Lewis Structure

1916 G.N. Lewis proposed that a covalent bond is formed when two electrons share an electron pair.
Single Bond, Double bond and a Triple Bond. [Link] (Bond pair)

An unshared pair of valence electrons is called “lone pair”

Octet Rule: Atoms share pairs until they have acquired an octet of valence electrons
1- Decide on number of electrons that are to be included in the structure by adding together numbers of all valence
electrons provided by the atoms.
2- Write the chemical symbols of the atoms in the arrangement that shows which atoms are bonded together.
(Generally less electronegative is the central atom but there are many well known exceptions such as H2O, NH3 etc.

3- Distribute electron in pairs so that one pair is forming a single bond. Then supply electron pairs until they complete
Octets
 Formal Charge
• Extent to which an atom (within a molecule) has lost or gained
electrons during covalent bond formation process.
A hypothetical charge that would result if all bonding electrons are
shared equally (Pure Covalent bonds).
Oxidation number is the hypothetical charge that would result if all
bonding electrons are assigned to a more electronegative atom
(imagine pure ionic bonds).
Formal Charge = [number of valence electrons in an isolated atom] - [(number of lone
pair electrons) + ½ (number of bonding electrons)]
A formal charge compares the number of electrons around a "neutral atom" (an atom not in a molecule) versus
the number of electrons around an atom in a molecule. Formal charge is assigned to an atom in a molecule by
assuming that electrons in all chemical bonds are shared equally between atoms, regardless of relative
electronegativity.

Formal Charge of N = (5 valence e-) - (2 lone pair e-) - (1/2 x 6

bond pair e-) = 0
 A neutral hydrogen atom has one valence electron. Each hydrogen atom in the molecule has no non-
bonding electrons and one bond.

Formal Charge of H = (1 valence e-) - (0 lone pair e-) - (1/2 x 2 bond pair e-) = 0

The sum of the formal charges of each atom must be equal to the overall charge of the molecule or ion.
In this example, the nitrogen and each hydrogen has a formal charge of zero. When summed the overall
charge is zero, which is consistent with the overall neutral charge of the NH3 molecule.
Typically, the structure with the most formal charges of zero on atoms is the more stable Lewis structure. In cases where
there MUST be positive or negative formal charges on various atoms, the most stable structures generally have negative
formal charges on the more electronegative atoms and positive formal charges on the less electronegative atoms. The
next example further demonstrates how to calculate formal charges for polyatomic ions.
Identify the number of valence electrons in each atom in the NH4+ ion. Use the Lewis electron
structure of NH4+ to identify the number of bonding and non-bonding electrons associated with each
atom
 The nitrogen atom in ammonium has zero non-bonding electrons and 4 bonds.

Formal Charge of N = (5 valence e-) - (0 lone pair e-) - (1/2 x 8 bond pair e-) = +1

Each hydrogen atom in has one bond and zero non-bonding electrons. The formal charge on each
hydrogen atom is therefore
 BH4-

Carbon
Carbon, the most important element for organic chemists. In the structures of methane, methanol, ethane, ethene,
and ethyne, there are four bonds to the carbon atom. And each carbon atom has a formal charge of zero. In other
words, carbon is tetravalent, meaning that it commonly forms four bonds.
Two other possibilities are carbpon radicals and carbenes, both of which have a formal charge of zero. A
carbon radical has three bonds and a single, unpaired electron. Carbon radicals have 7 valence electrons and
a formal charge of zero. Carbenes are a highly reactive species, in which a carbon atom has two bonds and
one lone pair of electrons, giving it a formal charge of zero.

Oxygen
The common arrangement of oxygen that has a formal charge of zero is when the oxygen atom has 2
bonds and 2 lone pairs. Other arrangements are oxygen with 1 bond and 3 lone pairs, that has a -1
formal charge, and oxygen with 3 bonds and 1 lone pair that has a formal charge of +1. All three
patterns of oxygen fulfill the octet rule.
 If it has two bonds and two lone pairs, as in water, it will have a formal charge of zero. If it has one bond and
three lone pairs, as in hydroxide ion, it will have a formal charge of -1. If it has three bonds and one lone pair,
as in hydronium ion, it will have a formal charge of +1.

