are in the F2 molecule? Write the Lewis structure
for F2.
2. How many valence electrons are in the Cl2 molecule? Write the Lewis structure
for Cl2.
3. How many valence electrons are there in the SiH4 molecule? Write the Lewis
structure for SiH4.
4. How many valence electrons are there in the SiCl4 molecule? Write the Lewis
structure for SiCl4.
5. How many valence electrons are there in the NH3 molecule? Write the Lewis
structure for NH3.
6. How many valence electrons are there in the NCl3 molecule? Write the Lewis
structure for NCl3.
7. How many valence electrons are there in the PH3 molecule? Write the Lewis
structure for PH3.
8. How many valence electrons are there in the PCl3 molecule? Write the Lewis
structure for PCl3.
9. Calculate the total number of electrons in the Lewis structures for each of the
following molecules:
CH3Cl, CH3COOH, HCOOH, HNNH, N2O4, PbCl4, C2H5OH

Problems
1. How many valence electrons are in the C6H12O6 molecule?
2. How many valence electrons are in the NH4+ ion?

3. How many valence electrons are in the O22– ion?

ChemActivity 13
Bond Characteristics
(Are All Bonds Created Equal?)

Model 1: Bond Order and Bond Energy.

Table 1. Bond-related data for selected molecules.

Molecule Lewis Structure Bond Bond Bond
Order Energy
(kJ/mole)
H2 H–H H–H 1 436

Cl2 Cl–Cl 1 243

H2O O–H 1 498

H3CCH3 C–C 1 376

C–H 1 420

C–C 2 720
H2CCH2
C–H 1 444

CO2 C–O 2 804

C–O 2 782
H2CO C–H 1 364

N2 N–N 3 945

C–C 3 962
HCCH
C–H 1 552

The bond energy is defined as the energy required to break the bond that holds
two adjacent atoms together in a molecule. The bond energy is usually expressed on
a molar basis (as the energy to break one mole of specified bonds).
 ChemActivity 13 Bond Characteristics 83

Critical Thinking Questions

1. Verify (using your checklist from CTQ 13 in CA 12) that the Lewis structure
for H2CCH2 given in Table 1 is valid. Explicitly describe how each checklist
item has been met.

2. There are three different bond orders present in Table 1. Give two examples of
each bond order from the molecules in Table 1.

3. What is the relationship between the bond order and the number of electrons
shared by two adjacent atoms?

4. The three different bond orders correspond to designations of single, double,

and triple bonds. What is the relationship between the bond order of a bond
and the designation of single, double, and triple bonds?

5. Rank the three types of bond designations from CTQ 4 in order of increasing
bond energy.

Information
Bonds that have higher bond energy are said to be stronger bonds. We say that
the bond strength of N2 is greater than the bond strength of Cl2.
84 ChemActivity 13 Bond Characteristics

Model 2: Bond Orders and Bond Energies for Additional

Selected Molecules.
Table 2. Bond-related data for selected molecules.
Molecule Lewis Structure Bond Bond Bond
Order Energy
(kJ/mole)

HF H–F 1 570

HCl H–Cl 1 432

HBr H–Br 1 366

HI H–I 1 298

Cl2 Cl–Cl 1 243

Br2 Br–Br 1 193

I2 I–I 1 151

H3CCH3 C–C 1 376

H2CCH2 C–C 2 720

CO2 C–O 2 804

H2CO C–O 2 782

N2 N–N 3 945

HCCH C–C 3 962

 ChemActivity 13 Bond Characteristics 85

Critical Thinking Questions

6. Consider the series HF, HCl, HBr, HI.
a) What is the bond order for each H–X bond in this series?

b) What trend is observed in bond energy in this series?

c) Bond length is defined as the distance between the nuclei of two bonding
atoms. Considering the relative size of F, Cl, Br, and I, what trend
would you predict in H–X bond length in this series? Explain your
reasoning.

7. Consider the series Cl2, Br2, I2.

a) What is the bond order for each X–X bond in this series?

b) What trend is observed in bond energy in this series?

c) Considering the relative size of Cl, Br, and I, what trend would you
predict in X–X bond length in this series? Explain your reasoning.

8. Which of the following statements appears to be true?

a) The longer the bond, the stronger the bond.
b) The shorter the bond, the stronger the bond.
Explain your reasoning by explicitly referring to your answers in CTQs 6 and 7
and the data in Table 1.
86 ChemActivity 13 Bond Characteristics

9. In Table 1,
a) What is the range of bond energies for all single bonds?

b) What is the range of bond energies for all double bonds?

c) What is the range of bond energies for all triple bonds?

