8/7/19

Chapter 8
Basic Concepts of Chemical Bonding 8.1 Chemical Bonds, Lewis Symbols,
& the Octet Rule

3 General Types of Bonds Lewis Symbols

Ionic • A simple way to show valence
• Electrostatic attraction between ions electrons in an atom
• Typically M + NM
Covalent
• Sharing of electrons • Also used to show bond formation:
• Typically NM + NM
Metallic
• “Sea of electrons”
• Example: Show the bonding between Ca and Br
• Electrons are delocalized (not
associated with a particular atom) and
free to move

Practice Problem 1 The Octet Rule

#15 a, b, & d Predict the chemical formula of the ionic • Atoms gain, lose, or share electrons until they are
compound formed between the following pairs of surrounded by 8 VE.
elements:
a) Al and F • All noble gases (except He) have 8 VE

b) K and S
• An octet consists of full s and p subshells.
d) Mg and N
• There are exceptions to this rule

1
 8/7/19

Energetics of Ionic Bond Formation

Consider the formation of NaCl:

• The 1st IE of sodium is 495 kJ/mol

(it takes 495 kJ/mol to remove an e- from Na, making Na+)

• The EA of chlorine is -349 kJ/mol

8.2 Ionic Bonding (we get 349 kJ/mol back by giving an e- to Cl, making Cl-)

• But these numbers don’t explain why the

reaction of sodium metal and chlorine gas to
form sodium chloride is so exothermic…

There must be a 3rd piece to the puzzle…. Lattice Energy

The energy required to completely separate a
○ What is as yet unaccounted for is the mole of a solid ionic compound into its gaseous
electrostatic attraction between the newly- ions.
formed sodium cation and chloride anion. MX(s) à M +(g) + X-(g)

○ This 3rd piece of the puzzle is called “lattice

energy”.

• The energy associated with electrostatic Which has the greater lattice energy? Explain.
interactions is represented by a modified form of
Coulomb’s Law: æQQ ö
Lattice Energy = k ç 1 2 ÷
æQQ ö è r ø
Lattice Energy = k ç 1 2 ÷
è r ø
○ k = proportionality constant
○ Q1 and Q2 = charges of the ions
○ r = shortest distance between the centers of the ions

• Lattice energy increases as the charge of the ions

increases.
• Lattice energy increases as the distance between
the two ions decreases.

2
 8/7/19

Practice Problem 2 Energetics of Ionic Bonding

Which compound in each of the following pairs of ionic • Lattice energy also helps
substances has the greatest lattice energy? Justify your answers.
explain the “octet rule.”
a) NaCl or KCl

b) LiF or LiCl • Metals, for instance, tend

to stop losing electrons
c) Mg(OH)2 or MgO
once they attain a noble
d) Fe(OH)2 or Fe(OH)3 gas configuration because
energy would be
e) NaCl or Na2O
expended that cannot be
f) MgO or BaS overcome by lattice
energies.

Practice Problem 3 Practice Problem 4

#20 NaCl and KF have the same crystal structure. The only #21 The ionic substances KF, CaO, and ScN are
difference between the two is the distance that separates isoelectronic (they have the same number of electrons).
cations and anions.
Examine the lattice energies for these substances and
account for the trends you observe.
a) The lattice energies of NaCl and KF are 788 kJ/mol and 808
kJ/mol, respectively. Based on lattice energies, would you Compound Lattice Energy (kJ/mol)

expect the Na-Cl or the K-F distance to be longer? KF 808

CaO 3414
Ion Radius (Å )
ScN 7547
b) Use the ionic radii to estimate the Na+ 1.16
Na-Cl and K-F distances. Does this K+ 1.52
estimate agree with the prediction Cl- 1.67
you made based upon the lattice energies? F- 1.19

Practice Problem 5 Practice Problem 6

#22 b) Using a periodic table, arrange the following #24 Explain the following trends in lattice energy:
substances according to their expected lattice a) CaF2 > BaF2
energies, listing them from lowest lattice energy to
the highest: ScN, KBr, MgO, NaF. Compare your list b) NaCl > RbBr > CsBr
with the data in table 8.2. c) BaO > KF

3
 8/7/19

• In covalent bonds atoms

share electrons.

• There are several

electrostatic interactions in
these bonds:
8.3 Covalent Bonding ○ Attractions between electrons
and nuclei
○ Repulsions between electrons
○ Repulsions between nuclei
Crash Course: Bonding

Why Atoms Form Covalent Bonds Lewis Structures

Why would like atoms come together? Is there a
Representations of molecules showing all electrons,
bonding force between them?
bonding and nonbonding.

