DR.

AHMED ATEF
01017577386

CHAPTER 8,9
BONDING: GENERAL
CONCEPTS & COVALENT
BONDING: ORBITALS
Chemistry Course
Grade 12
STEM
DR/ Ahmed Atef 01017577386

The Lewis Theory

• Valence electrons play a fundamental role in chemical bonding.
• Chemical bonding that results from the transfer of 1 or more electrons from
1 atom to another leading to the formation of positive and negative ions
is called ionic.
• Chemical bonding that involves the sharing of electrons is called covalent
(non-polar and polar).
• Electrons are transferred/ shared to the extent that each atom acquires an
especially stable electron configuration. Usually, the configuration of a
noble gas (8 outer shell electrons).

Lewis Dot Symbols

• When atoms form compounds, it is their valence electrons that actually
interact.
• A Lewis dot symbol consists of the element’s symbol surround by dots.
• Each dot represents a valence electron.

• Atoms combine in order to achieve a more stable electron configuration.

• Maximum stability results when a chemical species is isoelectronic with a
noble gas.

1|Page
DR/ Ahmed Atef 01017577386

• Dots are not paired until absolutely necessary.

• Ions may also be represented by Lewis dot symbols.

2|Page
DR/ Ahmed Atef 01017577386

Lewis dot symbols of the main group elements

Example
• Write Lewis dot symbols for (a) fluoride ion (F-), (b) potassium ion (K+),
and (c) sulfide ion (S2-).
Strategy: Starting with the Lewis dot symbols for each element, add dots (for
anions), or remove dots (for cations) as needed to achieve the correct charge on
each ion. Don’t forget to include the appropriate charge on the Lewis dot symbol.

3|Page
DR/ Ahmed Atef 01017577386

Drawing Lewis Structures

Follow these steps when drawing Lewis structure for molecules and
polyatomic ions.
1. Draw the skeletal structure of the compound. The least electronegative
atom is usually the central atom. Draw a single covalent bond between
the central atom and each of the surrounding atoms.
2. Count the total number of valence electrons present; add electrons for
negative charges and subtract electrons for positive charges.
3. For each bond in the skeletal structure, subtract two electrons from the
total valence electrons.
4. Use the remaining electrons to complete octets of the terminal atoms
by placing pairs of electrons on each atom. Complete the octets of the
most electronegative atom first.
5. Place any remaining electrons in pairs on the central atom.
6. If the central atom has fewer than eight electrons, move one or more
pairs from the terminal atoms to form multiple bonds between the
central atom and terminal atoms.

Write the Lewis structure of nitrogen trifluoride (NF3).

Step 1 – N is less electronegative than F, put N in center.
Step 2 – Count valence electrons N - 5 (2s22p3) and F - 7 (2s22p5)
5 + (3 x 7) = 26 valence electrons
Step 3 – Draw single bonds between N and F atoms and complete octets on N
and F atoms.
Step 4 - Check, are number of e- in structure equal to number of valence e- ?
3 single bonds (3x2) + 10 lone pairs (10x2) = 26 valence electrons

4|Page
DR/ Ahmed Atef 01017577386

Lewis Structures
• A Lewis structure is a representation of covalent bonding.
• Shared electron pairs are shown either as dashes or as pairs of dots.
• Lone pairs are shown as pairs of dots on individual atoms.

Multiple Bonds
• In a single bond, atoms are held together by one electron pair.
• In a double bond, atoms share two pairs of electrons.

5|Page
DR/ Ahmed Atef 01017577386

• A triple bond occurs when atoms are held together by three electron pairs.

• Bond length is defined as the distance between the nuclei of two covalently
bonded atoms.
• Multiple bonds are shorter than single bonds.
For a given pair of atoms:
• Triple bonds are shorter than double
bonds.
• Double bonds are shorter than single
bonds.

