Chemical Bonding I:
Basic Concepts
Chapter 9
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Valence electrons are the outer shell electrons of an
atom. The valence electrons are the electrons that
particpate in chemical bonding.
Group
e- configuration
# of valence e-
1A
ns1
2A
ns2
3A
ns2np1
4A
ns2np2
5A
ns2np3
6A
ns2np4
7A
ns2np5
7
9.1
Lewis Dot Symbols for the Representative Elements &
Noble Gases
9.1
The Ionic Bond
Li + F
1s22s11s22s22p5
e +
Li+ +
Li+ F [He]
1s
1s2[2Ne]
2s22p6
Li
Li+ + e-
F -
F -
Li+ F -
9.2
Electrostatic (Lattice) Energy
Lattice energy (E) is the energy required to completely separate
one mole of a solid ionic compound into gaseous ions.
E = k Q+Qr
Q+ is the charge on the cation
Q- is the charge on the anion
r is the distance between the ions
Lattice energy (E) increases
as Q increases and/or
as r decreases.
cmpd
MgF2
MgO
LiF
LiCl
lattice energy
2957 Q= +2,-1
3938 Q= +2,-2
1036
r F- < r Cl853
9.3
Born-Haber Cycle for Determining Lattice Energy
o
Hoverall
= H1o+ H2o+ H3o+ H4o+ H5 o
9.3
9.3
Chemistry In Action:
Sodium Chloride
Mining Salt
Solar Evaporation for Salt
A covalent bond is a chemical bond in which two or more
electrons are shared by two atoms.
Why should two atoms share electrons?
F
7e-
F F
7e-
8e- 8e-
Lewis structure of F2
single covalent bond
lone pairs
F F
lone pairs
lone pairs
lone pairs
single covalent bond
9.4
Lewis structure of water
H
O +
single covalent bonds
H O H
or
2e-8e-2eDouble bond two atoms share two pairs of electrons
O C O
or
double bonds
8e- 8ebonds
8edouble
Triple bond two atoms share three pairs of electrons
N N
triple
bond
8e-8e
or
triple bond
9.4
Lengths of Covalent Bonds
Bond Lengths
Triple bond < Double Bond < Single Bond
9.4
9.4
Polar covalent bond or polar bond is a covalent bond
with greater electron density around one of the two
atoms
electron poor
region
electron rich
region
e- poor
H
+
e- rich
F
-
9.5
Electronegativity is the ability of an atom to attract
toward itself the electrons in a chemical bond.
Electron Affinity - measurable, Cl is highest
X (g) + e-
X-(g)
Electronegativity - relative, F is highest
9.5
The Electronegativities of Common Elements
9.5
Variation of Electronegativity with Atomic Number
9.5
Classification of bonds by difference in electronegativity
Difference
Bond Type
Covalent
2
0 < and <2
Ionic
Polar Covalent
Increasing difference in electronegativity
Covalent
Polar Covalent
share e-
partial transfer of e-
Ionic
transfer e9.5
Classify the following bonds as ionic, polar covalent,
or covalent: The bond in CsCl; the bond in H2S; and
the NN bond in H2NNH2.
Cs 0.7
Cl 3.0
3.0 0.7 = 2.3
Ionic
H 2.1
S 2.5
2.5 2.1 = 0.4
Polar Covalent
N 3.0
N 3.0
3.0 3.0 = 0
Covalent
9.5
Writing Lewis Structures
1. Draw skeletal structure of compound showing
what atoms are bonded to each other. Put least
electronegative element in the center.
2. Count total number of valence e-. Add 1 for
each negative charge. Subtract 1 for each
positive charge.
3. Complete an octet for all atoms except
hydrogen
4. If structure contains too many electrons, form
double and triple bonds on central atom as
needed.
9.6
Write the Lewis structure of nitrogen trifluoride (NF3).
Step 1 N is less electronegative than F, put N in center
Step 2 Count valence electrons N - 5 (2s22p3) and F - 7 (2s22p5)
5 + (3 x 7) = 26 valence electrons
Step 3 Draw single bonds between N and F atoms and complete
octets on N and F atoms.
Step 4 - Check, are # of e- in structure equal to number of valence e- ?
3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons
F
9.6
Write the Lewis structure of the carbonate ion (CO 32-).
Step 1 C is less electronegative than O, put C in center
Step 2 Count valence electrons C - 4 (2s22p2) and O - 6 (2s22p4)
-2 charge 2e4 + (3 x 6) + 2 = 24 valence electrons
Step 3 Draw single bonds between C and O atoms and complete
octet on C and O atoms.
Step 4 - Check, are # of e- in structure equal to number of valence e- ?