Nitrogen
Nitrogen has two major bonding patterns, both of which fulfill the octet rule:

If a nitrogen has three bonds and a lone pair, it has a formal charge of zero. If it has four bonds (and no lone pair), it
has a formal charge of +1. In a fairly uncommon bonding pattern, negatively charged nitrogen has two bonds and two
lone pairs.
Phosphorus and Sulfur
Two third row elements are commonly found in biological organic molecules: phosphorus and sulfur. Although both of
these elements have other bonding patterns that are relevant in laboratory chemistry, in a biological context sulfur
almost always follows the same bonding/formal charge pattern as oxygen, while phosphorus is present in the form of
phosphate ion (PO43-), where it has five bonds (almost always to oxygen), no lone pairs, and a formal charge of zero.
Remember that elements in the third row of the periodic table have d orbitals in their valence shell as well as s and p
orbitals, and thus are not bound by the octet rule.
Halogens
The halogens (fluorine, chlorine, bromine, and iodine) are very important in laboratory and medicinal organic
chemistry, but less common in naturally occurring organic molecules. Halogens in organic compounds usually are
seen with one bond, three lone pairs, and a formal charge of zero. Sometimes, especially in the case of bromine,
we will encounter reactive species in which the halogen has two bonds (usually in a three-membered ring), two
lone pairs, and a formal charge of +1.
 CO2

1. C is less electronegative than O, so it is the central atom.

2. C has 4 valence electrons and each O has 6 valence electrons, for a total of 16 valence electrons.

3. Placing one electron pair between the C and each O gives O–C–O, with 12 electrons left over.

4. Dividing the remaining electrons between the O atoms gives three lone pairs on each atom:

This structure has an octet of electrons around each O atom but only 4 electrons around the C atom.

5. No electrons are left for the central atom.

6. To give the carbon atom an octet of electrons, we can convert two of the lone pairs on the oxygen atoms to bonding
electron pairs. There are, however, two ways to do this. We can either take one electron pair from each oxygen to
form a symmetrical structure or take both electron pairs from a single oxygen atom to give an asymmetrical structure:

Both Lewis electron structures give all three atoms an octet. How do we decide between these two possibilities? The
formal charges for the two Lewis electron structures of CO2 are as follows:

Both Lewis structures have a net formal charge of zero, but the structure on the right has a +1 charge on the more
electronegative atom (O). Thus the symmetrical Lewis structure on the left is predicted to be more stable, and it is, in
fact, the structure observed experimentally. Remember, though, that formal charges do not represent the actual
charges on atoms in a molecule or ion. They are used simply as a bookkeeping method for predicting the most stable
Lewis structure for a compound.
The Lewis structure with the set of formal charges closest to zero is usually the most stable.
 Formal Charge Oxidation state
1-CH4

2- CH3OH

3-HF

4- CO

5-H2

6- NaH
 [SCN]-
The thiocyanate ion (SCN−), which is used in printing and as a corrosion inhibitor against acidic gases, has at
least two possible Lewis electron structures. Draw two possible structures, assign formal charges on all atoms
in both, and decide which is the preferred arrangement of electrons.
We must calculate the formal charges on each atom to identify the more stable structure. If we begin
with carbon, we notice that the carbon atom in each of these structures shares four bonding pairs, the
number of bonds typical for carbon, so it has a formal charge of zero. Continuing with sulfur, we observe
that in (a) the sulfur atom shares one bonding pair and has three lone pairs and has a total of six
valence electrons. The formal charge on the sulfur atom is therefore 6 - (6 + 2/2) = -1. In (b), the sulfur
atom has a formal charge of 0. In (c), the sulfur atom has a formal charge of +1. Continuing with the
nitrogen, we observe that in (a) the nitrogen atom shares three bonding pairs and has one lone pair and
has a total of 5 valence electrons. The formal charge on the nitrogen atom is therefore 5 - (2 + 6/2) = 0.
In (b), the nitrogen atom has a formal charge of -1. In (c), the nitrogen atom has a formal charge of -2.
Which structure is preferred? Structure (b) is preferred because the negative charge is on the more
electronegative atom (N), and it has lower formal charges on each atom as compared to structure (c): 0, −1
versus +1, −2.
CH3NHO -
 O3

O O
O O O O

Neither structure is actually correct but can be redrawn to represent a structure

that is a hybrid of the two - a resonance structure.