10. Based on your answers to CTQs 6 – 9, explain how the following conclusion
can be reached. Refer explicitly to data from Table 1 in your response.
The most important determinant of bond strength is bond order. If the
bond orders are the same: the shorter the bond, the stronger the bond.
 ChemActivity 13 Bond Characteristics 87

Exercises
1. Which C–C bond is harder to break?

2. Which C–C bond is harder to break?

or

3. Which C–N bond is stronger?

or

4. Using grammatically correct sentences, describe the relationships between

bond order, bond energy, and the number of electrons shared in a bond.
5. The skeletal structures (structures that indicate the arrangement of atoms in a
molecule) for formaldehyde (on the left) and methanol (on the right) are shown
below:

Is the following statement true or false? (Explain your answer.)

It takes more energy to break the C–O bond in formaldehyde than to break
the C–O bond in methanol.
[Hint: draw the Lewis structure for each molecule.]
6. A rule of thumb states that about 300 kJ is required to break one mole of single
bonds.
Predict the bond energy of double bonds (in kJ/mole) based on this rule of
thumb. Predict the bond energy of triple bonds (in kJ/mole) based on this rule
of thumb. Compare your predictions to values in Table 1.
88 ChemActivity 13 Bond Characteristics

7. Consider molecules of the type

where X = F, Cl, Br, I.

a) Based on atomic radii, which do you expect to have the longest bond
length, C – F, C – Cl, C – Br, C – I? Which do you expect to have the
shortest bond length? Explain your reasoning.
b) Which do you expect to have the strongest bond, C – F, C – Cl, C – Br,
C – I? Which do you expect to have the weakest bond? Explain your
reasoning.
8. For each of the following, which has the stronger bond between the two bold
atoms? Give a brief explanation. (Hint: write the Lewis Structure for each
molecule.)
a) H3CH and H3SiH
b) N2 and O2
c) H2PH and HOH
d) HSH and HOH
e) HSH and HSeH
f) H2PH and H2NH
g) F2 and O2
9. Rank N2, P2, As2, in order from weakest to strongest bond.
10. Indicate whether each of the following statements is true or false and explain
your reasoning.
a) The bonds in NH3 are shorter than the bonds in NF3 .
b) The bonds in CCl4 are stronger than the bonds in CBr4 .
c) The carbon–nitrogen bond in H3CNH2 is easier to break than the
carbon-nitrogen bond in HCN.
Problem
1. Which molecule or ion has the strongest bond between the two atoms: OH– ;
HS– ; HF ; HCl ; HI ? Explain.
ChemActivity 14
Lewis Structures (II)
(Is One Lewis Structure Enough?)

Model 1: Lewis Structures and Characteristics of Some

Hydrocarbons.
Table 1. Calculated Bond Orders and Bond Lengths for Selected
Hydrocarbons.1
Molecule C–C C–C Bond C–C Bond
Bond Order Order Length
(Lewis) (calculated) (calculated)
(pm)

ethane, H3C – CH3 1.01 150

2 2.00 133

2.96 120
1 pm = 10–12 m

Critical Thinking Questions

1. Fill in the missing entries in the C–C Bond Order (Lewis) column in Table 1.
2. How do the calculated bond orders for ethane, ethene, and ethyne compare to
the bond orders predicted by the Lewis structures?

3. a) Based on the data in Model 1 for ethane, ethene, and ethyne, what is the
qualitative relationship between bond order and bond length?

b) Explain how your answer to part a is consistent with your conclusions

for CTQ 8 from CA 13.

1Excellentestimates of a wide variety of molecular properties can be calculated with sophisticated

molecular modeling software such as Gaussian and Spartan. These calculations yield bond orders and
bond lengths that are generally in good agreement with experimental evidence.
 ChemActivity 14 Lewis Structures (II) 91

4. Predict the C–C bond length for a molecule with a C–C bond order of 1.5.
Provide a justification (a mathematical expression or a statement) for your
prediction using data from Table 1.

Model 2: Benzene.
Table 2. Calculated Bond Orders and Bond Lengths for Benzene.
Molecule C–C C–C Bond C–C Bond
Bond Order Order Length
(Lewis) (calculated) (calculated)
(pm)

1 1.42 139
2 1.42 139
1 1.42 139
2 1.42 139
1 1.42 139
2 1.42 139

1 pm = 10–12 m
Critical Thinking Questions
5. How do the calculated bond orders for benzene compare to the bond orders
predicted by the Lewis structure?

6. Experimentally, we find that all six C–C bonds in benzene have the same bond
energy, 509 kJ/mole. Is this fact more consistent with the bond orders predicted
by the Lewis structure or with the calculated bond orders for benzene?

7. Experimentally (and consistent with the calculated bond lengths in Table 2), we
find that all six C–C bonds in benzene have the same length, 139 pm. Is this
fact more consistent with the bond orders predicted by the Lewis structure or
with the calculated bond orders? [Hint: refer to your answer for CTQ 4.]