6|Page
DR/ Ahmed Atef 01017577386

Drawing Lewis Structures

Example
• Draw the Lewis structure for carbon disulfide (CS2).
Setup
Step 1: C and S have identical electronegativities. We will draw the skeletal
structure with the unique atom, C, at the center.

Step 2: The total number of valence electrons is 16: 6 from each S atom and 4
from the C atom [2(6) + 4 = 16].
Step 3: Subtract 4 electrons to account for the bonds in the skeletal structure,
leaving us 12 electrons to distribute.
Step 4: Distribute the 12 remaining electrons as 3 lone pairs on each S atom.

Step 5: There are no electrons remaining after step 4, so step 5 does not apply.
Step 6: To complete carbon’s octet, use one lone pair from each S atom to make
a double bond to the C atom.

Solution

7|Page
DR/ Ahmed Atef 01017577386

Exceptions to the Octet Rule

Exceptions to the octet rule fall into three categories:
1. The central atom has fewer than eight electrons due to a shortage of
electrons.

• Elements in group 3A also tend to form compounds surrounded by fewer

than eight electrons.
• Boron, for example, reacts with halogens to form compounds of the general
formula BX3 having six electrons around the boron atom.
2. The central atom has fewer than eight electrons due to an odd
number of electrons.

• Molecules with an odd number of electrons are sometimes referred to as free

radicals.
Example
• Draw the Lewis structure of chlorine dioxide (ClO2).
Strategy The skeletal structure is

This puts the unique atom, Cl, in the center and puts the more electronegative O
atoms in terminal positions.
There are a total of 19 valence electrons (7 from the Cl and 6 from each of the
two O atoms). We subtract 4 electrons to account for the two bonds in the
skeleton, leaving us with 15 electrons to distribute as follows: three lone pairs on
each O atom, one lone pair on the Cl atom, and the last remaining electron also
on the Cl atom.
Solution

8|Page
DR/ Ahmed Atef 01017577386
3. The central atom has more than eight electrons.

• Atoms in and beyond the third period can have more than eight valence
electrons.
• In addition to the 3s and 3p orbitals, elements in the third period also have 3d
orbitals that can be used in bonding.
Example
• Draw the Lewis structure of boron triiodide (BI3).
Strategy The skeletal structure is

There are a total of 24 valence electrons (3 from the B and 7 from each of the
three I atoms). We subtract 6 electrons to account for the three bonds in the
skeleton, leaving 18 electrons to distribute in lone pairs on each I atom.
Solution

9|Page
DR/ Ahmed Atef 01017577386

• Draw the Lewis structure of arsenic pentafluoride (AsF5).

Strategy The skeletal structure already has more than an octet around the As
atom.

There are 40 total valence electrons [5 from As (Group 5A) and 7 from each of
the five F atoms (Group 7A)]. We subtract 10 electrons to account for the five
bonds in the skeleton, leaving 30 to be distributed. Next, we place three lone pairs
on each F atom, thereby completing all their octets and using up all the electrons.
Solution

• Draw the Lewis structure of xenon tetrafluoride (XeF4).

Strategy Follow the steps for drawing Lewis structures. The skeletal structure is

There are 36 total valence electrons (8 from Xe and 7 from each of the four F
atoms). We subtract 8 electrons to account for the bonds in the skeleton, leaving
28 to distribute. We first complete the octets of all four F atoms. When this is
done, 4 electrons remain, so we place two lone pairs on the Xe atom.
Solution

10 | P a g e
DR/ Ahmed Atef 01017577386
Lewis Structures for Molecules That Violate the Octet Rule I
1. Write the Lewis structure for PCl5.
Lewis Structures for Molecules That Violate the Octet Rule II
2. Write the Lewis structure for each molecule or ion.
a. ClF3
b. XeO3
c. RnCl2
d. BeCl2
e. ICl4 –

Let's Review Lewis Structures:

(Comments About the Octet Rule)
• The second-row elements C, N, O, and F should always be assumed to obey
the octet rule.
• The second-row elements B and Be often have fewer than eight electrons
around them in their compounds. These electron-deficient compounds are
very reactive.
• The second-row elements never exceed the octet rule since their valence
orbitals (2s and 2p) can accommodate only eight electrons.
• Third row and heavier elements often satisfy the octet rule but can exceed
the octet rule by using their empty valence d orbitals.
• When writing the Lewis structure for a molecule, satisfy the octet rule for
the atoms first. If electrons remain after the octet rule has been satisfied, then
place them on the elements having available d orbitals (elements in Period
3 or beyond).