B B
O O O
O O O O O O

A C A C

Resonance structures have the same relative placement of atoms

but different locations of bonding and non-bonding electron pairs.
Resonance structures are not real bonding depictions.
The actual molecule is a resonance hybrid, an average
of the resonance forms.

For O3, two of the electron pairs (one bonding, one non-
bonding) are delocalized (i.e., their density is spread over
the entire molecule). This effect yields two identical O-O
bonds, each consisting of a single bond (localized
electron
pair) and a partial double bond (from one of the
delocalized
electron pairs).
 Write resonance structures for the nitrate anion, NO3-.
Determine if other structures can be drawn in which the electrons
can be delocalized over more than two atoms.

Nitrate has 1(5) + 3(6) + 1 = 24 valence electrons.

O O O
N does not have an
octet; a pair of e- is
N N N used to form a
O O O O O O double bond.

O O O

N N N
O O O O O O
 NCO- has three possible resonance forms

N C O N C O N C O

A B C

Formal charges:
 -2 0 +1 -1 0 0 0 0 -1

N C O N C O N C O

Forms B and C have negative formal charges on N and O. These forms are
more important than Form A.
Form C has a negative charge on O which is more electronegative than N.
Therefore, Form C contributes the most to the resonance hybrid.
Lewis Structures for Exceptions to the Octet Rule

(a) Electron-Deficient Molecules: gaseous molecules containing

either Be or B as the central atom; have fewer than 8 electrons
around the Be or B (4 e- around Be and 6 e- around B) (BF3).

(b) Odd-Electron Molecules: have an odd number of valence

electrons; examples include free radicals, which contain a lone
(unpaired) electron and are paramagnetic (use formal charges to
locate the lone electron) (NO2).

(c) Expanded Valence Shells: for molecules that have more than
8 electrons around the central atom; use empty outer d orbitals;
occurs only with a central atom from Period 3 or higher (SF6,
PCl5).
 Writing Lewis Structures for Exceptions to the
Octet Rule

Write Lewis structures for (a) H3PO4 (b) ClO4- and (c) BFCl2, In
(a), decide on the most likely structure.
Draw the Lewis structures for the molecule and determine if there is
an element that is an exception to the “octet rule”. Note that (a)
contains P which is a Period-3 element and can have an expanded
valence shell.
(a) H3PO4 has two resonance forms, and formal charges
indicate the more important form.
-1
0 (b) BFCl2 has only one
0 +1 0 0
O O Lewis structure.
0 H O P O H 0 0 H O P O H 0

0
O
H
0
0 O
H
0 F
B
(ClO4)-
more stable Cl
0 Cl
0
lower formal charges
 Molecular Geometry
Molecules of different substances have diverse shapes. Atoms attach to one another
in various geometric arrangements. The overall molecular shape of a molecule is
determined by its bond angles in three dimensions. The shape of a molecule is very
important for its physical and chemical properties.

VSEPR Valence Bond Molecular Orbital

Theory Theory
 Valence-shell Electron-Pair Repulsion (VSEPR) Theory

A method to predict the shapes of molecules from their electronic structures, knowledge
of the groups of electrons around a central atom (Lewis structures do not depict shape),

Basic principle: each group of valence electrons around a central

atom is located as far away as possible from the others in order to
minimize repulsions

Both bonding and non-bonding valence electrons around

the central atom are considered.