8. What feature(s) of the Lewis structure of benzene, Table 2, is inconsistent with

the calculated C–C bond orders in Table 2?
92 ChemActiivity 14 Lew
wis Structure
es (II)

Mod
del 3: Re
esonance Structurres.
An
A alternatiive represen
ntation for benzene
b is ggiven in Figu
ure 1.
Figu
ure 1. Th
he resonan
nce hybrid representtation of be
enzene.

Neither
N stru
ucture I nor structure III alone provvides a good
d descriptio
on of the tru
ue
bond
ding of benzzene becausee each struccture alone predicts thaat there are two types o of
bond
ds in benzen ne – single bonds and double bon nds. Howevver, the calculated (an nd
experrimental) bo ond orders suggest thaat all of thee bonds in bbenzene are identical, iin
confllict with tha
at prediction
n.
A better desscription off the bondinng in benzenne is providded by a com mbination o of
strucctures I and II. Structurres I and II are known n as resonannce structurees. A doublee-
headed arrow is used to ind dicate reson
nance structtures. Each resonance sstructure is a
legitiimate Lewiss structure. When we drawd resonaance structuures, we leavve the atomms
in pla ace and chaange the reppresentationn for how tthe electron ns are arranged The besst
o the moleccule is takenn to be the aaverage of tthe resonancce
descrription of the structure of
d a resonancce hybrid. For the reson
strucctures, called nance structtures of ben nzene, abovee,
the bond
b order for
f each C–C bond is th he average o of the bondd order of a double bon nd
(2) and
a the bonnd order ofo a single bond (1), w which is 1..5. Thus, th he predicteed
properties for ea ach C–C bo ond in benzzene are halffway betweeen that of a C–C singlle
bond d and that of a C–C dou uble bond.
 ChemActivity 14 Lewis Structures (II) 93

Critical Thinking Questions

9. Based on the resonance hybrid model of Figure 1, why is the C–C bond order
(Lewis) 1.5? Explain your analysis.

10. As noted in the footnote for Table 1, the calculated bond orders and bond
lengths in Tables 1 and 2 are expected to be in good agreement with
experimental results. Given this assumption, which representation of benzene is
better—a single Lewis structure, as shown in Model 2, or the resonance hybrid
representation shown in Model 3? Explain your reasoning.
94 ChemActivity 14 Lewis Structures (II)

Exercises
1. Which C–C bond is shorter?

2. Which C–C bond is shorter?

or

3. Which C–N bond is longer?

or

4. Indicate whether the following statement is true or false and explain your
reasoning:
The carbon-oxygen bond length in H2CO is the same as the
carbon-oxygen bond length in CH3OH.
5. The molecular formula of cyclobutadiene is C4H4 and one of the resonance
structures is given below (on the left):

a) Give the other resonance structure for cyclobutadiene (on the right).
b) Based on the resonance structure representation, predict the C–C bond
order in cyclobutadiene.
c) Based on the resonance structure representation and the bond length
data for ethane and ethene in Table 1, predict the C–C bond length in
cyclobutadiene.
 ChemActivity 14 Lewis Structures (II) 95

Problems
1. Put the following molecules in order of increasing N–N bond length:
N2 ; HNNH ; H2NNH2 .
2. Put the following molecules in order of increasing bond length: N2 ; O2 ; F2 .
3. The typical bond length for a C–N single bond (bond order = 1) is 147 pm.
Based on this result, the typical bond length for a C–O single bond (bond order
= 1) is expected to be:
i) 143 pm
ii) 147 pm
iii) 151 pm
iv) 205 pm
v) impossible to estimate from the information given.
4. Is the experimental C–C bond energy for benzene, 509 kJ/mole, consistent with
the C–C bond energies given in Model 2 of ChemActivity 13? Explain your
reasoning.
Che
emActiv
vity 15
5
Lew
wis Structu
ures (IIII)
(Are All
A Lewis Sttructures Crreated Equaal?)

WA
ARM-UP
Mod
del 1: Forrmal Charrge and the
t Lewis
s Structurre of Watter.
The
T purposse of Lewiss structuress is to pro ovide a simmple model from whicch
prediictions abou
ut moleculaar structuree can be maade. The co oncept of foformal chargge
has been
b found to be useful for determ
mining the bbest Lewis sstructure forr a moleculee.
Formmal charges are assigned
d to atoms ini moleculees accordingg to a set of rules:
1.
1 formal charge
c = co
ore charge – number o
of assigned electrons
2.
2 Electron
ns are assign
ned as follow
ws:
i) Nonbonding
N electrons arre assigned to the attacched atom.
ii) Sh
hared electrons are even
nly divided between thee bonded attoms.
Because of the rules
r above,, the sum off the formaal charges on
n a moleculle or ion wiill
alway
ys be equal to the totall charge on the
t moleculle or ion.
We can
c assign ellectrons to calculate
c formal chargees for the Leewis structu
ure of H2O.