11 | P a g e
DR/ Ahmed Atef 01017577386

Formal charge
Sometimes, while drawing Lewis structures, you don't have observational data to
use. Formal charges can be used to find out what to choose.
Formal charge = (number of Valence shell e- of an atom) – [(number Bond
pair e-) + (number of unshared e-)]
For example, let’s take the first incorrect drawing of sulfuric
acid.
• Formal charge on S = 6 - 4 - 0 = 2
• Formal charge on H = 1 - 1 - 0 = 0
• Formal charge on O = 6 - 2 - 4 = 0 (on the ones
bonded to H)
• Formal charge on O = 6 - 1 - 6 = -1 (on the isolated ones)
We can disregard the ones with 0 formal charge.
• The ones that do have formal charge are sulfur and the isolated oxygens.
• Since the 2 oxygens are -1 and sulfur is 2, another bond goes from each
oxygen to the sulfur to cancel the formal charge. (2 + 2(-1)) = 0
• When several Lewis structures are possible, those with the smallest
formal charges are the most stable and are preferred.

Two possible skeletal structures of formaldehyde

(CH2O)

• An atom’s formal charge is the difference between the number of valence

electrons in an isolated atom and the number of electrons assigned to that
atom in a Lewis structure.

• The sum of the formal charges of the atoms in a molecule or ion must
equal the charge on the molecule or ion.

12 | P a g e
DR/ Ahmed Atef 01017577386

𝟏
• Formal charge on C = 4 -2 - x 6 = -1
𝟐
𝟏
• Formal charge on O = 6 -2 - x 6 = +1
𝟐

• formal charge on C = 4 -0 - ½ x 8 = 0
• formal charge on O = 6 - 4 - ½ x 4 = 0

Formal charge and Lewis’s structure

1. For neutral molecules, a Lewis structure in which there are no formal charges
is preferable to one in which formal charges are present.
2. Lewis structures with large formal charges are less plausible than those with
small formal charges.
3. Among Lewis structures having similar distributions of formal charges, the
most plausible structure is the one in which negative formal charges are placed
on the more electronegative atoms.

13 | P a g e
DR/ Ahmed Atef 01017577386

• Which is the most likely Lewis’s structure for CH2O?

• Formal charge can be used to determine the most reasonable Lewis

Structure when more than one possibility exists for a compound.
Formal charge = valence electrons – associated electrons
To determine associated electrons:
1. All the atom’s nonbonding electrons are associated with the atom.
2. Half the atom’s bonding electrons are associated with the atom.

• Determine the formal charges on each oxygen atom in the ozone molecule
(O3).

14 | P a g e
DR/ Ahmed Atef 01017577386

Rules Governing Formal Charge (Remember)

• To calculate the formal charge on an atom:
1. Take the sum of the lone pair electrons and one-half the shared electrons.
This is the number of valence electrons assigned to the atom in the
molecule.
2. Subtract the number of assigned electrons from the number of valences
electrons on the free, neutral atom to obtain the formal charge.
• The sum of the formal charges of all atoms in a given molecule or ion must
equal the overall charge on that species.
• If non-equivalent Lewis structures exist for a species, those with formal
charges closest to zero and with any negative formal charges on the most
electronegative atoms are considered to best describe the bonding in the
molecule or ion.

