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Octet Rule
Octet Rule
Cl-
Na+
ionic bond
Covalent Bonding
- two atoms each sharing electrons within a molecular orbital
FF
covalent bond
- both fluorine atoms own electrons within bond
OCTET RULE Generally atoms prefer electron configurations with 8 valence electrons.
- Filled s and p subshells
Atoms bond with each other so that every atom has 8 electrons in its outer shell.
- Atoms may take electrons from each other or they may share electrons.
Octet rule is able to explain a lot of chemistry. I. e., it is able to explain why certain
elements combine together in specific proportions.
Exceptions to the octet rule are plentiful.
LEWIS STRUCTURES
Only valence electrons are important in bonding.
Lewis dot structures show valence electrons surrounding atom.
We visualize the four valence orbitals of an atom as the sides of a box. Electrons are put
into orbitals according to Hunds rule.
Examples
Be has 2 valence electrons.
Be
Br
Br
Br
F
Ca
F-
2+
Ca
F-
F
Lewis structures are much more illuminating when we consider the sharing of electrons
(covalent bonding).
Lattice Energy energy of released when positive and negative ions form crystal lattice due
to their attraction for each other.
Creation of ionic compound can be decomposed into many small steps. I. e., lattice energy can
be decomposed into many smaller energy steps.
COULOMBS LAW
- fundamental law of physics (hugely important in chemistry)
E=k
q1q 2
r12
E energy of interaction
q1 charge of ion 1
q2 charge of ion 2
k proportionality constant
r12 distance between ion 1 and ion 2
COVALENT BONDING
- Atoms that are bonded share valence electrons.
- Sharing is what creates covalent bond.
- When atoms bond covalently, new entity termed molecule is formed.
Covalent Bonding in Diatomic Molecules
Hydrogen H2
H + H
- Since both atoms share electrons in bond, both atoms have 8 valence electrons, octet rule
is satisfied.
Hydrogen fluoride (hydrofluoric acid)
H +
Oxygen
- note that a molecule can have more than one covalent bond
Nitrogen
H
H
H
Ammonia
H
H
H +
H
N
H
Carbon Dioxide
Cl
Cl
+
Na
S
O
S
O
O
3-
3-
O
2+
2+
Fe
Fe
2+
O
Fe
H
H
RESONANCE
- Sometimes more than one correct Lewis structure can be drawn.
- In that case, actual structure is a blend of correct structures.
Example: Draw a Lewis structure for the nitrate ion, NO3# of e- = 5 + 3(6) + 1 = 24 eN is the central atom.
6N + 2 rule = 26 double bond is expected
O
N
O
N
O
- The oxygen atom on the left was chosen arbitrarily. Any of the three atoms could
have been used to form the double bond.
O
N
O
O
- Double-headed arrows indicate resonance structures.
- Double bond is not confined to a single O N pair.
- Double bond is distributed over all three O N pairs.
- Resonance is good, resonance makes a molecule more stable.
BOND LENGTHS
The length of the covalent bond depends on two items.
1. The atomic radii of the atoms involved in the bond.
Example:
d(C H) = 109 pm
r(H) = 37 pm
d(C F) = 133 pm
r(F) =
72 pm
d(C Cl) = 177 pm
r(Cl) = 100 pm
d(C Br) = 194 pm
r(Br) = 114 pm
d(C I) = 213 pm
r(I) = 133 pm
r(C) = 77 pm
2. The number of bonds between the atoms.
Example:
d(N N) = 146 pm
d(C C) = 154 pm
d(N = N) = 122 pm
d(C = C) = 134 pm
d(N N) = 110 pm
d(C C) = 121 pm
Generally, the shorter the bond length, the higher the bond dissociation energy.
d(C C) = 154 pm
d(C = C) = 134 pm
d(C C) = 121 pm
10
A generic atom
Example: CO2
Cl
Be
Cl
- Note: Only two electron sets around central atom since double bonds only count as one.
Geometries with three e- sets about central atom.
1. electron sets geometry trigonal planar
A generic atom
B
N
F
b) Bent (V-shaped)
- two bonding pairs and one nonbonding pair
Example: SO2
S
O
*Nonbonding e- pairs take up more room than bonding pairs. Therefore bond angle between
oxygen atoms is slightly less than 120.*
11
H
HH
3-D picture
2-D picture
Example: PO43O
O
O
P
OO
b) Trigonal Pyramidal
- 3 bonding pairs and 1 nonbonding pair
Example: NH3
H
N
H
N
H H H
12
Example: ClO3O
Cl
Cl
O O O
c) Bent (V-shaped)
- two bonding pairs and two nonbonding pairs
Example: H2O
H
O
H
O
Example: SF2
S
F
13
ELECTRONEGATIVITY
In covalent bonding, sharing of electrons is rarely perfect.
One atom will draw electrons closer to itself than the other atom.
Consider Methanol
H-
O
imperfect sharing
perfect sharing
Periodicity of Electronegativity
increasing
14
Atom B
Less than 2.20
Less than 1.70
Greater or = 1.70
Is one of
the atoms
greater or
equal to 2.20?
No
Bonding
metallic
ionic
covalent
Bonding is metallic
Yes
Is the
other atom
greater or
equal to 1.70?
No
Bonding is ionic
Yes
Bonding is covalent
Examples
2.1
H
1.0
Li
1.5
Be
2.0
B
2.5
C
3.0
N
3.5
O
4.0
F
Bonding is covalent
C = 2.5 F = 4.0
- Both nonmetal atoms want the electrons, so the compromise is a covalent bond
Li2O2 is used in subs to convert CO2 to O2.
Bonding is ionic
- Metal atom doesnt want electrons and nonmetal atom want electron, so ionic bonding is
a perfect result
BeH2 forms polymer [long chain] rather
than molecule.
Bonding is metallic
Be = 1.5 H = 2.1
- Both metals atoms dont want the electrons, so the valence electrons become delocalized
in a metallic bond
15
POLAR MOLECULES
A polar molecule has one side slightly positive and the other slightly negative.
Two conditions must be met in a polar molecule.
1.) Polar covalent bonds
2.) Correct geometry
To emphasize necessity of correct geometry, compare two examples.
GeO2
Ge = 2.0
Cl = 3.5
|Ge O| = 1.5
H2O
H = 2.1
O = 3.5
|H O| = 1.4
+ Ge O
+ HO
Ge
O
-
N
H H H
+
H
C
HH