Critical Thinking Que

estions
1. a) Expplain expliciitly why theere are eigh
ht electronss in the Lew
wis structurre
for H2O.

b) Com
mplete the following
f table based on
n the Lewiss structure o
of H2O.
Left H O ato
om Rigght H
atom attom
Co
ore charge
To
otal assigned electrons
Fo
ormal chargge
 ChemActiv
vity 15 Lew
wis Structures (III) 9
97

Info
ormation
The
T formal charge on each atom in the Lewiis structure of H2O is zero. Atom ms
with zero forma al charge do
o not have any
a additionnal designattion added to the Lewis
struccture. Thus, the Lewis structure
s of H2O, comp
plete with fo
ormal chargges, is:

Mod
del 2: The
e Lewis Structure
S of Carbo
on Monox
xide.

Critical Thinking Que

estions
2. a) Expplain explicitly why th
here is a to
otal of 10 electrons iin the Lewis
stru
ucture for CO.

b) Expplain why a Lewis struccture of CO

O with a singgle bond beetween C an nd
O and
a two lonne pairs of electrons o
on each ato om is not a valid Lewis
stru
ucture. (Hint: consider drawing
d thee Lewis stru
ucture that is described..)

c) ow explicitly
Sho y why the fo
ormal chargge on C is -11 and the fo
ormal chargge
on O is +1 for the
t Lewis sttructure of C
CO shown iin Model 2

Info
ormation
A formal ch
harge other than zero iss circled and
d written neext to the syymbol for th
he
atom
m. Thus, the completed Lewis struccture for carrbon monoxxide, CO, is:

There is no valid
d Lewis stru
ucture that can
c be mad
de for CO in
n which all o
of the formaal
ges are zero and the octtet rule is ob
charg beyed.
END OF
O WARM
M-UP
98 ChemActivity 15 Lewis Structures (III)

Model 3: Two Possible Lewis Structures for CO2.

O C O O C O

I II

Critical Thinking Questions

3. Use the rules in Model 1 to calculate the formal charges for each of the atoms
in structures I and II. Add formal charges to Model 3 as appropriate.

4. Show explicitly how the number of electrons in each of the two Lewis
structures for CO2 was determined.

5. a) Complete this table for the two possible structures of CO2 shown in
Model 3.

Structure I Structure II
Total number of
electrons in the
Lewis structure
Number of
electrons around
the carbon atom
Number of
electrons around
the left-hand
oxygen atom
Number of
electrons around
the right-hand
oxygen atom
b) Based on your answers above and your checklist, is each proposed
structure in Model 3 a valid Lewis structure for CO2? Explain why or
why not.
 ChemActivity 15 Lewis Structures (III) 99

Information
Experimentally, we find that both C–O bonds in CO2 are identical. The C–O bond
energy in CO2 is 804 kJ/mole for each C–O bond; that is, it requires 804 kJ to break
one mole of C–O bonds in CO2.

Critical Thinking Question

6. Based on the experimental results presented in the Information, which Lewis
structure, I or II, provides a better description of CO2? Explain your reasoning.

Information
Sometimes, as we have seen for CO2, there is more than one possible Lewis
structure (or set of resonance structures) for a molecule that is consistent with our
guidelines for constructing Lewis structures. By examining the situations in which
this occurs and comparing the competing Lewis structures with experimental
evidence about bond strengths and other molecular properties, a general rule is
observed: the best Lewis structure is the one (or ones if a resonance hybrid) with the
lowest formal charges. Thus, if a valid Lewis structure exists that has no formal
charge, it is the best Lewis structure representation possible.
Formal charges greater than ±1 are never found in good Lewis structures. A
Lewis structure is not considered complete unless the formal charges (other than
“0”) are indicated.
Critical Thinking Questions
7. a) Based on the concept of formal charge, which is the better Lewis
structure for CO2 (in Model 3)— I or II? Explain your reasoning.

b) Explain how your choice in part a is (or is not) consistent with the
experimental data.

8. If the net charge on a molecule is zero, must the formal charge on every atom
in the molecule equal zero? Why or why not?
100 ChemActivity 15 Lewis Structures (III)

9. Two Lewis structures for formic acid are given below.

a) According to the Information section preceding CTQ 7, which is the

better Lewis structure?

b) Experimental measurements of formic acid show that the C–O bond

length involving the oxygen with no hydrogen attached is 124 pm and the
C–O bond length involving the oxygen with a hydrogen attached is 131
pm. Explain how this information is or is not in agreement with your
answer to part a.

