Covalent Bonding-A Quick re-run
Covalent bonds result from the sharing of electrons
between two atoms.
• A covalent bond is a two-electron bond in which the
bonding atoms share valence electrons.
• A molecule is a discrete group of atoms held
together by covalent bonds. 1
Covalent Bonding-A Quick re-run
Unshared electron pairs are called nonbonded
electron pairs or lone pairs.
Atoms share electrons to attain the electronic
configuration of the noble gas closest to them
in the periodic table.
• H shares 2 e−.
• Other main group elements share e− until they
reach an octet of e− in their outer shell.
2
Covalent Bonding- Lewis Structures
Lewis structures are electron-dot structures for
molecules. They show the location of all valence e−.
3
Covalent Bonding-some principles
Covalent bonds are formed when two nonmetals
combine, or when a metalloid bonds to a nonmetal.
How many covalent bonds will a particular atom form?
• Hydrogen forms one bond, with its one valence e−.
• Atoms with one, two, or three valence e− form one,
two, or three bonds, respectively. These, (except for
H) will be electron-deficient, ie they will have less
than an octet of electrons- see next lecture
4
Covalent Bonding-some principles
Atoms with four or more valence electrons form enough
bonds to give an octet. For these atoms, the following
formula is used:
predicted
number of bonds = 8 – number of valence e−
For a central atom with an octet of electrons;
Number of bonds + Number of lone pairs = 4
Exceptions will be discussed later..
Lewis Structures
• A molecular formula shows the number and identity
of all of the atoms in a compound, but not which
atoms are bonded to each other.
• A Lewis structure shows the connectivity between
atoms, as well as the location of all bonding and
nonbonding valence electrons.
5
Lewis Structures
HOW TO Draw the “best” Lewis Structure –Using NO3- to illustrate
Step [1] Determine the total number of valence
electrons in the molecule
Step [2] Draw a skeleton for the molecule which connects
all atoms using only single bonds. The least
electronegative atom is placed centrally. The
central atom should be the atom with the most
available sites for bonding
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Lewis Structures
HOW TO Draw the “best” Lewis Structure –Using NO3- to illustrate
Step [3] Of the 24 valence electrons in NO3-, 6 were
required to make the skeleton. The remaining
18 electrons are placed on the terminal O
atoms to fulfil their octets
Step [4] Check to see if there are any remaining electrons.
If so, place them on the central metal. In this case
there are none, all 24 are used up!
8
Lewis Structures
HOW TO Draw the “best” Lewis Structure –Using NO3- to illustrate
Step [5] Are the octets of all the atoms filled? If not then fill the
remaining octets by making multiple bonds (make a lone
pair of electrons, located on a more electronegative
atom, into a bonding pair of electrons that is shared with
the atom that is electron deficient).
Step [6] Check that you have the lowest FORMAL CHARGES possible for
all the atoms, without violating the octet rule.
FORMAL CHARGES = (valence e) - (1/2 bonding e) - (lone electrons)
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Lewis Structures
HOW TO Draw the “best” Lewis Structure –Using NO3- to illustrate
Step [6]
FORMAL CHARGES = (valence e) - (1/2 bonding e) - (lone electrons)
So, for the nitrate ion,
the formal charges are
calculated as given on
the right
The double bonded O atom has a formal charge of zero (generally not
shown) 10
Lewis Structures
IMPORTANT
• No Lewis diagram is complete without formal charges
• Lewis diagrams are used to examine mechanisms of reactions so
knowing which parts of a molecule are electron deficient (+) and
which are electron rich (-) is very useful.
• It is best to have a formal charge of 0 for as many of the
atoms in a structure as possible. This is the most stable Lewis
structure
• The most stable Lewis structure of any polyatomic species is
the one in which the negative charge is on the most
electronegative atoms
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Lewis Structures
HOW TO Draw a Lewis Structure- Exercise
Draw Lewis structures for the following molecules:
Thionyl chloride, SOCl2 ; Nitrous acid, HNO2
Sulfur trioxide, SO3 ; Sulfuryl chloride, SO2Cl2
Nitrous acid
H attached to
the most
electronegative
Sulfuryl chloride atom
12
Sulfur trioxide
Lewis Structures
HOW TO Draw a Lewis Structure- Expanded Octet
You will have noticed that in sulfur trioxide and sulfuryl chloride,
the central S atom has more than 4 electron pairs., ie it has more
than an octet of electrons!
Sulfur trioxide Sulfuryl chloride
This phenomenon occurs when the central atom has empty
d-orbitals and can therefore accommodate more electron pairs
Consider the electron configuration for S:
1s22s22p63s23p4 (3d0)
Remember: At the third energy level l can have values 0,1,2;
meaning there are s-,p-, and d-orbitals.. 13
Lewis Structures
HOW TO Draw a Lewis Structure- Expanded Octet and Resonance
Consider Thionyl chloride Lewis Structure
A
Because S is able to expand its octet one of the
lone pairs on the oxygen atom the molecule
can be shared with the central S atom, thus leading B
to the formation of a S-O bond, resulting in double
S=O bond, and a total of 5 electron pairs around
the central S
The two molecular forms (A and B) of thionyl chloride are referred
to as resonance forms of thionyl chloride
14
Lewis Structures
HOW TO Draw a Lewis Structure- Expanded Octet and Resonance
The two forms are said to be in resonance with one another
A B
But which of the two is more stable than the other? To answer
that, we have to calculate the formal charges on each of the
atoms in each one of the molecules A and B (see next slide)
15
Lewis Structures
HOW TO Draw a Lewis Structure- Expanded Octet and Resonance
A B
Formal charges:
S: 6 - (½ x 6) - 2 = +1 S: 6 - (½ x 8) – 2 = 0
O: 6 – ( ½ x 2) – 6 = -1 O: 6 – ( ½ x 4) – 4 = 0
Cl: 7- ( ½ x 2) - 6 = 0 Cl: 7- ( ½ x 2) - 6 = 0
The formal charges of structure B are the closest to zero, so it is
the more stable resonance structure. 16