Lecture Presentation

Chapter 8

Basic Concepts of
Chemical Bonding

James F. Kirby
Quinnipiac University
Hamden, CT
© 2015 Pearson Education
 Chemical Bonds
• Three basic types of bonds
– Ionic
• Electrostatic attraction
between ions.
– Covalent
• Sharing of electrons.
– Metallic
• Metal atoms bonded to
several other atoms.
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Bonding
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 Lewis Symbols

• G. N. Lewis developed a method to denote potential

bonding electrons by using one dot for every valence
electron around the element symbol.
• When forming compounds, atoms tend to gain, lose,
or share electrons until they are surrounded by eight
valence electrons (the octet rule). Basic Concepts
of Chemical
Bonding
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 Ionic Formation
• Atoms tend to lose (metals) or gain
(nonmetals) electrons to make them
isoelectronic to the noble gases.

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 Energetics of Ionic Bonding—
Born-Haber Cycle
• Many factors affect the
energy of ionic bonding.
• Start with the metal and
nonmetal elements:
Na(s) and Cl2(g).
• Make gaseous atoms:
Na(g) and Cl(g).
• Make ions: Na+(g) and Cl–
(g).
• Combine the ions: NaCl(s). Basic Concepts
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Bonding
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 Energetics of Ionic Bonding
• We already discussed making ions (ionization
energy and electron affinity).
• It takes energy to convert the elements to atoms.
(endothermic)
• It takes energy to create a cation (endothermic).
• Energy is released by making the anion
(exothermic).
• The formation of the solid releases a huge amount
of energy (exothermic).
• This makes the formation of salts from the
elements exothermic. Basic Concepts
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 Lattice Energy
• That huge, exothermic transition is the reverse
of the lattice energy,
– the energy required to completely separate a mole
of a solid ionic compound into its gaseous ions.
• The energy associated with electrostatic
interactions is governed by Coulomb’s law:
Q1Q2
Eel = 
d
Basic Concepts
of Chemical
Bonding
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 Lattice Energy
• Lattice energy increases with:
– increasing charge on the ions
– decreasing size of ions

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 Covalent Bonding
• In covalent bonds, atoms
share electrons.
• There are several electrostatic
interactions in these bonds:
– attractions between electrons
and nuclei,
– repulsions between electrons,
and
– repulsions between nuclei.
• For a bond to form, the
attractions must be greater
than the repulsions. Basic Concepts
of Chemical
Bonding
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 Lewis Structures
• Sharing electrons to make covalent bonds can be
demonstrated using Lewis structures.
• We start by trying to give each atom the same
number of electrons as the nearest noble gas by
sharing electrons.
• The simplest examples are for hydrogen, H 2, and
chlorine, Cl2, shown below.

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 Electrons on Lewis Structures
• Lone pairs (lp): electrons located on
only one atom in a Lewis structure.
They are represented by two dots
clearly seperated from other electrons.
• Bonding pairs(bp): shared electrons in
a Lewis structure; they can be
represented by two dots or one line.

Basic Concepts
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 Multiple Bonds
• Some atoms share only one pair of electrons.
These bonds are called single bonds.
• Sometimes, two pairs need to be shared. These
are called double bonds.
• There are even cases where three bonds are
shared between two atoms. These are called
triple bonds.

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 Polar Covalent Bonds
• The electrons in a covalent bond are not always
shared equally.
• Fluorine pulls harder on the electrons it shares
with hydrogen than hydrogen does.
• Therefore, the fluorine end of the molecule has
more electron density than the hydrogen end.

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 Electronegativity
• Electronegativity is the ability of an atom in a
molecule to attract bonding electrons to itself.
• On the periodic table, electronegativity generally
increases as you go
– from left to right across a period.
– from the bottom to the top of a group.

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Bonding
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 Electronegativity and
Polar Covalent Bonds
• When two atoms share electrons unequally, a
polar covalent bond results.
• Electrons tend to spend more time around the
more electronegative atom. The result is a
partial negative charge (not a complete transfer
of charge). It is represented by δ–.
• The other atom is “more positive,” or δ+.

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 Polar Covalent Bonds
The greater the
difference in
electronegativity,
the more polar is
the bond.

Basic Concepts
of Chemical
Bonding
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 EXERCISE

Pr. Ex. 8.4/2) Which of the following bonds is the most polar:
S Cl, S  Br, Se Cl or Se  Br?