10. Based on what you have learned in CAs 14 and 15, there are changes or
additions that need to be made to the checklist that you wrote in CTQ 13 of
CA 12. In the space below provide a complete, revised checklist that can be
used to determine if a Lewis structure is correct and that it is the best Lewis
structure.
 ChemActiv
vity 15 Lew
wis Structures (III) 10
01

Exe
ercises
1. Some of th
he followingg Lewis stru
uctures are missing forrmal chargees. Fill in th he
formal cha
arges (other than zero) where need ded. Then u use your cheecklist (from
m
CTQ 10) to
o verify thatt each Lewis structure ggiven is corrrect.

2. The followwing Lewis structure

s forr CO has no
o formal ch
harges. Expllain why this
is not a vallid Lewis strructure.

3. The Lewis structure fo

or ozone, O3, is

a) What is the O–
–O bond ord
der in ozonee?
b) Thee bond lenggth of a noormal oxygeen-oxygen ssingle bond d is 148 pm
m.
Thee bond lengtth of a norm
mal oxygenn-oxygen doouble bond iis 121 pm. IIs
the oxygen-oxyygen bond length
l in ozzone, 128 pm
m, consisten
nt with thesse
ues? Explain your reasoning.
valu
4. Indicate whether
w the following statement is true or false and eexplain you
ur
reasoning.
The carb
bon-nitrogeen bond in H3CNH2 is easier to brreak than th
he carbon-
nitrogen
n bond in HCN.

Prob
blem
1. a) Provide the best
b Lewis structure ((include ressonance strructures an
nd
mal chargess as necessarry) for the aacetate anio
form on, CH3COO –
O . Estimatte
the C–O bond length
l based on the infformation ggiven in CTQ
Q 9.
b) What is the carrbon-oxygen
n bond ordeer in the aceetate ion?
ChemActivity 16
Lewis Structures (IV)
(Eight or More Than Eight? That Is The Question!)

Model 1: The Lewis Structure for the Nitrate Ion.

O N O O N O O N O
O O O

Experimental measurements show that all three N–O bonds in NO–3 are identical.
The N–O bond order is 4/3 for each bond.
Critical Thinking Questions
1. a) How many valence electrons does one nitrogen atom have?
b) How many valence electrons do three oxygen atoms have?
c) How many valence electrons does one NO3 molecule have?

d) How many valence electrons does one NO–3 ion have?

e) How was the number of electrons used for each resonance structure
shown in Model 1 calculated?

2. Why is a resonance hybrid representation of NO–3 better than just a single

structure? Refer explicitly to information presented in Model 1 as part of your
answer.

3. How was the N–O bond order of 4/3 calculated for NO–3 ?
 ChemActivity 16 Lewis Structures (IV) 103

Model 2: Extended Octets.

Figure 1. Atoms in the third, fourth, and fifth periods can have extended
octets.

The sum of the bonding and lone-pair electrons for atoms in the third, fourth,
and fifth periods is sometimes greater than eight, particularly for atoms in the center
of a molecule.
Critical Thinking Questions
4. Show explicitly that the Lewis structures in Figure 1 have the correct number
of electrons and that the formal charges on each atom are correct.

5. What is the sum of the bonding electrons and nonbonding electrons for each of
the central atoms in Figure 1?

6. Considering the valence shell for these atoms, explain why C, N, O and F can
accommodate only eight electrons (sum of the bonding and lone-pair electrons)
in Lewis structures.

7. Considering the valence shell again, why can atoms in the third (or greater)
period accommodate more than eight electrons (sum of the bonding and
nonbonding electrons)?
104 ChemActivity 16 Lewis Structures (IV)

8. Revise (as necessary) your checklist that can be used to determine if a Lewis
structure is correct and that it is the best Lewis structure.

Exercises
1. How many valence electrons are in each of the following? SO3 ; SO2– 2–
3 ; SO4 ;
HSO–4 ; NH+ +
4 ; C6H6 ; C14H12N4O2S ; C14H12N4O2S ; C6H5NH3 ; CCl4;
+

ClO–4 .

2. How many valence electrons are in the NO–2 ion? The best Lewis structure for
NO–2 includes two resonance structures. Draw these structures (include formal
charges). What is the N–O bond order?
3. Which has the shorter N–O bond length, NO–2 or NO–3 ?
4. How many valence electrons are in SO3? Draw the best Lewis structure for
SO3. (Hint: all formal charges are zero in the best Lewis structure for this
molecule.) What is the S–O bond order?
5. Draw the best Lewis structure (include resonance structures and formal
charges when necessary) for: SO2; CO2– –
3 ; SiCl4 ; OH ; HCN.
6. Some of the following Lewis structures are missing formal charges. For each
of the following pairs, fill in the formal charges and decide which Lewis
structure is better.
 ChemActivity 16 Lewis Structures (IV) 105

7. There are six good resonance structures for SO2–

4 . One of them is given below.
Draw the other five. What is the S–O bond order in SO2–
4 ?

