Chapter 5

Basic Concepts of Chemical Bonding
1
Types of Bonds
Chemical Bond – a strong attraction between atoms
Ionic Bond – an electrostatic interaction where one atom
donates an electron to the other
Covalent Bond – atoms share electrons
Metallic Bond – atoms bonded to several others and
electrons can move freely.
2
Types of Bonding
3
• In a Lewis structure, we represent the valence electrons of
main-group elements as dots surrounding the symbol for the
element – aka electron dot structures
• the symbol of the element is used to represent the nucleus
and inner electrons
• dots around the symbol represent valence electrons
• first four dots are for the two s orbital electrons and two p
orbital electrons, the final three dots represent paired p
orbital electrons
Lewis Structures of Atoms
• Li • Be • •
B



C




N





O






F







Ne







4
5
Lewis Dot Symbols
Ionic Bonding
• lattice energy is a measure of stabilization
• lattice energy – the energy required to completely separate
1 mol of solid ionic components into its gaseous ions.
• NaCl (s)  Na
+
(g) + Cl

(g) DH = +788kJ/mol
• the reverse
• Na
+
(g) + Cl

(g)  NaCl (s) DH = –788kJ/mol
ionic substances are brittle, crystalline, with high melting points

Na

Cl






+
[Ne] 3s
1
[Ne] 3s
2
3p
5
Na
+

Cl







–1
[Ne]

[Ar]

6
7
Ionic Bonding
• The magnitude of the lattice energy of an ionic solid
depends on the charges of the ions, their sizes, and their
arrangement in the solid.
• The potential energy of two interacting charges is given by
Eel =
k Q
1
Q
2
d

k = 8.99 x 10
9
J-m

C
2
Q
1
Q
2
= are the charges on atom 1 and atom 2, d is the distance
between them, and
The Crystal Structure of Sodium Chloride
8
Lattice Energy Diagram for Sodium Chloride
lattice energy
Born – Haber
Cycle
9
5.2
10
Covalent Bonding
most substances have covalent type bonding – which means
they share electrons.
• Electrons that are shared by atoms are called bonding pairs
• Electrons that are not shared by atoms but belong to a
particular atom are called lone pairs – aka nonbonding
pairs
.
.
. .
O S O .
.
.
.
.
.
.
.
. . . .
. .
Bonding pairs
Lone pairs
11
Electronegativity
• electronegativity – the ability of an atom in a
molecule to attract electron density toward itself
increase
increase
12
• follows electron affinity
Electronegativities of the Elements
13
Electronegativity Difference and Bond Type
• pure covalent - electronegativity between bonded atoms is
0 – equal sharing
―100%‖
0 0.4 2.0 4.0
4% 51%
Percent Ionic Character
Electronegativity Difference
• nonpolar covalent – electronegativity between bonded
atoms is 0.1 to 0.4
• polar covalent – electronegativity between bonded atoms is
0.5 to 1.9
• ionic – electronegativity between bonded atoms is larger
than or equal to 2.0
14
14
Polar Covalent Bonds
• Though atoms often form compounds by sharing electrons,
the electrons 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.
15
• When two atoms share electrons unequally, a bond dipole
results.
• The dipole moment, , produced by two equal but
opposite charges separated by a distance, r, is calculated:
• It is measured in debyes (D).
Polar Covalent Bonds
 = Qr
16
The greater the difference in electronegativity, the more polar is
the bond.
Polar Covalent Bonds
17
Lewis Structures
Lewis structures are representations of molecules showing
all electrons, bonding and nonbonding.
18
Lewis Structures
2. Determine the central atom
3. Write symbols for the atoms and show which atoms are
attached to each other and connect them with a single bond (a
dash representing two atoms) – subtract from total (2 per dash)
4. Complete octet around all the atoms bonded to the central atom
Subtract from the total
5. Place any leftover electrons around the central atom.
6. for any atom lacking an octet form double or triple bonds
1. Sum valence electrons from all atoms – add or subtract e

’s
for charge
19
Writing Lewis Structures
1. Find the sum of valence electrons of all atoms in the
polyatomic ion or molecule.
PCl
3

Keep track of the electrons:

5 + 3(7) = 26
• If it is an anion, add one electron for each negative charge.
• If it is a cation, subtract one electron for each positive
charge.
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2. The central atom is the least electronegative element that
isn’t hydrogen. Connect the outer atoms to it by single
bonds.
Keep track of the electrons:
P
Cl
Cl
Cl
26 − 6 = 20
1


=
Writing Lewis Structures
21
3. Fill the octets of the outer atoms.
Keep track of the electrons:

26 − 6 = 20; 20 − 18 = 2
Writing Lewis Structures
22
4. Put left over electrons around the central atom.
Keep track of the electrons:

26 − 6 = 20; 20 − 18 = 2 place extra e

around central atom;
2 − 2 = 0
Writing Lewis Structures
23
5. If you run out of electrons before the central atom has
an octet form multiple bonds until it does.
Writing Lewis Structures
24
• To determine the best Lewis structure assign formal
charges.
• For each atom, count the electrons in lone pairs and half the electrons
it shares with other atoms.
• Subtract that from the number of valence electrons for that atom: the
difference is its formal charge.
Writing Lewis Structures
25
• The best Lewis structure is the one with the fewest
charges.
• It is best to put a negative charge on the most
electronegative atom.

Writing Lewis Structures
26
Resonance
This is the best Lewis structure that can be drawn for ozone,
O
3
.
27
Resonance
• But this is at odds with the true, observed structure of
ozone.
• both O—O bonds are the same length.
• both outer oxygens have a charge of −1/2.
28
Resonance
• One Lewis structure cannot accurately depict a molecule
like ozone.
• We use multiple structures, resonance structures, to
describe the molecule.
29
Resonance
Just as green is a synthesis of blue
and yellow…
…ozone is a synthesis of these two
resonance structures.
30
Resonance
• In truth, the electrons that form the second C—O bond in
the double bonds below do not always sit between that C
and that O, but rather can move among the two oxygens
and the carbon.
• They are not localized; they are delocalized.
31
Resonance
• The organic compound benzene, C
6
H
6
, has two resonance
structures.
• It is commonly depicted as a hexagon with a circle inside
to signify the delocalized electrons in the ring.
32
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).
33
Odd Number of Electrons
Though relatively rare and usually quite unstable and
reactive, there are ions and molecules with an odd number
of electrons.
34
• Consider BF
3
:
• 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 BF
3
.
35
Fewer Than Eight Electrons
• Therefore, structures that put a double bond between boron
and fluorine are much less reasonable than the one that
leaves boron with only 6 valence electrons.
36
More Than Eight Electrons
• The only way PCl
5
can exist is if phosphorus has 10
electrons around it.
• It is allowed to expand the octet of atoms on the third row
or below. Presumably d orbitals in these atoms participate
in bonding.
• The octet rule works really well for C, N, O, and F. Atoms
after period 2 may or may not have an octet.
37
Even though we can draw a Lewis structure for the phosphate
ion that has only 8 electrons around the central phosphorus,
the better structure puts a double bond between the
phosphorus and one of the oxygens.
More Than Eight Electrons
38
• This eliminates the charge on the phosphorus and the charge
on one of the oxygens.
More Than Eight Electrons
• The lesson is: When the central atom is on the third row or
below and expanding its octet eliminates some formal
charges, do so.
39
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 the bond enthalpy.
• The bond enthalpy for a Cl—Cl bond, D(Cl— Cl), is
measured to be 242 kJ/mol.
40
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