Fall 2022

CHAPTER 9
Chemical Bonding I:
Lewis Theory

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Types of Chemical Bonds
• Ionic Bond: electron transferred from metal to non-metal to form cation/anion pair

• Covalent Bond: electrons shared between non-metals

• Metallic Bond: valence electrons delocalized over many metal nuclei

2
Electron Dot Diagrams
• We are not representing structures this way in CHEM 1000

3
Drawing Lewis Structures for Molecular Compounds
• Covalent bonds between atoms form molecular compounds
• Sharing of electrons between neighboring atoms can form octets (non-H)
• A shared electron pair (2 electrons) forms a single chemical bond,
represented by a straight line between the atoms
• Pairs of electrons not involved in bonding are called lone pairs, please do
not draw with a dash (-)
• No molecular geometry is implied

• Examples of Lewis structures with single bonds – convince yourself all atoms
have full octets (except H)

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Drawing Lewis Structures for Molecular Compounds
• In some cases, double or triple covalent bonds can form in order to achieve
full octets on all non-H atoms

• Double bond (=): four electrons shared as two pairs

• Triple bond (≡): six electrons shared as three pairs

• Examples of molecules with double or triple bonds – convince yourself all

atoms have a full octet
• Do not exceed 8 electrons around a second-row element

5
Polling question
Which of the following Lewis structures contains an atom that lacks a
full octet? (not counting hydrogen atoms)

A) C)

B) D)

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Drawing Lewis Structures for Molecular Compounds
The following steps are a general guide on how to draw Lewis structures for a
simple molecule from scratch

• Calculate the total number of valence electrons in the entire molecule

• Draw one single bonded between each pair of bonded atoms

− If molecule has >2 atoms, identify the “central atom” (never hydrogen)

− Central atom is usually the atom with the lower group number (NF3)

− If all atoms in the same group, then central atom is usually the atom with the
higher period number (ICl2)

− Sometimes the way the formula is written gives a clue (H3COH)

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Drawing Lewis Structures for Molecular Compounds
• Calculate the number of valence electrons remaining after accounting for 2
electrons in each single bond

• Distribute remaining electrons, in pairs, among the remaining terminal atoms

first, then to the central atom if any remain (do not exceed octets, do not
place lone pairs on hydrogen)

• If any atoms lack octets, form double or triple bonds as needed by moving
lone pairs into new bonds as needed

• The best way to learn is practice, practice, practice!

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Drawing Lewis Structures for Molecular Compounds
• Valence electron counts for atoms comes from the periodic table:

Valence electrons: 1 2 3 4 5 6 7 8

9
Drawing Lewis Structures for Molecular Compounds
• Example 1: Draw the Lewis structure for ammonia (NH3)

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Drawing Lewis Structures for Molecular Compounds
• Example 2: Draw the Lewis structure for nitrogen gas (N2)

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Drawing Lewis Structures for Polyatomic Ions
• Polyatomic ions contain atoms bonded covalently with an overall charge on
the entire structure (e.g. ClO-, NH4+, SO42-)

• Procedure is almost identical to neutral molecules, but add or subtract

valence electrons from the total count

• Draw a square bracket around the structure to indicate the charge

• Valence electron count examples:

ClO- :

NH4+ :

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Drawing Lewis Structures for Molecular Compounds
• Example 3: Draw the Lewis structure for hypochlorite (ClO-)

13
Drawing Lewis Structures for Ionic Compounds
• Transfer electrons from metal to non-metal to achieve octets on each ion

• Example: sodium sulfide (Na2S)

14
The Ionic Bonding Model
• Forming ionic solids from their constituent elements is usually highly
exothermic
Na(s) + ½ Cl2 (g) → NaCl (s) ΔfH°= -411 kJ/mol
• Can not be explained solely by transferring an electron from sodium to
chlorine , which is slightly endothermic
• Instead, can be explained by the strongly exothermic process of combining
Na+ and Cl- in the gas phase to form the ionic solid (lattice energy)

15
Born-Haber Cycle
• To estimate lattice energy , we set up a hypothetical series of steps that can
produce NaCl(s) from Na(s) and Cl2 (g) with known enthalpy values
• We can use Hess’s law to solve for the unknown enthalpy value

Na(g) + Cl- (g) → NaCl (s) ΔrH°= ? (lattice energy)

Reaction 1: Formation of gaseous sodium from solid sodium

Na(s) → Na(g) ΔrH1°= 108 kJ/mol

Reaction 2: Formation of a chlorine atom from a chlorine molecule

½ Cl2 (g) → Cl(g) ΔrH2°= 122 kJ/mol
Note: We will see where this value comes from in section 9.6
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Born-Haber Cycle
Reaction 3: Ionization of gaseous sodium to form gaseous sodium ion
Na(g) → Na+(g) + e- ΔrH3°= 496 kJ/mol

Reaction 4: Addition of an electron to gaseous chlorine atom to form gaseous

chloride ion
Cl(g) + e- → Cl-(g) ΔrH4°= -349 kJ/mol
* remember, positive electron affinity values from chapter 8 correspond to
negative ΔH values

Reaction 5: Formation of solid NaCl from gaseous Na+ and Cl- (lattice energy)

Na+(g) + Cl- (g) → NaCl (s) ΔrH5°= ?