8. Write a Lewis structure for each of the following (include resonance structures
and formal charges; skeleton structures are given);
H2CO (methanal) H2CCH2 (ethene)

HCCH (ethyne or acetylene) NH2CH2COOH (glycine, an amino

acid)

bromobenzene cyclohexene

HNO2 (nitrous acid) N2H5+

H–O–N–O
106 ChemActiivity 16 Le
ewis Structurres (IV)

9. Find the error

e in eacch of the following
f L
Lewis structu
ures. Givee the correcct
Lewis struccture.

10. It is possib
ble to constrruct a Lewiis structure for XeO4 tthat has sin
ngle bonds tto
each of th he O atomss and no lo one pairs oon the Xe aatom. Draw w this Lewis
structure, including
i fo
ormal charges as relevaant, and then why this is noot
n explain w
the best Leewis structurre representtation.

Prob
blems
1. For each of
o the folloowing species, provide the best LLewis structture (includ
de
resonance structures and
a formall charges wh here necesssary) and determine thhe
bond orderr between th
he central attom and an
n attached attom:
a) PO43–

b) O3 –
ClO
c) TeC
Cl4

d) CO32–
2. Identify tw
wo elementss that can represent ““X” if X haas one lonee pair in th
he
molecule XBr
X 4.

3. Estimate, as
a best you can, the C–O
C bond leength in thee carbonatee ion, CO32 ,
given that the C–O bo
ond length in
i methanoll is 143 pm and that thhe C–O bon nd
ormaldehyd
length in fo de, H2CO, iss 116 pm. E
Explain youur reasoningg.
Che
emActiv
vity 17
7

olecular Sh
Mo hapes
s
What Shapes Do Molecu
(W ules Have?)

Mod
del 1: Bond Angle ctron Domains.
e and Elec
A bond ang ngle made by
gle is the an b three co onnected nuuclei in a m
molecule. B
By
convention, the bond angle is considereed to be bettween 0° and 180°.

Table 1. Bond angles and ng domains

a bondin s in selected molecu
ules.
Mollecular Lewis
L Struccture Bond Angle No o. of No. of
Forrmula )1
(calculated)
( Bon nding N
Nonbondingg
Dom mains Domains
(ceentral (central
attom) atom)

CO
C 2 O C O ∠OCO
∠ = 18 0° 2 0

HC
CCH ∠HCC
∠ = 18 0° 2 0

H2CCCH
C 2 ∠CCC
∠ = 1800° 2 0

C
Cl N N Cl ∠C
ClNN = 1177.4° 2 1
ClN
NNCl

∠ONO
∠ = 1220°
O–3
NO O N O 3 0

H2CCH
C 2 ∠H
HCH = 1211.1° 3 0

Table 1 contiinues on thee next page

1Excellent estimatess of a wide varriety of moleccular propertiees can be calcu

ulated with sophisticated
moleccular modelingg software succh as Gaussian n and Spartann. These calcullations yield b
bond angles
that are
a generally inn good agreem ment with expeerimental evid dence.
108 ChemActiivity 17 Mo
olecular Shapes

Mollecular Leewis Structu

ure Bonnd Angle No. o of No. of
Forrmula (callculated) Bondiing N
Nonbonding
Domaains Domains
(central aatom) (ceentral atom))

CH
C 4 ∠HCH
H = 109.45° 4 0

∠HCH
H = 109.45°
CH
H3F ∠HCF
F = 109.45° 4 0

∠HCH
H = 109.45°
CH
H3Cl ∠HCC
Cl = 109.45° 4 0

CCl
C 4 ∠ClCC
Cl = 109.45°°
4 0

NH
N 3 ∠HNH
H = 107° 3 1

∠HNH
H =106.95° 3 1
NH
H2F ∠HNF
F = 106.46°

H2O ∠HOH
H = 105° 2 2

Critical Thinking Que

estions
1. Show expliicitly that th
he number of electronss in the Lew
wis structuree of ClNNC
Cl
is correct in
n Table 1 an
nd that the formal
f charrge on each atom is corrrect.
 ChemActivity 17 Molecular Shapes 109

2. Complete the table below based on the information in Table 1.

Molecule Central Number of atoms Number of lone pairs of

Atom bonded to a central electrons on a central atom
atom
CO2 C 2
ClNNCl N 1
NO–3
NH3
CH4
H2O

3. Compare the results in the table from CTQ 2 to the information in Table 1.
a) How is the number of bonding domains on a given atom within a
molecule (such as those in Table 1) determined?

b) How is the number of nonbonding domains on a given atom within a

molecule (such as those in Table 1) determined?

