CHEM 151

LECTURE 4

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BASIC CONCEPTS OF CHEMICAL BONDING
• Why are some substances chemically bonded molecules and others
an association of ions?
• depends upon the electronic structures of the atoms
• nature of the chemical forces within the compounds
• A broad classification of chemical forces:
• Ionic bonds
• Covalent bonds
• Metallic bonds

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BASIC CONCEPTS OF CHEMICAL BONDING
• Ionic bonds - electrostatic forces that exist between ions of opposite
charge
typically involves a metal with a nonmetal
• Covalent bonds - results from the sharing of electrons between two
atoms
typically involves one nonmetallic element with another
• Metallic bonds
found in solid metals (copper, iron, aluminum)
each metal bonded to several neighboring groups
bonding electrons free to move throughout the 3-dimensional structure

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Lewis Symbols and the Octet Rule

• Valence electrons reside in the outer shell and are the electrons
which are going to be involved in chemical interactions and bonding.
• Electron-dot symbols (Lewis symbols):
• convenient representation of valence electrons
• allows you to keep track of valence electrons during bond formation
• consists of the chemical symbol for the element plus a dot for each valence
electron

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 Lewis Symbols and the Octet Rule

Sulfur
• Electron configuration is [Ne]3s23p4, thus there are six valence
electrons.
• Its Lewis symbol would therefore be:

Note:
The dots (representing electrons) are placed on the four sides of the atomic symbol (top,
bottom, left, right). Each side can accommodate up to 2 electrons
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The Octet Rule
• Atoms often gain, lose, or share electrons to achieve the same
number of electrons as the noble gas closest to them in the periodic
table
• Because all noble gasses (except He) have filled s and p valence
orbitals (8 electrons), many atoms undergoing reactions also end up
with 8 valence electrons.
• This observation has led to the Octet Rule:
• Atoms tend to lose, gain, or share electrons until they are surrounded by 8
valence electrons
• Note: there are many exceptions to the octet rule (He and H, for example),
but it provides a useful model for understanding the basis of chemical
bonding.
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Exceptions to the Octet Rule
There are three general ways in which the octet rule breaks down:
1. Molecules with an odd number of electrons
2. Molecules in which an atom has less than an octet
3. Molecules in which an atom has more than an octet
• Odd number of electrons
Draw the Lewis structure for the molecule nitrous oxide (NO):
1. Total electrons: 6+5=11
2. Bonding structure:
3. Octet on "outer" element:
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Exceptions to the Octet Rule

4. Remainder of electrons (11-8 = 3) on "central"

atom:

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Exceptions to the Octet Rule
5. There are currently 5 valence electrons around the nitrogen.
• A double bond would place 7 around the nitrogen, and a triple bond
would place 9 around the nitrogen.
• We appear unable to get an octet around each atom.
• Less than an octet (most often encountered with elements of Boron
and Beryllium)
• Draw the Lewis structure for boron trifluoride (BF3):
1. Add electrons (3*7) + 3 = 24

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Exceptions to the Octet Rule
2. Draw connectivities:

3. Add octets to outer atoms:

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Exceptions to the Octet Rule

4. Add extra electrons (24-24=0) to central atom:

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Exceptions to the Octet Rule
However,
• In this structure with a double bond, the fluorine atom is sharing
extra electrons with the boron.
• The fluorine would have a '+' partial charge, and the boron a '-' partial
charge, this is inconsistent with the electronegativities of fluorine and
boron.
• Thus, the structure of BF3, with single bonds, and 6 valence electrons
around the central boron is the most likely structure

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BF3 reacts strongly with compounds which have an unshared
pair of electrons which can be used to form a bond with the
boron:

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More than an octet (most common example of exceptions to the octet
rule)
• PCl5 is a legitimate compound, whereas NCl5 is not.

Expanded valence shells are observed only for elements in period 3

(i.e. n=3) and beyond
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More than an octet (most common example of exceptions to the octet
rule)
• The 'octet' rule is based upon available ns and np orbitals for valence
electrons (2 electrons in the s orbitals, and 6 in the p orbitals)
• Beginning with the n=3 principle quantum number, the d orbitals
become available (l=2)
• The orbital diagram for the valence shell of phosphorous is:

Third period elements occasionally exceed the octet rule by using

their empty d orbitals to accommodate additional electrons
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More than an octet (most common example of exceptions to the octet
rule)
Size is also an important consideration:
• The larger the central atom, the larger the number of electrons which can
surround it
• Expanded valence shells occur most often when the central atom is bonded
to small electronegative atoms, such as F, Cl and O.

• Draw the Lewis structure for ICl4-

1. Count up the valence electrons: 7+(4*7)+1 = 36 electrons
2. Draw the connectivities:

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More than an octet (most common example of exceptions to the octet
rule)

3. Add octet of electrons to outer atoms:

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More than an octet (most common example of exceptions to the octet
rule)

4. Add extra electrons (36-32=4) to central atom:

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• 5. The ICl4- ion thus has 12 valence electrons around the central
Iodine (in the 5d orbitals)

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