AXmEn symbolism: A = central atom, X = surrounding atoms,

E = non-bonding electrons (usually a lone pair)
 • Draw Lewis Structure and decide on shape
• Valence electrons repel each other
• Geometry around the central atom

Steric Number (SN)

Number of atoms bonded to central atom + number of lone pairs

Double and triple bonds are counted as one bond only

VSEPR can be applied to all resonance structures

A- Molecules without lone pairs

B- Molecules with lone pairs

 Electron pairs (bonding and nonbonding electrons) repel one
another, as a result , the electron pairs remain as far apart as
possible from another as possible to minimize the repulsion.

• Two electron pairs in the valence orbital are arranged linearly

• Three electron pairs are organized in a trigonal planar arrangement
• Four electron pairs are organized in a tetrahedral arrangement
• Five electron pairs are arranged in a trigonal bipyramid
• Six electron pairs are organized in an octahedral arrangement

The repulsion of lone pair electrons is grater than the repulsion of bond pair electrons
Applying the VSEPR theory.

• draw a plausible Lewis structure of the molecule or polyatomic ion.

• Determine the number of unshared electron pairs and numbers of bonds around
the central atom ( multiple bonds count as a single bond)
• Establish the geometrical orientation of the electron pairs around the central atom
as linear, trigonal planar, tetrahedral,, trigonal bipyramid or octahedral
• Describe the molecular geometry
 The steps in determining a molecular shape

Molecular Step 1
formula

Lewis Step 2 Count all e- groups around the

structure central atom A
Note lone pairs and
Electron-group Step 3
arrangement double bonds
Count bonding and
Bond Step 4 non-bonding e-
angles
groups separately.

Molecular
shape
(AXmEn)
Five basic molecular shapes

Ideal bond angles are shown for each shape.

The single molecular shape of the linear
electron-group arrangement

Examples:
CS2, HCN, BeF2

Figure 10.6
 The two molecular shapes of the trigonal planar
electron-group arrangement

Class

Examples: Shape
SO2, O3, PbCl2, SnBr2
Examples:
SO3, BF3, NO3-, CO32-
 Factors Affecting Actual Bond Angles

Observed bond angles are consistent with theoretical angles when (a)
the atoms attached to the central atom are the same and (b) when all
electrons are bonding electrons of the same order.

120o 122o
H larger EN H
Effect of Double Bonds 120
o
C O 116o C O
ideal H H
greater
electron actual
density

Effect of Non-bonding Pairs

Sn
Lone pairs (unshared electron pairs)
Cl Cl
repel bonding pairs more strongly
than bonding pairs repel each other.
95o
The three molecular shapes of the tetrahedral
electron-group arrangement

Examples:
CH4, SiCl4,
SO42-, ClO4-

Examples: Examples:
NH3 H 2O
PF3
OF2
ClO3
H 3O + SCl2
Lewis structures and molecular shapes
The four molecular shapes of the trigonal bipyramidal electron-
group arrangement

Examples:
Examples:
SF4
PF5
XeO2F2
AsF5
IF4+
SOF4
IO2F2-

Examples:
Examples:
XeF2
ClF3
I 3-
BrF3
IF2-

Figure 10.10
General trend for electron-pair repulsions for similar molecules
with a given electron-group arrangement:

Lone pair - lone pair > lone pair - bonding pair > bonding
pair - bonding pair
The three molecular shapes of the octahedral
electron-group arrangement

Examples:
SF6
IOF5

Examples: Examples:
BrF5 XeF4
TeF5- ICl4-
XeOF4

Figure 10.11
Molecular Shapes With More Than One Central Atom

Combinations of the molecular shapes observed

when a single central atom is present

Examples: CH3-CH3 (ethane) and CH3CH2OH (ethanol)

 The tetrahedral
centers of ethane
 The tetrahedral
centers of ethanol
 Determine the shape around each of the central atoms in
acetone, (CH3)2C=O.

tetrahedral O tetrahedral
H H
H C C C H
H H
trigonal planar
O
H > 120o
C H
H C C
H HH