4. The bond angles in Table 1 can be placed in three groups, each group with a
range of no more than 5°. What are these three groupings?

5. What correlation can be made between the values in the last two columns in
Table 1 and the groupings identified in CTQ 4?
110 ChemActivity 17 Molecular Shapes

Model 2: Models for Methane, Ammonia, and Water.

Use a molecular modeling set to make the following molecules: CH4; NH3;
H2O. (In many modeling kits: carbon is black; oxygen is red; nitrogen is blue;
hydrogen is white. Nonbonding electrons are not represented in these models.)
Critical Thinking Questions
6. Sketch a picture of the following molecules based on your models: CH4; NH3;
H2O.

7. Describe (with a word or short phrase) the shape of each of these molecules:
CH4; NH3; H2O.
 ChemA
Activity 17 Molecular Shapes 11
11

Mod
del 3: Types of Electron Domains.
The
T electron ns around an
a atom in a molecule can be tho ought of as being placeed
in do
omains. Theere are two electrons
e in
n a nonbondiing domain, sometimes called a lonne
pair. A single boond domain contains twwo electronss shared bettween two aatoms. Therre
are four
fo electron ns in a doub
ble bond dommain and sixx electrons in a triple bbond domainn.
Eachh domain of electrons tends to reepel other d domains off electrons. Domains o of
electrrons around a centrall atom will orient them mselves to minimize tthe electron n-
electrron repulsio
on between the domain ns.

Figu
ure 1. Minimization
n of electro
on-electro n repulsion leads to a unique
ge
eometry fo
or two, thre
ee, and fou
ur domains s of electro
ons.

Critical Thinking Que

estions
8. Based on Figure
F 1, wh
hat bond an
ngle is expeccted for a mo
olecule conttaining:
a) two
o domains of electrons?
b) threee domains of electronss?
c) fourr domains of
o electrons??
112 ChemActivity 17 Molecular Shapes

9. Complete the table below.

Total number Predicted bond Calculated
Molecular
Lewis Structure of electron angle bond angle
Formula
domains (from Figure 1) (from Table 1)

CH4

NH3

H2O

NO–3

CO2

10. Individually, determine which of the following statements appears to be true.

There may be more than one. Then, reach a team consensus.
i) When the central atom has no lone pairs, the bond angle predicted by
the Lewis structure is equal to the observed (calculated) bond angle.
ii) When the central atom has one or more lone pairs, the bond angle
predicted by the Lewis structure is slightly larger than the observed
(calculated) bond angle.
iii) When the central atom has one or more lone pairs, the bond angle
predicted by the Lewis structure is slightly smaller than the observed
(calculated) bond angle.
 ChemA
Activity 17 Molecular Shapes 13
11

11. Based on your answeer to CTQ 9, predict the bond aangle for each of thesse
species:
a) O3

b) H2CO
C

c) NF3

Info
ormation
The
T names for molecu ular shapes are based o on the posittion of the atoms in th
he
moleecule—not on
o the positiion of the ellectron dom
mains.

Figu
ure 2. Th
he Lewis structure,
s electron
e do
omains, an
nd molecullar shape
off H2O.
114 ChemActiivity 17 Mo
olecular Shapes

Figu
ure 3. Fiive commo
on molecullar shapes
s.

Critical Thinking Que

estions
12. Considerin
ng the geom metries descrribed in Figgure 1, explaain why thee bond anglle
in bent mo
olecules is ex
xpected to be
b close to eiither 109° o
or 120°.

13. Using grammmatically correct senntences, expplain how th

he shape off a moleculle
can be pred
dicted from its Lewis sttructure.
 ChemActivity 17 Molecular Shapes 115

Exercises
1. a) Draw the Lewis structure for NH3.
b) How many electron domains does the nitrogen atom have in NH3?
c) Make a sketch of the electron domains in NH3.
d) Examine the drawing for the molecular shape of H2O given in Figure 2;
make a similar drawing for NH3.
e) Name the shape of the NH3 molecule and give the approximate bond
angles.
2. a) Draw the Lewis structure for CH4.
b) How many electron domains does the carbon atom have in CH4?
c) Make a sketch of the electron domains in CH4.
d) Examine the drawing for the molecular shape of H2O given in Figure 2;
make a similar drawing for CH4.
e) Name the shape of the CH4 molecule and give the approximate bond
angles.
3. a) Draw the Lewis structure for SO2.
b) How many electron domains does the sulfur atom have in SO2?
c) Make a sketch of the electron domains in SO2.
d) Examine the drawing for the molecular shape of H2O given in Figure 2;
note that the electron domain geometry is different for SO2 and make a
similar drawing for SO2.
e) Name the shape of the SO2 molecule and give the approximate bond
angles.
4. Draw the Lewis structure, sketch the molecules, predict the molecular shape,
and give the bond angles for: PH3 ; CO2 ; SO3 ; SO32– ; N2 ; HF ; H3O+ ;
NH2F ; CCl4 ; O2 ; CO2–
3 .