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Born-Haber Cycle
Add all five reactions together, and solve for the unknown value

Na(s) → Na(g) ΔrH1°= 108 kJ/mol

½ Cl2 (g) → Cl(g) ΔrH2°= 122 kJ/mol
Na(g) → Na+(g) + e- ΔrH3°= 496 kJ/mol
Cl(g) + e- → Cl-(g) ΔrH4°= -349 kJ/mol
Na+(g) + Cl- (g) → NaCl (s) ΔrH5°= ?
______________________
Na(s) + ½ Cl2 (g) → NaCl (s) ΔfH°= -411 kJ/mol

ΔfH°= ΔrH1°+ ΔrH2°+ ΔrH3°+ ΔrH4°+ ΔrH5°

ΔrH5°= -788 kJ/mol, highly exothermic
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Trends in Lattice Energies
• We can examine trends in lattice energies of various ionic
compounds

• Trends can be explained by trends in ionic radii of cations and

anions

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Trends in Lattice Energies
• As ions get larger, the bonding distance increases and lattice
energy becomes less exothermic

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Trends in Lattice Energies
• As magnitude of charges on ions increase, lattice energy
becomes much more exothermic by Coulomb’s law

• Ca2+ larger than Na+ and O2- larger than F- but the higher
magnitudes of charges on Ca and O more than compensate
• Usually a more significant effect than size

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Polling question
Arrange the following in order of increasing magnitude of lattice
energy (least exothermic to
most exothermic): NaI, KI and MgO

A) NaI < KI < MgO

B) NaI < MgO < KI
C) KI < NaI < MgO
D) KI < MgO < NaI
E) MgO < KI < NaI

22
Ionic Bonding: Models and Reality
• Solid ionic compounds exist as a crystalline lattice of cations and
anions
• Ions are fixed in place, strong forces of attraction give rise to very
high melting points (m.p. of NaCl = 800°C)

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Ionic Bonding: Models and Reality
• Solid ionic compounds do
not conduct electricity
• Dissolving ionic compounds
in water separates the
cations and anions, making
them mobile
• Aqueous solutions of ionic
compounds conduct
electricity

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Covalent Bond Energies
• Bond energy is the amount of energy required to break 1 mol of
bonds between two atoms in the gas phase
• Examples
Cl2 (g) → 2 Cl(g) ΔrH = 243 kJ/mol
HCl (g) → H(g) + Cl(g) ΔrH = 431 kJ/mol

• Bond energies always positive (takes energy to break a bond)

• H-Cl bond stronger than Cl-Cl bond

• Some tabulated bond energies are average values taken from

many different compounds
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Covalent Bond Energies

• Will need to use table

9.1 to solve some
textbook problems

• Compare single vs.

double vs. triple bonds
for nitrogen

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Covalent Bond Energies
• Can use bond energy values from table to estimate enthalpy
changes for a chemical reaction
Example:
H3C-H(g) + Cl-Cl(g) → H3C-Cl(g) + H-Cl(g)

ΔrH is the sum of the enthalpy changes of breaking and forming the
various bonds in the molecules as reaction progresses from
reactants to products

Bonds broken:
Bonds formed:
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Covalent Bond Energies
Bonds broken: C-H and Cl-Cl
Bonds formed: C-Cl and H-Cl

Using table 9.1,

• ΔrH (broken bonds) =

• ΔrH (formed bonds) =

• Overall ΔrH =

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Covalent Bond Energies
In general,

ΔrH = ∑ ΔrH (bonds broken) + ∑ ΔrH (bonds formed)

• When using table 9.1, all bonds formed must be converted to

negative values

• A reaction is exothermic when weaker bonds break and stronger

bonds form in their place

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Let’s work a problem
Hydrogen gas can be produced by the following reaction:

CH4 (g) + 2 H2O (g) → 4 H2 (g) + CO2 (g)

Using bond energies, calculate ΔrH for this reaction (in kJ/mol)

30
Covalent Bond Lengths
• The tabulated bond length is an average distance between two
particular atoms in a large number of compounds

• For a particular pair of atoms, triple bonds shorter than double

bonds, shorter than single bonds

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Covalent Bond Lengths
• For diatomic molecules of formula X2, bond length increases as
atoms get larger

• Not covering bond vibrations (p. 352-354) in CHEM 1000

32
Electronegativity and Bond Polarity
• In most molecules the bonding is not 100% ionic nor 100%
covalent

• Unequal sharing of electrons in a bond means one atom is slightly

positive (δ+) and the other slightly negative (δ-).