Practice Problem 7:
Use Lewis symbols and Lewis structures to diagram the
formation of PF3 from P and F atoms.
• A bond will form if a system can lower its total energy
• p-p and e-e repulsions are not favorable
• p-e attractions are favorable
• System seeks to minimize the repulsions and maximize the
attractions (lowest energy)

Multiple Bonds Multiple Bonds

Bond Strength / Bond “Bond
• In a multiple bond, the electron density between Bond Energy Length Order”

the two nuclei increases. • Single 1

SMALLER BOND
WEAKER /

ENERGY

LONGER BOND

○ 2 shared e-
• Because of this, the nuclear repulsions decrease
and the nucleus-electron attractions increase. • Double 2
4 shared e-
LARGER BOND

○
STRONGER /

SHORTER BOND
ENERGY

• The nuclei move closer together and the bond

length is shorter. • Triple 3
○ 6 shared e-

4
 8/7/19

Though atoms often form compounds by sharing

electrons, the electrons are not always shared
equally.

Non-Polar Covalent Bonds

○ Electrons shared equally
○ Ex: F2

8.4 Bond Polarity & Electronegativity Polar Covalent Bonds

○ Unequal sharing of electrons
○ Ex: HF
o F is much more electronegative than H,
so there is more electron density around F

Electronegativity Polarity of the Hydrogen Halides

• The ability of an Greater the EN difference, the more polar the bond
atom in a molecule
to attract electrons
to itself.
• Generally,
electronegativity
increases as you
go…
○ …across a row.
○ …up a family.

Bond Polarity and Dipole Moments Electronegativity and Bond Type

Molecules with a center of positive charge and a center
of negative charge are said to have a dipole moment All polar bonds have some ionic
(Use arrows to represent) character, and the difference
between ionic and covalent bonding
Molecules with dipole
is not distinct but rather a continuum.
moments will align
themselves with an

Rough Guidelines:
electric field (see
figure b)

n 0-0.5 = non-polar covalent

(little to no difference in EN)—not very common
Polar bonds don’t always mean polar molecules: n 0.6-1.9 = polar covalent
(moderate difference in EN)—very common
n >2.0 = ionic
(large difference in EN—no sharing at all)
Crash Course: Bond Polarity

5
 8/7/19

The difference in electronegativity is not the only Practice Problem 8

factor in determining if a bond should be Without using electronegativity values, predict the order of
designated as ionic or covalent. increasing electronegativity in each of the following groups of
elements.

Generally, bonds between a metal and nonmetal a) C, N, O

are ionic, and bonds between two nonmetals are
covalent. b) S, Se, Cl

c) Si, Ge, Sn
Examination of the properties of a compound is
the best way to characterize the type of bonding. d) Tl, S, Ge

Practice Problem 9 Practice Problem 10

Without using electronegativity values, predict which #38 By referring only to the periodic table, select
bond in each of the following groups will be the most
polar.
a) The most electronegative element in group 6A
a) C-F, Si-F, Ge-F b) The least electronegative element in the group Al,
Si, P
b) P-Cl or S-Cl c) The most electronegative element in the group Ga,
P, Cl, Na
c) S-F, S-Cl, S-Br
d) The element in the group K, C, Zn, F that is most
likely to form an ionic compound with Ba.
d) Ti-Cl, Si-Cl, Ge-Cl

Steps for writing Lewis structures

1. Find the sum of valence electrons of all
atoms in the polyatomic ion or molecule.
○ If it is an anion, add one electron for each negative
charge.
○ If it is a cation, subtract one electron for each positive
charge.

8.5 Drawing Lewis Structures PCl3

5 + 3(7) = 26

6
 8/7/19

2. Choose the central atom. The central atom is the 4. Fill the octet of the central atom.
least electronegative element that isn’t hydrogen.
Connect the outer atoms to it by single bonds.

5. If you run out of electrons before the central atom

has an octet…
3. Fill the octets of the outer atoms.

…form multiple bonds until it does.

Practice Problem 11 So what if there are multiple valid ways to draw the
Lewis structure?
#46 Write Lewis structures for the following:
Use Formal Charge
a) H 2CO (both H atoms are bonded to C)
To calculate:
b) H 2O 2 ■ All unshared electrons are assigned to the atom on which
they are found.
c) C2F6 (contains a C-C bond) ■ For any bond—single, double, or triple—half of the
bonding electrons are assigned to each atom in the bond.
d) AsO 33- ■ Subtract the # of electrons assigned to that atom from
the # of VE in the individual atom.
e) H 2SO 3 (H is bonded to O)
f) C2H 2

Practice Problem 12
The best Lewis structure:
Write all possible Lewis structures for O2F2. Assign
○ is the one with the fewest / lowest charges.
formal charges to the atoms. Choose the best Lewis
○ puts a negative charge on the most electronegative atom. structure.