5. Explain why ∠HCC = 180° in HCCH.

6. Explain why ∠ClNN = 117° in ClNNCl.
116 ChemActivity 17 Molecular Shapes

7. Predict the bond angles around each atom designated with an arrow in glycine
(an amino acid).

8. Predict the bond angles around each atom designated with an arrow in para-
aminobenzoic acid (PABA used in sunscreens).

Problems
1. a) Predict the HCC bond angle in the acetate ion, CH3COO–.
b) Predict the OCO bond angle in the acetate ion.
2. Predict the bond angle in each of the following where N is the central atom and
name the shape of the molecule or ion:
a) NO2+
b) N2O
c) NO2Cl

d) NH2–.
ChemActivity 18
Hybrid Orbitals
Model: Hybridization of Orbitals.
Many chemists describe the arrangement of electron pairs around an atom in a
molecule using different terminology than what we are using. The electron pairs
(either bonding pairs or lone pairs) around the central atom in a molecule are said to
be in orbitals that are constructed from combining two or more of the usual set of
atomic orbitals (s, p, d) for the atom. These constructed orbitals are said to be
hybridized from the original atomic orbitals, and they are referred to as hybrid
orbitals. The construction of hybrid orbitals is beyond the scope of this
ChemActivity, but one key point can be made:
There is a conservation of orbitals. That is, if one s-orbital and one p-
orbital are used—two hybrid orbitals (called sp hybrid orbitals) are
made. The central atom is said to be sp-hybridized. If one s-orbital
and two p-orbitals are used—three hybrid orbitals (called sp2 hybrid
orbitals) are made. The central atom is said to be sp2-hybridized.

Table 1. Characteristics of some hybrid orbitals.

Number Arrangement of
Hybrid of Hybrid Component Angle Between Hybrid
Orbitals Orbitals Orbitals Orbitals Orbitals
in Set in Set
sp 2 one s, one p 180° linear

sp2 3 one s, two p 120° trigonal planar

sp3 4 one s, three p 109.45° tetrahedral

The hybridization assigned to the central atom is based on the experimental bond
angle.
• If the experimental bond angle is about 109°, we say that the central atom is
sp3-hybridized.
• If the experimental bond angle is about 120°, we say that the central atom is
sp2-hybridized.
• If the experimental bond angle is about 180°, we say that the central atom is
sp-hybridized.
118 ChemActiivity 18 Hy
ybrid Orbitals
s

Critical Thinking Que

estions
1. The geomeetry of the methane
m molecule is sho
own below.

a) What is the preedicted H–C

C–H bond aangle?
b) What is the exp
pected hybriidization off the carbon
n atom?

2. The Lewis structure off the water molecule

m is shown belo
ow.

a) What is the preedicted H–O

O–H bond aangle?
b) What is the exp
pected hybriidization off the oxygen
n atom?

3. One of the resonance structures

s or the nitratte ion, NO–3 , is shown below.
fo

a) What is the preedicted O–N

N–O bond aangle?
b) What is the exp
pected hybriidization off the nitrogeen atom?

Exe
ercises
1. For the mo
olecule H2S:
a) Dra
aw the Lewiis structure.
b) What is the tottal number of
o electron d
domains ab
bout the central S atom?
c) What is the arrrangement of
o the domaains?
d) What is the preedicted bond
d angle in th
his moleculee?
e) What is the mo
olecular shap
pe?
f) What is the exp
pected hybriidization off S?
 ChemActivity 18 Hybrid Orbitals 119

2. Draw the Lewis structure, determine the arrangement of the electron domains,
and give the expected hybridization of the central atom in each of the
following: H2S ; CO2–
3 ; CCl4 ; SO2 ; CO2 ; PH3 ; H2CO.
3. Give the expected hybridization around each atom designated with an arrow in
glycine (left; an amino acid) and para-aminobenzoic acid (right; PABA used in
sunscreens).

Problems
1. Determine the H–O–O bond angle in hydrogen peroxide, HOOH. Give the
hybridization on each oxygen atom.
2. For benzene, give
a) the hybridization on all carbon atoms.
b) all bond orders.
c) all bond angles.