Lewis Structures

Lewis Theory

 Electrons, especially those of the outermost (valence) electronic shell, play a fundamental role
in chemical bonding
 In some cases, electrons are transferred from one atom to another. Positive and negative ions
are formed and attract each other through electrostatic forces called ionic bonds
 In other cases, one or more pairs of electrons are shared between atoms. A bond is formed by
sharing of electrons between atoms is called a covalent bond
 Electrons are transferred or shared in such a way that each atom acquires a stable electron
configuration. Usually, this is a noble gas configuration, one with eight valence electrons, or an
octet
o Hydrogen is only limited to 2 outer-electrons

IONIC BONDING – electrons are transferred from one atom to another; usually involves compounds
with metal and nonmetal atoms

* take note that the transfer is FROM metal atom (which forms the cation) TO nonmetal atom (which
forms the anion)

GUIDELINES:

Step 1: Draw the Lewis symbol for each atom, according to the valence electrons the atoms have.

Examples:

Step 2: Transfer the electrons from the metal atoms to nonmetal atoms, such that the nonmetal atom
will have a total of 8 electrons.

Step 3: Write the corresponding cations and anions formed due to the transfer of electrons.

Chem 16 Notes. RMCG

Examples:

COVALENT BONDING– pair of electrons are shared between two atoms; usually involves two or more
nonmetal atoms

 Sometimes, multiple covalent bonds (double or triple bonds) are needed

o Multiple covalent bonds are formed most readily by C, N, O, P and S atoms.

GUIDELINES:

Step 1: Determine the total number of valence electrons that must appear in the structure. Take note if
the given is compound (neutral / 0 charge), cation (+ charge), or anion (- charge).

Examples:

Chem 16 Notes. RMCG

 for NH3: 5 v. e (from N) + 3 v. e (from 3H) = 8 v. e

for NH4+: 5 v. e (from N) + 4 v. e (from 4H) – 1 v.e (due to the positive charge of the ion) = 8 v.e

for CO32-: 4 v.e (from C) + 18 v.e (from 3O) + 2 v.e (due to the negative charge of the ion) = 24 v.e

for H3O+: 6 v.e (from O) + 3 v.e (from 3H) - 1 v.e (due to the positive charge of the ion) = 8 v.e

Step 2: Determine the central and terminal atoms.

- Central atom – bonded to two or more atoms

o Can expand octet valence shell (can have more than 8 valence electrons)
o Have the lowest electronegativity
 TREND in periodic table: electronegativity increases from left to right; decreases
from top to bottom
 Carbon atoms are always central atoms
- Terminal atoms – bonded to just one other atom
o Hydrogen atoms are always terminal atoms

Examples:

for NH3: N is the central atom; H is the terminal atom

for NH4+: N is the central atom; H is the terminal atom

for CO32-: C is the central atom; O is the terminal atom

for H3O+: O is the central atom; H is the terminal atom

Step 3: Draw a plausible structure.

a. Form a single bond to connect every terminal atom to the central atom
o Formation of a single bond involves 2 electrons
b. After forming bonds, distribute the remaining v.e starting from the terminal to central atoms
c. Determine which atoms need more electrons in order to obey octet rule.
o Add multiple bonds (double or triple bonds) between the atom in need of electrons and
the atom which can share electrons

Examples:

For NH3: total v.e = 8

Chem 16 Notes. RMCG

* The 2 remaining valence electrons are distributed around N atom since H atoms can only
accommodate 2 electrons / form 1 covalent bond. N follows the octet rule.

For NH4+: total v.e = 8 electrons

* All of the valence electrons were used in the formation of covalent bonds. Hence, no excess electrons
were distributed around N atom. N follows octet rule.

For CO32-: total v.e =24 v. e

Chem 16 Notes. RMCG

* from Figure b, it can be seen that all 3 O atoms already obey octet rule while C atom needs additional
2 electrons. However, all of the valence electrons are already used / distributed

* from Figure c, a double bond between C and O is formed in order to provide the needed electrons of
C. (O atom shares one pair of electrons to C atom in order for C atom to complete octet)

* from Figure c, take note that C atom can form double bonds with any of the 3 O atoms. All of the
possible configurations or structures of the molecule or ion are referred to as the resonance structures.

For H3O+: total v.e = 8 v.e

Step 4: Calculate formal charge for each atom.

- FC = # of v.e of the atom - # of lone pair electrons – ½ # of electrons in covalent bond

- The total sum of the formal charges of each atoms must be equal to the final charge of the given
compound.