Note: The sum of the formal charges must equal the net charge!

7
 8/7/19

Practice Problem 13
#87 Although I3- is known, F3- is not. Using Lewis
structures, explain why F3- does not form.

8.6 Resonance Structures

Resonance Structures • One Lewis structure cannot

accurately represent a molecule
• This is the Lewis structure like ozone.
we would draw for ozone, • We “refine” the Lewis structure by
O 3: using resonance structures to
describe these types of molecules.

• But this structure is at odds

with experimental data that
shows both O-O bonds are
identical in length (and
Just as green is a synthesis of blue and yellow,
strength). ozone is a synthesis of these two Lewis
structures.

Practice Problem 14 Practice Problem 15

#48 Write a Lewis structure for PF3. Is the octet rule #52 Consider the nitryl cation, NO2+. Write one or more
satisfied for all the atoms in your structure? appropriate Lewis structures. Are resonance
Determine the formal charges of the P and F atoms. structures needed to describe the structure? With
what familiar molecule is it isoelectronic?

8
 8/7/19

Practice Problem 16
#53 Predict the ordering of the C-O bond lengths in CO,
CO2, and CO32-.

8.7 Exceptions to the Octet Rule

Exceptions to the Octet Rule Practice Problem 17

• Ions or molecules with an odd number of SF6, ClF5, and XeF4 are three compounds whose central
electrons atoms do not follow the octet rule. Draw Lewis
structures for these compounds.

• Ions or molecules with less than an octet:

H, B, Be

• Ions or molecules with more than eight valence

electrons (an expanded octet)
o Elements with d orbitals available (periods 3-7)

Less Than an Octet • Therefore, structures that put a double bond between boron
and fluorine are much less important than the one that leaves
Consider BF3: boron with only 6 valence electrons.
○ Giving boron a filled octet places a negative
charge on the boron and a positive charge on
fluorine.
○ This would not be an accurate picture of the
distribution of electrons in BF3.

• The lesson is: if filling the octet of the central atom results in a
negative charge on the central atom and a positive charge on
the more electronegative outer atom, don’t fill the octet of the
central atom.

9
 8/7/19

More Than an Octet Practice Problem 18

• Even though we can draw a Lewis structure for the
phosphate ion that has only 8 electrons around the central
#64 a) Describe the molecule chlorine dioxide, ClO2,
phosphorus, the better structure puts a double bond using three possible resonance structures. b) Do any
between the phosphorus and one of the oxygens. of these resonance structures satisfy the octet rule
for every atom in the molecule? Why or why not? c)
Using formal charges, select the resonance
structure(s) that is (are) the most important.

• This eliminates the charge on the phosphorus and the charge

on one of the oxygens.
• The lesson is: when the central atom in on the 3rd row or
below and expanding its octet eliminates some formal
charges, do so.

• Most simply, the strength of a bond is measured

by determining how much energy is required to
break the bond.
• This is the bond enthalpy (or bond energy).
• The bond enthalpy for a Cl-Cl bond, D(Cl-Cl), is
measured to be 242 kJ/mol.
• Bond enthalpies are positive b/c breaking bonds is
8.8 Strengths of Covalent Bonds endothermic.

Bond Enthalpies Enthalpy of Reaction

• Bond energies can be used to calculate
approximate enthalpies of reaction.
Note:
These are average
bond enthalpies, not • Breaking bonds is endothermic, so use + energy
absolute bond
enthalpies; the C-H values
bonds in methane,
CH 4, will be a bit
different than the
C-H bond in
chloroform, CHCl3
• Forming bonds is exothermic, so use – energy
values

ΔH = ΣD(bonds broken)-ΣD(bonds formed)

D = bond energy/mol

10
 8/7/19

Example: Using Bond Enthalpies to Estimate Bond Enthalpy and Bond Length
Enthalpy of Reaction
CH 4 (g) + Cl2 (g) ¾¾® CH 3Cl (g) + HCl (g)

In this example, one C-H bond and one Cl-Cl bond are broken;
one C-Cl and one H-Cl bond are formed.

So, DH = [D(C-H) + D(Cl-Cl)] - [D(C-Cl) + D(H-Cl)]

= [(413 kJ) + (242 kJ)] - [(328 kJ) + (431 kJ)] • We can also measure an average bond length for
different bond types.
= (655 kJ) - (759 kJ)
• As the number of bonds between two atoms
= -104 kJ increases, the bond length decreases.

Practice Problem 19
#70 a) Use bond enthalpies to estimate the
enthalpy change for the reaction of hydrogen
with ethene:
H 2(g) + C2H 4(g) à C2H 6(g)

b) Calculate the standard enthalpy change for this

reaction, using heats of formation. Why does
this value differ from that calculated in a)?

11