CHM 101

General Chemistry 1

Valence Forces
by

Miss Senami Anko

Department of Chemistry
Lagos State University
 Lewis Dot Symbols
• Valence electrons determine an
element’s chemistry.

• Lewis dot symbols represent the

valence electrons of an atom as
dots arranged around the atomic
symbol.

• Most useful for main-group

elements
2
Write Lewis dot symbols for the following:

(a) N

(b) S2−

(c) K+

3
Write Lewis dot symbols for the following:

•
(a) N •N
••
•

−
• 2
(b) S2− S
•
•
•
•
•••

(c) K+ +
K

4
 Ionic Bonding
• Ionic bond: Electrostatic force that
holds oppositely charge particles
together.

• Formed between cations and anions.

• Example
• ••
Na• + Cl Na++
•
•

Cl

•
•
•
•
•
• •−
• •

5
• Lattice energy = The energy required to
completely separate one mole of a solid
ionic compound into gaseous ions.

- + + -
+ -
- + - + - +
- + + -

NaCl(s) → Na+(g) + Cl−(g) ΔHlattice = +788 kJ/mol

Because they are defined as an amount of

energy, lattice energies are always positive.
6
• Coulombic
attraction:
Q1 ⋅Q2 Q = amount of charge
F∝ 2 d = distance of
d
separation
Q1
∙ ∙ Q2
d

• Lattice energy (like a coulombic force) depends

on
• Magnitude of charges
• Distance between the charges

7
 Covalent Bonding

• Atoms share electrons to form

covalent bonds.
H• + •H H H or H–H

•
•
• In forming the bond the atoms achieve
a more stable electron configuration.

8
• Octet: Eight is a “magic” number of
electrons.

• OctetRule: Atoms will gain, lose,

or share electrons to acquire eight
valence electrons
Examples:• ••
Cl• Na++
•
•

Cl

•
•
•
•
Na• + • •−
• •
• •
H• + H• + •O• HO
•
•
•
•
• • H
• •
9
•Lewis
Structures
HH H–H

•
•
H• + •H

• • •• ••
Cl• Cl•Cl Cl Cl Cl
•
•

•
•

•
•
•
•
•
•
•
•
•
•
• •• ••• •• •• •• –
•• + •• ••

Shared electrons ⇒ Bonds

Non-bonding valence electrons ⇒ Lone
pairs

10
• Multiple Bonds
- The number of shared electron pairs is the
number of bonds.
•• •• •• ••
Cl Cl Cl Cl
•
•
•
•
•
•

•
•
•
•
•• ••– Single Bond
•• ••
•• •• • •
O C O=C=O Double
•
•
•
•
•
•

•• •• • •
O Bond
• •
N N N N Triple Bond
•
•
•
•
•
•
•
•
•
•
•
•
•

11
 • Bond strength and bond
length
bond strength single < double < triple

bond length single > double > triple

N–N N=N N≡ N

Bond Strength 163 kJ/mol 418 kJ/mol 941

kJ/mol
Bond Length 1.47 Å 1.24 Å 1.10 Å

12
 Electronegativity and
Polarity
• Nonpolar covalent bond= electrons
are shared equally by two bonded
atoms
• Polar covalent bond = electrons are
shared unequally by two bonded
atoms

13
• Electronegativity: ability of an
atom to draw shared electrons to
itself.
- More electronegative elements attract electrons
more strongly.
• relative scale
• related to IE and EA
• unitless
• smallest Cs 0.7
electronegativity: F 4.0
• largest electronegativity:

14
• Dipole moments and partial charges
- Polar bonds often result in polar molecules.
- A polar molecule possesses a dipole.
- dipole moment (μ) = the quantitative measure of
a δ+ δ-
H–F dipole μ =
+Q Qr ∙ –Q
∙
r

SI unit: coulomb•meter (C• HF 1.82 D

m) common unit: debye (D) HCl 1.08 D
HBr 0.82 D
1 D = 3.34 × 10−30 HI 0.44 D
C• m 15
 Drawing Lewis Structures
1) Draw skeletal structure with the central atom
being the least electronegative element.

2) Sum the valence electrons. Add 1 electron for

each negative charge and subtract 1 electron for
each positive charge.

3) Subtract 2 electrons for each bond in the

skeletal structure.

4) Complete electron octets for atoms bonded to the

central atom except for hydrogen.

5) Place extra electrons on the central atom.

6) Add multiple bonds if atoms lack an octet.

