Chapter 7

Molecular Geometry

1
 Lewis Dot Symbols
• Lewis proposed that atoms combine to achieve a more stable configuration
(isoelectronic with a noble gas). The Lewis dot symbol consists of the symbol of an
element and one dot for each valence electron.
.
14Si [Ne]3s23p2 . Si. .
• There are two main types of
chemical bonds: ionic bond and
covalent bond.

• Ionic Bond is the electrostatic force between oppositely charged ions. Involve complete
transfer of electrons from one atom to another. Normally formed between a metal and a
nonmetal.

• Covalent Bond is formed when two atoms share one or more pairs of electrons. Normally
formed between nonmetals.

2
• A Lewis structure is a representation of covalent bonding and show how valence electrons
are arranged among atoms in a molecule/polyatomic ion. Lewis structures reflect the idea
that stability of a compound relates to the octet rule.
Shared electrons pairs (bonding pairs)
represented by two dots (:) or by a single line
(-) between two atoms.
Unshared electron pair (lone pairs or
nonbonding pairs) are shown as pairs of dots
on individual atoms.
• Octet rule: An atom other than hydrogen tends to form bonds until it is surrounded by
eight valence electrons, attain octets (or duets for hydrogen).

• In the Lewis structure, two atoms may share two or more pairs of electrons to get octets and
held together by multiple bonds; double bond arises when two atoms share two pairs of
electrons , triple bond arises when two atoms share three pairs of electrons.

3
 Drawing Lewis Structures
1- Calculate the total number of valence electrons by summing the number of valence
electrons for each atom (for a polyatomic ion, add one electron for each negative
charge and subtract one electron for each positive charge)
For PCl3, the total number of valence electrons = 5 + (3 x 7) = 26 e

2- Draw a skeletal structure by joining atoms by single covalent

bonds; The least electronegative element is usually the central
element, hydrogen atoms are always terminal atoms. For each
bond in the skeletal structure, subtract two from the total number
3 single bonds (3x2) = 6 e‒
of valence electrons. 6 of 26 valence e‒ used

3- Complete the octets around all the atoms (duets for H)

bonded to the central atom.

4- Place any valence electrons remaining on the central atom. 9 lone pairs (9x2)= 18 e‒
If there are not enough electrons to give the central atom an 6+18= 24 of 26 valence e‒ used
octet, try multiple bonds. Use one or more of the unshared
pairs of electrons on the atoms bonded to the central atom to
form double or triple bonds.
1 lone pair on central atom4= 2 e‒
24+2=26 of 26 valence e‒ used
Example: Write the Lewis structure for CO2.
Solution : the total number of valence electrons is 4 + (2 x 6) = 16
.. .. .. ..
O—C —O O—C —O O—C —O

..
..

..
..
.. .. .. ..
2 single bonds = 4 e‒ 6 lone pairs = 12 e‒

.. = C = O
4 of 16 valence e‒ used 4+12= 16 of 16 valence e‒
O

..

..
used
..
C lacks an octet, move lone pair from the Os to form
double bonds.

Example: Write the Lewis structure for the carbonate ion (CO32-)
Solution: the total number of valence electrons = 4 + (3 x 6) +2 = 24 e-

3 single bonds = 6 e‒ 9 lone pairs = 18 e‒

carbon lacks an octet, move lone pair from one of
6 of 24 valence e‒ used 6+18= 24 of 24 valence e‒
used terminal O to form double bond.
These are referred to as resonance forms since the
double bond can form equally well with any of the
three oxygen atom. The actual structure is
intermediate between these resonance structures 5
Example: Write two resonance structures for ozone O3
Solution: the total number of valence electrons = (3 x 6) = 18 e-

2 single bonds = 4 e‒ 6 lone pairs = 12 e‒ resonance forms of O3

4 of 18 valence e‒ used 4+12= 16 of 18 valence e‒
used

Formal Charge and Lewis Structure

• An atom’s formal charge (FC) is the electrical charge difference between the valence
electrons in an isolated atom and the number of electrons assigned to that atom in a
Lewis structure.
FC = Valence electrons – ( unshared electrons + ½ bonding electrons)

• In cases where more than one Lewis structure seems possible, formal charges are used
to determine which one is the most acceptable according to the following guidelines.