• This leads to a polar covalent bond

33
Electronegativity and Bond Polarity

• Electronegativity is a measure of an atom’s ability to attract

electron towards itself in a chemical bond

• Electronegativity values for elements have an arbitrary maximum

value of 4.0 for fluorine (the most electronegative element)

• Electronegativity values exhibit a periodic trend

34
Electronegativity and Bond Polarity
Roughly follows the
same trends as
atomic radii

Least EN atom = Fr/Cs

Most EN atom = F

35
Electronegativity and Bond Polarity
• Degree of polarity in a chemical bond depends on
electronegativity difference (ΔEN) between the two atoms
• Values given below are a rough guide, there are no “firm
boundaries”

• Not covering dipole moment / percent ionic calculations

36
Resonance Structures
• When drawing the Lewis structure for ozone (O3) there are two possible
“equally correct” structures in which every atom has a full octet:

• Experiments show O3 exists as an “averaged structure” of these two Lewis

structures

• These are the resonance (canonical) structures of ozone

37
Resonance Structures
• Ozone does not rapidly transform from one resonance structure to another

• Ozone always exists as a resonance hybrid which has characteristics of

both structures

38
Resonance Structures
• Resonance structures only differ in the placement of their valence electrons
on paper

• Resonance hybrids demonstrate electron delocalization throughout the

molecule – very important for organic chemistry (CHEM 2020)!

39
Resonance Structures
• In CHEM 1000, be on the lookout for multiple possible structures that can be
drawn when creating double/triple bonds to achieve full octets
Example: Draw a valid Lewis structure for NO3- and include two additional
resonance structures

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Resonance Structures

41
Formal Charge
• A semi-fictitious charge assigned to atoms in a Lewis structure
• Assumes 100% equal sharing of electrons in covalent bonds, even with
differences in electronegativity
• All formal charges must sum to the overall charge on the molecule/ion

Formal charge = # of valence electrons in atom – (number of nonbonding

electrons + ½ number of bonding electrons)

Example: formal charges in HF molecule

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Formal Charge
• Formal charges are useful for comparing resonance structures to determine
which one is “most important” to the overall resonance hybrid

When comparing competing resonance structures…

• As many atoms should have full octets as possible

• Keep magnitudes of formal charges as small as possible
• When charges can’t be avoided, negative formal charges better reside on the
more electronegative atom

43
Formal Charge
• Consider drawing the Lewis structure for cyanate anion, OCN-
• Three potential Lewis structures, all have full octets on all atoms

• Structures A, B, C are resonance structures of cyanate

• Let’s assign formal charges to each atom in each structure

44
Polling question
Which of these three resonance structures for cyanate is the best (most
important) structure?

45
Formal Charge
• Going back to the ozone (O3) example, convince yourself that
both these resonance structures are equally important!

46
Odd Electron Species
• Consider the Lewis structure of nitric oxide (NO), 11 valence
electrons in total

• Nitrogen atom has 7 electrons around it, incomplete octet

• One electron not paired with the rest, called a free radical

• Free radicals usually more reactive molecules

47
Incomplete Octets
• For some compounds, atoms may not be able to achieve a full
octet, making them highly reactive

Example: BH3 (6 valence electrons in molecule)

48
Incomplete Octets
• Other compounds with incomplete octets may have resonance
structure(s) with full octets

Example: BF3 (24 valence electrons in molecule)

49
Hypercoordinate (Hypervalent) Compounds
• Atoms in the third row or lower on periodic table often form
compounds that seem to exceed the octet rule

Examples: AsF5 (40 valence electrons) and SF6 (48 valence electrons)

• Larger size of third (and lower) row atoms allows more groups to
be accommodated around them
50
Hypercoordinate (Hypervalent) Compounds
• Atoms contain “expanded octets” but actual bonding descriptions
are more complicated
• These compounds usually contain a large central atom with
bonded groups being much more electronegative
• Ionic resonance structures can be drawn to obey the octet rule,
but introduces charges

51
Hypercoordinate (Hypervalent) Compounds
• Another example is the Lewis structure of sulfuric acid, H2SO4

• This is one valid form in which all atoms have octets

• This is another valid form in which the octet on S has been expanded,
eliminating all formal charges

52
Tro Textbook Convention
• Which structure would we draw? Read the question carefully!

• Tro 9-71: “Draw a Lewis structure … If needed, expand the octet on the
central atom to lower the formal charge”

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