Chapter 8 Objectives and Topics

¡ Differentiate between different types of bonding, (covalent, ionic, and metallic) and
understanding properties that relate to specific types of bonds.
¡ Estimate Lattice energy for ionic compounds

¡ Estimate relative bond order, bond length, strength and energy

¡ Calculate estimates of enthalpy of reaction from bond energies
¡ Understand what properties make a compound a good fuel source

¡ Understand electronegativity and use EN values to estimate ionic character in a bond and
recognize polar bonds/molecules
¡ Generate Lewis structures for covalent molecules and ions (including oxyacids and
exceptions to the octet rule: one electron species, incomplete octets, and expanded octets)
¡ Evaluate resonance structures
¡ Determine formal charge of atoms in Lewis structures
¡ PROBLEM SET 3: all questions GRADED QUIZ 3: 4, 5, 6 GRADED QUIZ 4: 1, 2, 3, 4, 5,

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Chemical Bonding
¡ Atoms bond together to form molecules or
extended structures.
¡ Why do bonds form?
¡ electrostatic attractions:

Between cations and anions, in ionic solids

Between electrons and nuclei of neighbouring
atoms, in molecules

¡ Quantum mechanical reasons:

Good orbital overlap

Balance of bonding and antibonding interactions

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 Periodic Properties Summary

Metals Nonmetals
Few valence electrons Many valence electrons

Low IE High IE

Less negative EA More negative EA

Summary: Tend to loss electrons Summary: Tend to gain electrons

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Types of Bonds

¡ Simplified view:

¡ Metal + nonmetal Ionic

¡ Nonmetal + nonmetal Covalent
¡ Metal + metal Metallic bonds

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Types of Bonds

¡ Ionic, covalent, and metallic bonding are idealized

models of bonding. Most real substances exhibit
bonding character that is intermediate between
these extremes.1

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Ionic Bonding: metals + nonmetals
¡ electrons are transferred completely from one atom to another
¡ cations and anions, arranged to form, not molecules, but an
extended structure

¡ Consider the formation of LiF(s) or NaCl(s). Use Lewis symbols to

portray valence electrons and ensure that the octet rule is
followed.
Li F à Li F

¡ The cations and anions are held by attractive electrostatic

!!!"
forces (given by Coulomb’s law, E µ , where q1 and q2 are the
"
ion charges and d is the separation between them).
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Ionic Bonding: Lattice Energy

¡ Even though the formation of ions from the elemental metals and nonmetals requires a
large input of energy, a great deal of energy is released when these ions combine to
form the ionic solid.

¡ The lattice energy is the energy released when the gaseous ions combine to form the
ionic solid, and this is proportional to the electrostatic energy.
¡ Na+(g) + Cl–(g) ® Na+Cl–(s) DH = –770 kJ/mol

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Example
¡ Which compound has the greatest magnitude of lattice energy? NaCl, NaI, and MgO.
!! !"
Eµ "

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Physical Properties of Ionic Solids
¡ Explain how this ionic bonding model accounts for the physical properties of ionic
solids:
¡ hard and rigid: attractive electrostatic forces are very strong and extend indefinitely
¡ brittle: external force moves like charges close together creating repulsive force (see figure A
and B below)

¡ poor electrical conductors in the solid state, but good

conductors when molten or dissolved in solution:

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Covalent Bonding (overview): nonmetals + nonmetals

¡ electrons are shared between atoms (localized in the space between them)

¡ bonded atoms form a molecule

¡ Consider the hypothetical formation of HF(g). Use Lewis symbols to portray valence
electrons and ensure that the octet rule is followed.

¡ Covalent compounds typically exist as liquids or gases with low mp or bp. This is
harder to explain, because we need to consider the distinction between the strong
covalent bonds within molecules and the weak forces between molecules.

© Department of Chemistry, University of Alberta (2024) 10

Metallic Bonding: metals + metals

¡ electrons are highly delocalized and

shared by all atoms
¡ bonded atoms are held together by a
“sea of electrons” in an extended
structure
¡ Metallic compounds are typically
malleable and ductile have moderately
high mp and bp, and conduct
electricity well. Explain how this
model accounts for these properties.