a. Lewis structure with small (or zero) formal charges on individual atoms is
better than that with large ones.
b. Negative formal charges are more likely to occur on the more electronegative
elements. 6
Example: Draw the most likely Lewis structure for formaldehyde (CH2O).
Solution: The two possible structures are:
(a) (b)

For C: CF= 4‒ [2 + (½ x 6)]= ‒ 1 For C: CF= 4‒ [0 + (½ x 8)]= 0

For O: CF= 6‒ [2 + (½ x 6)]= + 1 For O: CF= 6‒ [4 + (½ x 4)]= 0
For H: CF= 1‒ [0 + (½ x 2)]= 0 For H: CF= 1‒ [0 + (½ x 2)]= 0
Structure (b) is the more likely structure because it carries no formal charges.

Example: Which of the following is the most plausible Lewis structure of

cyanate ion (OCN‒)?
Solution:

Structures A and B have the least amount of formal charge and are therefore to be
preferred over Structure C. Structure A is preferable to B because it has the negative
formal charge on the more electronegative atom. 7
Exceptions to the Octet Rule:
(1) Odd-Electron Species: molecules containing an odd number of valence electrons.
Example: NO and NO2

The unpaired electron is put on the N atom, giving both atoms a formal charge of zero
(2) Incomplete Octets: There are a few species in which the central atom violates the octet
rule, it is surrounded by two or three electron pairs rather than four.
Example: BeF2 and BF3

(3) Expanded Octets: Molecules in which the central atom is surrounded by more than
four pairs of valence electrons.
Example: PCl5 and SF6
In molecules of this type, the terminal atoms
are most often halogens (F, Cl,Br, I), the central
atom is a nonmetal in the third, fourth, or fifth
period of the periodic table. All these atoms
have d orbitals available for bonding. 8
Molecular Geometry
• Molecular geometry is the three-dimensional arrangement of atoms in a molecule and
can be predicted based on the valence-shell electron-pair repulsion (VSEPR) model.
• According to the VSEPR model, the valence-shell electron pairs are arranged about
each atom so that electron pairs are kept as far away from one another as possible, thus
minimizing electron-pair repulsions.
• In general, each nonbonding pair, single bond, or multiple bond
produces a single electron domain around the central atom in a 3 electron domains on
the central O atom
molecule.
• The arrangement of electron domains about the central atom is called electron-domain
geometry. In contrast, the molecular geometry is the arrangement of only electron
domains due to bonds.

9
10
11
Example:
Use the VSEPR model to predict the molecular geometry of (a) O3, (b) SnCl3‒.
Solution

there are three electron domains about

the central O atoms. about the central
Sn atoms.

12
Effect of Nonbonding Electrons and Multiple Bonds on Bond Angles

13
Shapes of Larger Molecules

14
 Practice on Chapter 7
Q1. __________ bond involve complete transfer of electrons from one atom to another
a) ionic b) covalent c) metallic d) hydrogen
Q2. A double bond consists of __________ pairs of electrons shared between two atoms.
a) 1 b) 2 c) 3 d) 4
‒
Q3. The ion NO has __________ valence electrons
a) 12 b) 14 c) 15 d) 16
Q4. Which is a correct Lewis structure for hydrogen cyanide, HCN?
a) b) c) d)
Q5. The Lewis structure of NH3 shows __________ nonbonding electron pair(s) on N.
a) 0 b) 1 c) 2 d) 3
Q6. Resonance structures differ by __________.
a) number and placement of electrons b) number of electrons only
c) placement of atoms only d) placement of electrons only
Q7. The formal charge on carbon in is __________.
a) 0 b) +1 c) +2 d) +3
2‒
Q8. The formal charge on sulfur in SO4 is _____, where the Lewis structure of the ion is:
a) -2 b) 0 c) +2 d) +4
Q9. Which of these compounds does not follow the octet rule?
a) NF3 b) CF4 c) PF5 d) AsH3
Q10. The molecular geometry of __________ is tetrahedral.
a) CCl4 b) PH3 c) BeCl2 d) O3
Q11. The molecular geometry of the CS2 molecule is __________.
a) linear b) bent c) tetrahedral d) trigonal planar

15