Example
• The widespread use of fertilizers has resulted in the contamination of
some groundwater with nitrates, which are potentially harmful. Nitrate
toxicity is due primarily to its conversion in the body to nitrite (NO 2-),
which interferes with the ability of hemoglobin to transport oxygen.
Determine the formal charges on each atom in the nitrate ion (NO3-).
Strategy Follow the six steps to draw the Lewis structure of (NO3-). For each
atom, subtract the associated electrons from the valence electrons.
Setup

The N atom has five valence electrons and four associated electrons (one from
each single bond and two from the double bond). Each singly bonded O atom has
six valence electrons and seven associated electrons (six in three lone pairs and
one from the single bond). The double bonded O atom has six valence electrons
and six associated electrons (four in two lone pairs and two from the double
bond.)

15 | P a g e
DR/ Ahmed Atef 01017577386
Solution
The formal charges are as follows: +1 (N atom), -1 (singly bonded
O atoms), and 0 (doubly bonded O atom).

• Based on formal charge, identify the best and the worst structures for the
isocyanate ion below:

Solution
Step 1: Assign formal charges on each atom using the formula
Formal charge = valence electrons – associated electrons

Step 2: Determine the best and worst structure.

16 | P a g e
DR/ Ahmed Atef 01017577386
Think About It
For a molecule, formal charges of zero are preferred. When there are nonzero
formal charges, they should be consistent with the electronegativities of the atoms
in the molecules. A positive formal charge on oxygen, for example, is
inconsistent with oxygen’s high electronegativity.
Example

Example
• Give possible Lewis structures for XeO3, an explosive compound of xenon.
Which Lewis structure or structures are most appropriate according to the
formal charges?
• Solution For XeO3 (26 valence electrons) we can draw the following possible
Lewis structures (formal charges are indicated in parentheses):

• Based on the ideas of formal charge, we would predict that the Lewis
structures with the lower values of formal charge would be most
appropriate for describing the bonding in XeO3.

17 | P a g e
DR/ Ahmed Atef 01017577386

Resonance Structures
• Sometimes, a single Lewis structure does not adequately represent the
true structure of a molecule.
• Consider the carbonate ion, CO32-
• carbon (C) has 4 valence electrons × 1 carbon = 4 e-
oxygen (O) has 6 valence electrons × 3 oxygens = 18 e-
• The ion has an overall negative two charge, so we add 2 e- to give a total
of 24 e- to be placed in the Lewis structure.
Carbon is the central atom; the three oxygens are bound to it and electrons
are added to fulfill the octets of the outer atoms.

• All the available electrons have been used but carbon is electron deficient - it
only has six electrons around it. So………………………

• We share a non-bonding
electron pair on some oxygen
with the carbon to create a
double bond and thereby
fulfill carbon's octet.

18 | P a g e
DR/ Ahmed Atef 01017577386

• Three equivalent Lewis structures (formal charges are included) can be drawn
for the carbonate ion. The true structure of the carbonate ion is an average of
the three resonance structures connected by a double headed arrow and
enclosed in brackets.

• This can also be represented by a resonance hybrid

where a dashed line is used to indicate the
delocalized electrons.

• A resonance structure is one of two or more Lewis structures for a single

molecule that cannot by represented accurately by only one Lewis
structure.

• Resonance structures are a human invention.

• Resonance structures differ only in the positions of their electrons.
Example
• High oil and gasoline prices have renewed interest in alternative methods
of producing energy, including the “clean” burning of coal. Part of what
makes “dirty” coal dirty is its high sulfur content. Burning dirty coal
produces sulfur dioxide (SO2), among other pollutants. Sulfur dioxide is
oxidized in the atmosphere to form sulfur trioxide (SO3), which
subsequently combines with water to produce sulfuric acid – a major
component of acid rain. Draw all possible resonance structures of sulfur
trioxide.

19 | P a g e
DR/ Ahmed Atef 01017577386
Strategy Following the steps for drawing Lewis structures, we determine that a
correct Lewis structure for SO3 contains two sulfur-oxygen single bonds and one
sulfur-oxygen double bond.