Examples:

For NH3:

FC of N = 5 – 2 – 3 = 0

FC of H = 1 – 0 – 1 = 0

Total FC = 0 + 0 = 0

* Total FC is consistent with the charge of NH3. Hence, generated Lewis structure is correct.

for NH4+:

FC of N = 5 – 0 – 4 = 1

FC of H = 1 – 0 – 1 = 0

Total FC = 1 + 0 = 1

* Total FC is consistent with the charge of NH4+. Hence, generated Lewis structure is correct.

Chem 16 Notes. RMCG

* A positive sign is written near N atom since the calculated FC is 1.

for CO32-:

FC of C = 4 – 0 – 4 = 0

FC of O (attached to single bond) = 6 – 6 – 1 = -1

FC of O (attached to single bond) = 6 – 6 – 1 = -1

FC of O (attached to double bond) = 6 – 4 – 2 = 0

Total FC = -1 + -1 = -2

* Total FC is consistent with the charge of CO32-. Hence, generated Lewis structure is correct.

* A negative sign is written near single-bonded O atoms since the calculated FC for each is -1.

for H3O+: O is the central atom; H is the terminal atom

FC of O = 6 – 2 – 3 = 1

FC of H = 1 – 0 – 0 = 0

Total FC = 1 + 0 = 1

* Total FC is consistent with the charge of H3O+. Hence, generated Lewis structure is correct.

* A positive sign is written near O atom since the calculated FC is 1.

Exceptions to the Octet Rule

- Odd-electron species
- Incomplete octets
o The number of species with incomplete octets is limited to some beryllium, boron, and
aluminum compounds
 B atom in BF3 gas only six electrons in its valence shell

Chem 16 Notes. RMCG

- Expanded valence shells
o Usually involves nonmetal atoms of the third period and beyond that are bonded to
highly electronegative atoms

Chem 16 Notes. RMCG

Shape of Molecules
Valence – Shell Electron Pair Repulsion (VSEPR) Theory

- Electron pairs repel each other, whether they are in chemical bonds (bond pairs) or unshared
(lone pairs). Electron pairs assume orientations about an atom to minimize repulsions
o The closer together two groups of electrons are forces, the stronger the repulsion
between them
o Lone pair electrons spread out more than bond-pair electrons do
 Order or repulsive forces:

Lone pair – lone pair > lone pair – bond pair > bond pair – bond pair

- Two general types of geometry:

o Electron-group geometry – geometric distributions of electrons
o Molecular geometry – geometric arrangement of the atomic nuclei

Chem 16 Notes. RMCG

* E refers to the lone pair electrons while X refers to any atom which forms bonds with the central atom, A

Chem 16 Notes. RMCG

Examples:

1. NH3
- Has 4 electron groups (3 bond pair e. g and 1 lone pair e. g)
o Electron group: tetrahedral
- Has AX3E form
o Molecular geometry: trigonal pyramidal

2. NH4+
- Has 4 electron groups (4 bond pair e. g)
o Electron group: tetrahedral
- Has AX4 form
o Molecular geometry: tetrahedral

3. CO32-
- Has 3 electron groups (3 bond pair e.g)

* the double bond is taken as a single bond pair e. g

o Electron group: trigonal planar

- Has AX3 form
o Molecular geometry: trigonal planar

4. H3O+
- Has 4 electron groups (3 bond pair e. g and 1 lone pair e. g)
o Electron group: tetrahedral
- Has AX3E form
o Molecular geometry: trigonal pyramidal

5. H2O
- Has 4 electron groups (2 bond pair e. g and 2 lone pair e. g)
o Electron group: tetrahedral
- Has AX2E2 form
o Molecular geometry: bent

6. HCN
- Has 2 electron groups (2 bond pair e. g)

* Take note that the lone pair is not counted as e. g since N is not the central atom

* Take note that the triple bond is counted only as 1 bond pair

Chem 16 Notes. RMCG

 o Electron group: linear
- Has AX2
o Molecular group: linear

Hybridization
# of electron group Hybridization

4 sp3

3 sp2

2 sp

Examples:

1. NH3
- N has 4 electron groups (3 bond pair e. g and 1 lone pair e. g)
o N is sp3 hybridized

2. NH4+
- N has 4 electron groups (4 bond pair e. g)
o N is sp3 hybridized

3. CO32-
- C has 3 electron groups (3 bond pair e.g)
o C is sp2 hybridized
- O (single bond) has 4 electron groups
o O is sp3 hybridized
- O (double bond) has 3 electron groups
o O is sp2 hybridized

4. H3O+
- O has 4 electron groups (3 bond pair e. g and 1 lone pair e. g)
o O is sp3 hybridized

Chem 16 Notes. RMCG

5. HCN
- C has 2 electron groups (2 bond pair e. g)
o C is sp hybridized
- N has 2 electron groups
o N is sp hybridized

Chem 16 Notes. RMCG