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Example
¡ Describe the type of bonding
1. hypochlorous acid
2. sodium hydroxide
3. KNa2

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 Covalent Bonding

¡ In a covalent bond, what forces are involved

in the sharing of electrons? Consider the
D
hypothetical formation of an H2 molecule A
from two isolated H atoms:
B
¡ 2 H(g) ® H2(g) DH = –432 kJ/mol
A. No interaction
C
B. Greatest force - attraction of nucleus of
one atom to electron of the other atom
C. Optimal distance – balance attractive and
repulsive forces
D. Greatest forces - electron-electron and
nucleus-nucleus repulsion

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Bond Energy
¡ The bond energy (BE) of a bond A-B is the energy required to overcome the attraction of
the two atoms A and B:
¡ bond breaking:
¡ A-B(g) ® A(g) + B(g) DH = positive BE (endothermic)
¡ bond making:
¡ A(g) + B(g) ® A-B(g) DH = negative BE (exothermic)

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 Bond Energy – Multiple Bonds
¡ Besides a single covalent bond, stronger multiple bonds can also form. The bond order is
related to its length and energy.

ethane ethylene acetylene

structure

bond single double triple

bond order 1 2 3

bond length (pm) 154 134 121

bond energy (kJ/mol) 347 614 839

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Example
¡ Rank the relative bond lengths and strengths: Si–F, Si–C, Si–O.

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 Bond Energies
Average bond lengths and
energies are listed for different
bonds.

¡ In a chemical reaction,
atoms are rearranged when
bonds are broken in
reactant molecules
(absorbing energy) and
made in product molecules
(releasing energy).
¡ The net energy (or enthalpy)
change results from the
difference in bond energies:
DH°rxn = S BE(bonds broken) – S
BE(bonds formed)

© Department of Chemistry, University of Alberta (2024) 17

Example
¡ Compare the heats of combustion for methane vs. methanol. Which is a better fuel?
Combustion is when a fuel burns in the presence on O2 to provide energy. The products
are CO2(g) and H2O(g).

© Department of Chemistry, University of Alberta (2024) 18

Example
¡ Compare the heats of combustion for methane vs. methanol. Which is a better fuel?

CH4(g) + 2 O2(g) à CO2(g) + 2 H2O(g)

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Example
¡ Compare the heats of combustion for methane vs. methanol. Which is a better fuel?

CH3OH(g) + 3/2 O2(g) à CO2(g) + 2 H2O(g)

∆°𝐻 = Σ𝐵𝐸#$%&'%(' − Σ𝐵𝐸)#*"+&'

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Example
¡ What do these results suggest about the kinds of bonds that need to be present in a good
fuel (a substance that reacts with oxygen to release a lot of energy)? Weaker bonds in
reactants lead to better fuel

¡ How do fats and carbohydrates compare as fuels?

C12H22O11 (sucrose) C57H104O6 (triolein)

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 Electronegativity

¡ Most bonds are intermediate, having both ionic and covalent character. What
determines the extent of sharing of electrons?
¡ Electronegativity (EN or c): The relative ability of an atom, bonded within a molecule, to
attract shared electrons to itself.
¡ In his approach, Pauling noted that the bond energy in H–F was greater than the
average of H–H and F–F and attributed the extra stability to an electrostatic (ionic)
contribution arising from the difference in electronegativity.
¡ In a polar covalent bond, the more EN atom takes a greater share of the bonding e– and
acquires a partial negative charge (d–), whereas the less EN atom acquires a partial
positive charge (d+).
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Trends in Electronegativity
Can you make sense of the
trends?

Similar to trends in Electron

Affinity (a property of single
atoms)
Electronegativity is a property
of bonded atoms.

It is useful to remember:
F > O > Cl, N > Br > I, C, S > H

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Electronegativity Difference, ΔEN
¡ Electronegativity differences, DEN, can be related to degree of ionic vs. covalent character
in a bond.

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Example
¡ Rank the bond polarity in these substances: SCl2, PCl3, SiCl4.

© Department of Chemistry, University of Alberta (2024) 25

Dipole Moments

¡ Molecules such as HF with partial charges, d+ and d–, separated by a

distance d, possess a dipole moment, μ = dd. Molecules with dipole
moments are aligned in an electric field.

¡ Molecules with more than two atoms may or may not have an overall
dipole moment, depending on how the bond dipoles add vectorially.

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Example
¡ Draw bond dipoles and predict overall dipole moments.