Basic Concepts
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 Dipoles
• When two equal, but
opposite charges are
separated by a distance, a
dipole forms.
• A dipole moment, ,
produced by two equal but
opposite charges separated
by a distance, r, is
calculated:
 = Qr
• It is measured in debyes (D). Basic Concepts
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Bonding
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Is a Compound Ionic or Covalent?
• Simplest approach: Metal + nonmetal is ionic;
nonmetal + nonmetal is covalent.
• There are many exceptions: It doesn’t take into
account oxidation number of a metal (higher
oxidation numbers can give covalent bonding).
• Electronegativity difference can be used; the table
still doesn’t take into account oxidation number.
• Properties of compounds are often best: Lower
melting points mean covalent bonding, for
example. Basic Concepts
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 Writing Lewis Structures
(Covalent Molecules)
1. Sum the valence

PCl3 electrons from all

atoms, taking into
account overall
charge.
– If it is an anion, add
one electron for each
negative charge.
Keep track of the electrons: – If it is a cation,
subtract one electron
Basic Concepts

5 + 3(7) = 26 for each positive ofBonding

Chemical

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 Writing Lewis Structures

2. Write the symbols for

the atoms, show
which atoms are
attached to which,
and connect them
with a single bond (a
line representing two
Keep track of the electrons: electrons).
Basic Concepts

26 − 6 = 20 of Chemical
Bonding
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 Writing Lewis Structures

3. Complete the
octets around all
atoms bonded to
the central atom.

Keep track of the electrons:

Basic Concepts

26 − 6 = 20; 20 − 18 = 2 of Chemical
Bonding
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 Writing Lewis Structures

4. Place any leftover

electrons on the
central atom.

Keep track of the electrons:

Basic Concepts

26 − 6 = 20; 20 − 18 = 2; 2 − 2 = 0 of Chemical
Bonding
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 Writing Lewis Structures
5. If there are not enough electrons to give the
central atom an octet, try multiple bonds.

Basic Concepts
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Bonding
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 EXERCISE

Pr. Ex. 8.7/2) Draw the Lewis structure for (a) NO+ and
(b) CH4

Pr. Ex. 8.8/2) Draw the Lewis structure for (a) ClO2- and
(b) PO43-

Pr. Ex. 8.6/1,2) Draw the Lewis structure for CH2Cl2 and CO2.

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 Exceptions to the Octet Rule
• There are three types of ions or
molecules that do not follow the
octet rule:
– ions or molecules with an odd number of
electrons,
– ions or molecules with less than an octet,
– ions or molecules with more than eight
valence electrons (an expanded octet).

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 Odd Number of Electrons

Though relatively rare and usually quite

unstable and reactive, there are ions and
molecules with an odd number of electrons.

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 Fewer Than Eight Electrons
• Elements in the second period before carbon can
make stable compounds with fewer than eight
electrons.
• Consider BF3:
– 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.

Basic Concepts
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Bonding
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 Fewer Than Eight Electrons
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.

Basic Concepts
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Bonding
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 More Than Eight Electrons
• When an element is in period 3 or below in the
periodic table (e.g., periods 3, 4, 5, etc.), it can use
d-orbitals to make more than four bonds.
• Examples: PF5 and phosphate below
(Note: Phosphate will actually have four resonance
structures with five bonds on the P atom!)

Basic Concepts
of Chemical
Bonding
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 EXERCISE

Ex: Draw the Lewis structures for I3-and ICl4- .

Basic Concepts
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Bonding
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 Covalent Bond Strength
• Most simply, the strength of a bond is
measured by determining how much energy
is required to break the bond.
• This is called the bond enthalpy.
• The bond enthalpy for a Cl—Cl bond, D(Cl
— Cl), is measured to be 242 kJ/mol.
• We write out reactions for breaking one
mole of those bonds:
– Cl—Cl → 2 Cl•
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 Average Bond Enthalpies
• Average bond
enthalpies are positive,
because bond breaking
is an endothermic
process.
• Note that these are
averages over many
different compounds;
not every bond in
nature for a pair of
atoms has exactly the Basic Concepts
of Chemical
same bond energy. Bonding
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 Using Bond Enthalpies to Estimate
Enthalpy of Reaction
• One way to estimate H
for a reaction is to use the
bond enthalpies of bonds
broken and the new
bonds formed.
• Energy is added to break
bonds and released when
making bonds.
• In other words, Hrxn = (bond enthalpies of
all bonds broken) − (bond enthalpies of all Basic Concepts
bonds formed). of Chemical
Bonding
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 Example

From the figure on the last slide

CH4(g) + Cl2(g)  CH3Cl(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.

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 Answer

H = [D(C—H) + D(Cl—Cl)] − [D(C—Cl) +

D(H—Cl)]
= [(413 kJ) + (242 kJ)] − [(328 kJ) + (431 kJ)]
= (655 kJ) − (759 kJ)
= −104 kJ

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 Bond Enthalpy and Bond Length
• We can also measure an average bond
length for different bond types.
• As the number of bonds between two atoms
increases, the bond length decreases.

Basic Concepts
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Bonding
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END OF THE CHAPTER EXERCISES:

Chapter 8: 15, 17-20, 36, 38, 39, 41, 42, 47, 48, 49, 51, 53,
63, 69, 90

Basic Concepts
of Chemical
Bonding
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