< 120o
VSEPR theory cannot predict actual bond angles
Fails in many transition metal compounds
d block elements have bigger size atoms and some lone pairs are sterochemically in active
 Valence Bond Theory
First quantum mechanical theory of bonding
Two electron wave functions
Constructive and destructive interference
Energy of Interaction Between Two H Atoms
Energies of attraction and
repulsion as functions of distance Potentia
between two H atoms are shown l energy
here.
The minimum of the attraction +346 kJ mol –1
force occur at
H–H bond length of 74 pm, at
which, the antibonding orbital is antibonding
+346 kJ mole–1 above 0, energy
when H atoms are far apart.
distance

–346 kJ mol –1

H – H bond

51
Valence bond method considers the covalent bond as a result of
overlap of atomic orbitals. Electrons stay in regions between the
two atoms.
s-s s-p s-d p-p p-d
H-HH-C H-Pd C-C Se-F
Li-H H-N in Pd P-P
H-F hydride

[Link]
 The wave function

In valance bond theory, the wave function of an electron pair is

formed by superimposing the wave functions for the
separated fragments of the molecule.

For every dynamical system, there exists a wave function Ψ that is a continuous, square-integrable, single-valued function of

the coordinates of all the particles and of time, and from which all possible predictions about the physical properties of the

system can be obtained.

Square-integrable means that the normalization integral is finite

If we know the wavefunction we know everything it is possible to know.

 Wave functions of electrons add up for a bond

Superposition of waves
The bond can be pictured due to high probability that the two electrons will be
found between the nuclei and hence bind them together.

A covalent bond forms when the orbtials of two atoms overlap and are occupied by a
pair of electrons that have the highest probability of being located between the
nuclei. A set of overlapping orbitals has a maximum of two electrons that must have
opposite spins. The greater the orbital overlap, the stronger (more stable) the bond.
The valence atomic orbitals in a molecule are different from those in isolated atoms.

Wave patterns represented by the terms XA (1) XB(2) interferes constructively with XA (2) XB(1)

 = [A X(1) + BX(2)]

 Overlap of orbitals

Electrons in atomic oribitals of the same symmetry / orientation on neighboring atoms are paired
to form sigma and Pie bonds

N2

Electronic configuration 2s2, 2pz1, 2py1, 2px1

One p-oribital can make sigma bond but other two cannot make sigma bonds
Sigma bond

Pie Bond
 Polyatomic molecules
H2O
H 1s1

O 2s2, 2pz2, 2py1, 2px1

 C electronic configuration

b) Hybridization
(c) Hypervalency (Exceptions to octet rule)
• C2 molecule:
Diatomic carbon or dicarbon. Chemical formula C=C.
It is a gas that only exists above 3,642 °C below which it aggregates
into graphite or fullerenes. It occurs in carbon vapor, for example in electric
arcs.

A 2012 paper by Shaik et al. has suggested that a quadruple bond exists in

diatomic carbon.

From a Lewis point of view, there is no reason why carbon can't form a
quadruple bond
• This model satisfies the Octet Rule and leaves no electrons for further
bonding. But it implies that C2 is a perfectly stable molecule, like N2,  and
that just isn't the case. C2 is highly reactive and can only be studied under
high-vacuum conditions, when it can avoid meeting other molecules for
long enough to be detected.

• In VB theory, carbon cannot form a quadruple bond because it doesn't have

enough atomic orbitals pointing in the right directions. Furthermore, the s
atomic orbitals must be hybridized (as sp3, sp2 or sp hybrids) so that they
may point in some direction.
• Valence-bond theory predicts two possible bonding states for C2: a double
bond with all electrons paired, and a triple bond with two unpaired
electrons. These are called resonance structures, and both must be
considered as partial representations of the real situation.
1. Write an acceptable Lewis
structure for the molecule.
2. Determine the number of
VSEPR objects around all
central atoms and determine
the geometry around the
atom.
3. Construct hybrid orbitals
suitable for the predicted
bonding.
4. Link orbitals together to make
bonds.
5. Describe the bonding. Include
the names of the orbitals
involved in each bond. Draw
pictures of the bonds formed
by the overlap of these
orbitals.