3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons
Step 5 - Too many electrons, form double bond and re-check # of e -
C
O
2 single bonds (2x2) = 4
1 double bond = 4
8 lone pairs (8x2) = 16
Total = 24
9.6
Two possible skeletal structures of formaldehyde (CH2O)
H
An atoms formal charge is the difference between the
number of valence electrons in an isolated atom and the
number of electrons assigned to that atom in a Lewis
structure.
formal charge
on an atom in
a Lewis
structure
total number
of valence
electrons in
the free atom
total number
of nonbonding
electrons
1
2
total number
of bonding
electrons
The sum of the formal charges of the atoms in a molecule
or ion must equal the charge on the molecule or ion.
9.7
-1
+1
formal charge
on an atom in
a Lewis
structure
C 4 eO 6 e2H 2x1 e12 e-
total number
of valence
electrons in
the free atom
2 single bonds (2x2) = 4
1 double bond = 4
2 lone pairs (2x2) = 4
Total = 12
total number
of nonbonding
electrons
formal charge
on C
= 4 -2 - x 6 = -1
formal charge
on O
= 6 -2 - x 6 = +1
1
2
total number
of bonding
electrons
9.7
H
H
0
C
formal charge
on an atom in
a Lewis
structure
0
O
C 4 eO 6 e2H 2x1 e12 etotal number
of valence
electrons in
the free atom
2 single bonds (2x2) = 4
1 double bond = 4
2 lone pairs (2x2) = 4
Total = 12
total number
of nonbonding
electrons
formal charge
on C
= 4 - 0 - x 8 = 0
formal charge
on O
= 6 -4 - x 4 = 0
1
2
total number
of bonding
electrons
9.7
Formal Charge and Lewis Structures
1. For neutral molecules, a Lewis structure in which there
are no formal charges is preferable to one in which
formal charges are present.
2. Lewis structures with large formal charges are less
plausible than those with small formal charges.
3. Among Lewis structures having similar distributions of
formal charges, the most plausible structure is the one in
which negative formal charges are placed on the more
electronegative atoms.
Which is the most likely Lewis structure for CH2O?
-1
+1
H
H
0
C
0
O
9.7
A resonance structure is one of two or more Lewis structures
for a single molecule that cannot be represented accurately by
only one Lewis structure.
What are the resonance structures of the
carbonate (CO32-) ion?
C
O
C
O
O
-
C
O
O
-
9.8
Exceptions to the Octet Rule
The Incomplete Octet
BeH2
BF3
B 3e3F 3x7e24e-
Be 2e2H 2x1e4e-
Be
3 single bonds (3x2) = 6
9 lone pairs (9x2) = 18
Total = 24
F
9.9
Exceptions to the Octet Rule
Odd-Electron Molecules
NO
N 5eO 6e11e-
The Expanded Octet (central atom with principal quantum number n > 2)
SF6
S 6e6F 42e48e-
S
F
6 single bonds (6x2) = 12
18 lone pairs (18x2) = 36
Total = 48
9.9
Chemistry In Action: Just Say NO
NO2- (aq) + Fe2+ (aq) + 2H+ (aq)
NO (g) + Fe3+ (aq) + H2O (l)
N2 (g) + O2 (g)
2NO (g)
The enthalpy change required to break a particular bond in one
mole of gaseous molecules is the bond energy.
Bond Energy
H0 = 436.4 kJ
H2 (g)
H (g) + H (g)
Cl2 (g)
Cl (g) + Cl (g) H0 = 242.7 kJ
HCl (g)
H (g) + Cl (g) H0 = 431.9 kJ
O2 (g)
O (g) + O (g) H0 = 498.7 kJ
N2 (g)
N (g) + N (g) H0 = 941.4 kJ
Bond Energies
Single bond < Double bond < Triple bond
9.10
Average bond energy in polyatomic molecules
H2O (g)
OH (g)
H (g) + OH (g) H0 = 502 kJ
H (g) + O (g)
H0 = 427 kJ
502 + 427
= 464 kJ
Average OH bond energy =
2
9.10
Bond Energies (BE) and Enthalpy changes in reactions
Imagine reaction proceeding by breaking all bonds in the
reactants and then using the gaseous atoms to form all the
bonds in the products.
H0 = total energy input total energy released
= BE(reactants) BE(products)
9.10
H2 (g) + Cl2 (g)
2HCl (g)
2H2 (g) + O2 (g)
2H2O (g)
9.10
Use bond energies to calculate the enthalpy change for:
H2 (g) + F2 (g)
2HF (g)
H0 = BE(reactants) BE(products)
Type of
bonds broken
Type of
bonds formed
Number of
bonds broken
Bond energy
(kJ/mol)
Energy
change (kJ)
1
1
436.4
156.9
436.4
156.9
Number of
bonds formed
Bond energy
(kJ/mol)
Energy
change (kJ)
568.2
1136.4
H0 = 436.4 + 156.9 2 x 568.2 = -543.1 kJ
9.10