But the double bond can be put in any one of three positions in the molecule.

Example

Think About It Always make sure that resonance structures differ only in the
position of the electrons, not in the positions of the atoms.

Example
Resonance Structures
• Describe the electron arrangement in the nitrite anion (NO2- ) using the
localized electron model.

20 | P a g e
DR/ Ahmed Atef 01017577386

Valence Shell Electron Pair Repulsion (VSEPR)

Theory
Molecular Shape
• VSEPR theory assumes that the shape of a molecule is determined by the
repulsion of electron pairs.

• Based on Electron Dot (Lewis structures)

• Theory predicts shapes of compounds
• abbreviated VSEPR
• VSEPR stands for Valence Shell Electron Pair Repulsion
• VSEPR predicts shapes based on electron pairs repelling (in bonds or by
themselves)
• Electrons around the central nucleus repel each other. So, structures have
atoms maximally spread out.

Shapes

21 | P a g e
DR/ Ahmed Atef 01017577386

22 | P a g e
DR/ Ahmed Atef 01017577386

23 | P a g e
DR/ Ahmed Atef 01017577386

Examples
Name Shape Molecular geometry
Methane Tetrahedral
‘‘No lone pairs’’

Ammonia Trigonal Pyramidal

‘‘One lone pair’’

Water Bent or V shaped

‘‘Two lone pairs’’

Carbon dioxide Linear

24 | P a g e
DR/ Ahmed Atef 01017577386

Structures of molecules with 4 electron pairs around

the central atom

Example
• Prediction of Molecular Structure II
When phosphorus reacts with excess chlorine gas, the compound phosphorus
penta-chloride (PCl5) is formed. In the gaseous and liquid states, this substance
consists of PCl5 molecules, but in the solid state it consists of a 1:1 mixture of
PCI4+ and PC16 - Ions. Predict the geometric structures of PCl5, PCI4+, and
PC16 -.

25 | P a g e
DR/ Ahmed Atef 01017577386

• Prediction of Molecular Structure III

Because the noble gases have filled s and p valence orbitals, they were not
expected to be chemically reactive. In fact, for many years these elements were
called then gases because of this supposed inability to form any compounds.
However, in the early 1960s several compounds of krypton, xenon, and radon
were synthesized. For example, a team at the Argonne National Laboratory
produced the stable colourless compound xenon tetrafluoride (XeF4). Predict its
structure and whether it has a dipole moment.

SQUARE PLANAR STRUCTURE

Solution
• The Lewis structure for XeF4.

• The xenon atom in this molecule is surrounded by six pairs of electrons,

which means an octahedral arrangement.

26 | P a g e
DR/ Ahmed Atef 01017577386

• The structure predicted for this molecule will depend on how the lone pairs
and bonding pairs are arranged. The bonding pairs are indicated by the
presence of the fluorine atoms. Since the structure predicted differs in the two
cases, we must decide which of these arrangements is preferable. The key is
to look at the lone pairs. In the structure in part (a), the lone pair–lone pair
angle is 90 degrees; in the structure in part (b), the lone pairs are separated by
180 degrees. Since lone pairs require more room than bonding pairs, a
structure with two lone pairs at 90 degrees is unfavourable. Thus, the
arrangement in Fig. 8.20(b) is preferred, and the molecular structure is
predicted to be square planar. Note that this molecule is not described as being
octahedral. There is an octahedral arrangement of electron pairs, but the atoms
form a square planar structure. Although each Xe—F bond is polar
(fluorine has a greater electronegativity than xenon), the square planar
arrangement of these bonds causes the polarities to cancel. Thus, XeF4 has no
dipole moment, as shown in the margin.

• We can further illustrate the use of the VSEPR model for molecules or ions
with lone pairs by considering the triiodide ion (I3-).