16
 What is the Lewis structure of NO3−
?) Draw skeletal structure with
1 O

–
central atom being the least O–N–O
electronegative.
2) Sum valence electrons. Add 1 for each
negative charge and subtract 1 for each
positive charge.
24
− −
NO3 ⇒ (1 × 5) + (3 × 6) + 1 = 24 valence e
e− −
−6e

: –
Complete electron octets for :O:
3) Subtract 2 for each bond in the
atoms bonded to the central atom skeletal 18

: :
: :
except for hydrogen. :O – N –O: −
structure. 4) e
5) Place extra electrons on
the central atom. –

: –
6) Add multiple bonds if :O:
24

:
atoms lack an octet. : :
:O – N = O: −
e17
 Lewis Structures and
Formal Charge
• The electron surplus or deficit, relative to the free
atom, that is assigned to an atom in a Lewis
structure. Total Total Total
Formal valence
= electrons − non-
−
1 bonding
Charge bonding 2 electrons
electrons

: :
Example: H2O = H:O:
H
H: orig. valence e− = 1 O: orig. valence e− = 6
− non-bonding e− = −0 − non-bonding e− = −4
− 1/2 bonding e− = −1 − 1/2 bonding e− = −2
formal charge = 0 formal charge = 0
Formal charges are not “real” charges.
18
Example: Formal charges on the atoms in ozone

O = 6 − 4 − 12 (4
O OO =0 )
O = 6 − 2 − 1(6)
= +1 2

O = 6 − 6 − 1(2)
= −1 2

19
∙ Formal charge guidelines
– A Lewis structure with no formal charges is
generally better than one with formal
charges.
– Small formal charges are generally better than
large formal charges.
– Negative formal charges should be on
the more electronegative atom(s).
Example:
H

H C O H or C O ?

Answer: H
− + H
•• ••
H C O •
H C O
•
H •
31
Identify the best structure for the isocyanate ion
below:

–
(a) :C = N =
O:
−2 +1 0

:C ≡ N – O: –
(b)
−1 +1 −1

:C – N ≡ O:
(c) –
−3 +1 +1

21
Identify the best structure for the isocyanate ion
below:

–
(a) :C = N =
O:
−2 +1 0

:C ≡ N – O: –
(b)
−1 +1 −1

:C – N ≡ O:
(c) –
−3 +1 +1

22
 Resonance
• Resonance structures are used when two or
more equally valid Lewis structures can be
written
Example:. NO
2 –

:
:
: :
:O – N = O:

These two bonds are known to be

identical.
–

:
Solution
:

: :
:
:
: :

–:O = N – O:
: :O – N = O:
Two resonance structures, their average or the
resonance hybrid, best describes the nitrite
ion.
The double-headed arrow indicates resonance. 23
Additional Examples
Carbonate:
CO32−

Benzene: C6H6

or

24
 Exceptions to the Octet
Rule

• Exceptions to the octet rule fall into

three categories:
– Molecules with an incomplete octet
– Molecules with an odd number
of electrons
– Molecules with an expanded octet

25
• Incomplete Octets
Example: BF3 (boron trifluoride)
BF3 ⇒ (1 × 3) + (3 × 7) = 24 val.
e−
:

:
–

:
:
:

:
:F –:F:
B –:F:
F: :F – B = F:
+1
:
:

:
no -1
octet
– Common with Be, B and Al compounds, but
they often dimerize or polymerize.
Cl Cl Cl
Example: Be Be Be Be
Cl Cl Cl
26
• Odd Numbers of Electrons
Example: NO (nitrogen monoxide or nitric oxide)
NO ⇒ (1 × 5) + (1 × 6) = 11 valence

e− :N
0 0
.= .
−1+ 1Are these both
:N = equally
O: O: good?
Example: NO (nitrogen dioxide)
better
2

NO2 ⇒ (1 × 5) + (2 × 6) = 17 val.
−
0 0 0 0e 0 0 0 + 1 −1 −1 + 1 0
. . . .
:O = N – :O – N = O: :O = N – O: :O – N =
O: best O:
Are these all equally good?

27
• Expanded Octet
– Elements of the 3rd period and beyond have
d-orbitals that allow more than 8 valence
electrons.
:F: F

–
F
SF6 −
S 48 valence e

–
= F
(S has 12 valence
F
:F: electrons )

:
22 valence e−
:

XeF2 = :F – Xe – F:
:

:
:

(Xe has 10 valence

electrons)

28