¡ CO2

¡ H2O

¡ CCl4
C

¡ CHCl3 C

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Lewis Structures: Features

¡ A Lewis structure is a diagram showing the electron pairs in a molecule

¡ Only valence electrons are included

¡ For main-group elements, the number of valence electrons equals the “group number” or “group
number minus 10.” The nucleus and core electrons are represented by the symbol of the
element, and the valence electrons are represented by dots.
¡ A pair of bonding electrons (or a bond pair) between two atoms is a single covalent
bond and is shown by a line. A pair of non-bonding electrons on one atom is a lone
pair and is shown by two dots.
¡ Electrons are distributed so that atoms acquire a stable electron configuration, usually
an octet (8 e–) for most atoms (but 2 e– for H atoms). Multiple bonds (double or triple
bonds) may need to be formed.

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 CH2O
Lewis Structures: Procedure
1. Determine the total number of valence electrons.
¡ Add or subtract electrons if the molecule is an anion or a cation.
2. Determine how atoms are connected.
¡ Identify the central atom(s) and terminal atoms. The central atom is usually the least electronegative
atom.
¡ H and F are always terminal atoms, and form only one bond.
3. Draw a skeletal structure by joining atoms with single bonds.
¡ Subtract 2 electrons for each single bond.
4. Distribute the remaining electrons in pairs.
¡ First, complete octets around the terminal atoms (except H).
¡ Then, distribute the remaining electrons, if any, around the central atoms.
¡ A common mistake is to put too many electrons (in the mad rush to give every atom an octet), forgetting
that you must work with exactly the total number of valence electrons that are available (Step 1).
5. Too few electrons?
¡ Convert lone pairs from terminal atoms to form multiple bonds with central atoms (to attain octets).
© Department of Chemistry, University of Alberta (2024) 29
Formal Charge

¡ When there are several possible Lewis structures that can be drawn, we can assess which is the
“best” one (the most important contributor) by calculating formal charges. This is a bookkeeping
device for keeping track of electrons and is used to estimate the charges on the bonded atoms in a
molecule.
1. Each atom is assigned electrons which “belong” to them.
¡ Lone-pair (unshared) electrons belong entirely to the atom where they are found.
¡ Bond-pair (shared) electrons are split evenly between the bonded atoms.
2. The formal charge on an atom is the difference between the number of valence electrons in the
free atom and the number of assigned electrons in the bonded atom in the molecule:
¡ formal charge = (valence e– in free atom) – (assigned e– in bonded atom) It is not necessary to
= (valence e– in free atom) – (lone pair e– + ½ bond pair e–) “memorize” this formula.

3. For a neutral molecule, the sum of the formal charges is zero. For an ion, the sum of the formal
charges equals the charge on the ion.

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Lewis Structures: Examples
COF2 CH2CH2 CN–

total no. of electrons

skeletal structure

no. of electrons left

completed Lewis
structure

formal charges

© Department of Chemistry, University of Alberta (2024) 31

Resonance
¡ Often, more than one plausible Lewis structure can be drawn, as in ozone:

¡ The true structure is a resonance hybrid of the contributing Lewis

structures. The concept of resonance accounts for the fact that bonding
electron density can be delocalized over more than two atoms.
¡ The most important Lewis structures have:
1. complete octets
2. low formal charges
3. negative formal charges borne by more electronegative atoms
4. separated like charges

© Department of Chemistry, University of Alberta (2024) 32

Examples
NO3- NO2+ NH2CN
total no. of electrons

skeletal structure

no. of electrons left

possible Lewis
structures

and formal charges

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Exceptions to the Octet Rule
1. Odd-electron species
¡ Place unpaired e– on the least electronegative atom.
¡ Example: nitrogen dioxide, chlorine dioxide

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Exceptions to the Octet Rule (continued)

2. Incomplete octets
¡ Be, B, Al may have less than an octet.
¡ Example: BF3, AlCl3

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Exceptions to the Octet Rule (continued)

3. Expanded valence shells

¡ 3rd-period (or heavier) elements may have 10 or 12
electrons around them.
¡ Examples: ClF3, SO42-, H2SO4

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Formal Charge & Oxidation Number
¡ What is the difference between formal charge and oxidation number? Consider CN–.

formal charge oxidation number

Calculated by assuming electrons in bond are Calculated by assuming electrons in bond are
shared evenly associated with more electronegative atom

Corresponds to covalent extreme (electrons Corresponds to ionic extreme (electrons not

shared 50/50) shared)

© Department of Chemistry, University of Alberta (2024) 37