• The central iodine atom has five pairs around it, which requires a trigonal
bipyramidal arrangement. Several possible arrangements of lone pairs are
shown in the Figure below. Note that structures (a) and (b) have lone pairs
at 90 degrees, whereas in (c) all lone pairs are at 120 degrees. Thus
structure (c) is preferred. The resulting molecular structure for I3- is
linear:

27 | P a g e
DR/ Ahmed Atef 01017577386

The VSEPR Model and Multiple Bonds

For the VSEPR model, multiple bonds count as one effective electron pair.
Example:
• Structures of Molecules with Multiple Bonds
Predict the molecular structure of the sulfur dioxide molecule. Is this molecule
expected to have a dipole moment?

Molecules Containing No Single Central Atom

• So far, we have considered molecules consisting of one central atom
surrounded by other atoms. The VSEPR model can be readily extended to
more complicated molecules, such as methanol (CH3OH). This molecule is
represented by the following Lewis structure:

• The molecular structure can be predicted from the

arrangement of pairs around the carbon and oxygen
atoms. Note that there are four pairs of electrons
around the car-bon, which requires a tetrahedral
arrangement The oxygen also has four pairs,
which requires a tetrahedral arrangement.
However, in this case the tetrahedron will be slightly
distorted by the space requirements of the lone pairs.

28 | P a g e
DR/ Ahmed Atef 01017577386

Hybridization
• the concept of mixing atomic orbitals to form new hybrid orbitals suitable for
the qualitative description of atomic bonding properties.
The sp hybrid atomic orbitals
• The sp hybrid atomic orbitals are possible states of electron in an atom,
especially when it is bonded to others. These electron states have half 2s and
half 2p characters
• For example, the molecule H-Be-H is formed due to the overlapping of two
1s orbitals of 2 H atoms and the two sp hybridized orbitals of Be. Thus, the H-
Be-H molecule is linear.

The sp2 hybrid orbitals

• The energy states of the valence electrons in atoms of the second period are in
the 2s and 2p orbitals. If we mix two of the 2p orbitals with a 2s orbital, we
end up with three sp2 hybridized orbitals. These three orbitals lie on a plane,
and they point to the vertices of an equilateral triangle as shown here.
• When the central atom makes use of sp2 hybridized orbitals, the compound so
formed has a trigonal shape. BF3 is such a molecule:

29 | P a g e
DR/ Ahmed Atef 01017577386

The sp3 hybrid orbitals

• Mixing one s and all three p atomic orbitals produces a set of four equivalent
sp3 hybrid atomic orbitals. The four sp3 hybrid orbitals points towards the
vertices of a tetrahedron, as shown here in this photograph
• In the case of methane, the three 2p orbitals of the carbon atom are combined
with its 2s orbital to form four new orbitals called " sp 3 " hybrid orbitals.

Hybridization Involving Multiple Bonds

• Only a maximum of two electrons can occupy any orbital whether it is an
atomic orbital or a molecular orbital due to electron-electron repulsion.
• When we draw a double or a triple-bond between two atoms, we imply that
either four or six electrons are directly between these two atoms.
• Since this is impossible, we must have these extra electrons off to the side in
what we refer to as pi bonds.
• Therefore, all multiple bonds are composed of two different kinds of
molecular bonds called pi-bonds and sigma-bonds.
• The sigma-bond is defined as the linear overlap of atomic orbitals (hybrids
except for hydrogen) in which two electrons are directly between the two
bonded nuclei.
• Pi-bonds are defined as the parallel overlap of p-orbitals. A double bond has
one sigma-bond and one pi-bond. A triple bond thus consists of a sigma-bond
and two pi-bonds with the pi-bonds in different planes

30 | P a g e
DR/ Ahmed Atef 01017577386

Examples
• The Localized Electron Model III
Describe the bonding in the triiodide ion I3- .
• The Localized Electron Model IV
How is the xenon atom in XeF4 hybridized?
• The Localized Electron Model V
For each of the following molecules or ions, predict the hybridization of each
atom, and describe the molecular structure.
a. CO
b. BF4-
c. XeF2

31 | P a g e