Study unit 3: Chemical bonding and bonding theories / Molecular

Geometry
• we can classify substances into two broad categories, ionic or molecular:
• Ionic compounds, such as ordinary table salt (NaCl), consist of electrically
charged particles (ions) that bind to each other by electrostatic forces of
attraction.

• In molecular substances, such as water (H2O), the atoms are held to each
other by the sharing of electrons.

• Electron transfer and the formation of ions leads to ionic bonding), while
other combinations bind by electron sharing leads to covalent bonding).

• A chemical bond (maily ionic and covalent bonds) refers to the forces
holding atoms together to form molecules.
• ionic compounds are composed of just two elements: a metal (which
forms the cations) and a nonmetal (which forms the anions).

• For example, NaCl is a binary ionic compound: Na is an Alkali metal,

while Cl is a non-metal.
• Many metallic elements have relatively low ionization potentials and
lose electrons easily. These elements lie to the left in a period or
near the bottom of a group on the periodic table.

• Nonmetal atoms have relatively high electron affinities and thus

readily gain electrons lost by metal atoms, thereby filling their
valence shells. Nonmetallic elements are found in the upper-right
corner of the periodic table.
 Ionic bonds
• Ionic bonds are chemical bonds formed by the electrostatic attraction
between positive and negative ions.

• It is formed when an electron (or electrons) from the valence shell of

one atom is transferred to the valence shell of another atom.

• The atom that loses an electron becomes a positive ion (cation) and
the atom that gains the electron becomes a negative ion (anion).

• The charges of these ions result in an electrostatic attraction between

them and the formation of an ionic bond.
Recall
• A cation (a positive ion) forms when a neutral atom loses one or
more electrons from its valence shell, and an anion (a negative ion)
forms when a neutral atom gains one or more electrons in its valence
shell.
 The Formation of Ionic Compounds

• when sodium chloride is formed from its elements, each sodium atom (a
metal) loses one electron to form a sodium ion, Na+, and each chlorine
atom (non-metal) gains one electron to become a chloride ion, Cl-

• Once formed, these ions become tightly packed together, because their
opposite charges attract.

• This attraction between positive and negative ions in an ionic compound is

what we call an ionic bond.

• Ionic bonding results from the electrostatic attraction of oppositely

charged ions that are typically produced by the transfer of electrons
between metallic and nonmetallic atoms.
Example 7.1: Determining the Electronic Structures of Cations
• Write the electron configurations of Cr3+ and Zn2+. Write
 Covalent Bonding

• Nonmetal atoms frequently form covalent bonds with other nonmetal

atoms. For example, the hydrogen molecule, H2, contains a covalent bond
between its two hydrogen atoms.

• covalent bonds a different type of bonding results from the mutual

attraction of atoms for a “shared” pair of electrons.

• Covalent bonds are formed between two atoms when both have similar
tendencies to attract electrons to themselves (i.e., when both atoms have
identical or fairly similar ionization energies and electron affinities).
Non-polar covalent bonds or pure covalent
bond
• Non-polar covalent bonds are covalent bonds in which the bonding
electrons are equally shared between the bonded atoms.

• This type of covalent bond occurs between atoms of equal or

comparable electronegativities.

• Examples H2, Cl2, and other diatomic molecules.

polar covalent bond,
• Polar covalent bonds are covalent bonds in which there is unequal sharing
• of electrons due to a difference in the electronegativity (Δχ) of the two atoms.
• Polar covalent bonds are formed mostly between non-metals.

• When the atoms linked by a covalent bond are different, the bonding electrons
are shared, but no longer equally.

• Bonding electrons are more attracted to one atom than the other, giving rise to a
shift of electron density toward that atom. This unequal distribution of electrons
is known as a polar covalent bond, characterized by a partial positive charge on
one atom and a partial negative charge on the other.

Cl is more electronegative than H (notice that both are non-metals)

Electronegativity
• Whether a bond is nonpolar or polar covalent is determined by a property
of the bonding atoms called electronegativity.

• Electronegativity is a measure of the tendency of an atom to attract

electrons (or electron density) towards itself. The more strongly an atom
attracts the electrons in its bonds, the larger its electronegativity.

• Electrons in a polar covalent bond are shifted toward the more

electronegative atom; thus, the more electronegative atom is the one with
the partial negative charge.
• The absolute values of the electronegativity differences between the
atoms in the bonds H–H, H–Cl, and Na–Cl are 0 (nonpolar), 0.9 (polar
covalent), and 2.1 (ionic), respectively.

• The degree to which electrons are shared between atoms varies from
completely equal (pure covalent bonding) to not at all (ionic bonding).
 Coordinate covalent bonds
• Coordinate covalent bonds / dative covalent bond are covalent bonds
between two atoms in which both electrons that form the bond come
from the same atom.

• This type of covalent bond is therefore present whenever both bond-pair

electrons are donated by a single atom.

• When the ammonium ion, NH4+, is formed, the fourth hydrogen is

attached by a dative covalent bond, because only the hydrogen's nucleus is
transferred to the nitrogen.
 Hydrogen bonding
• A weak bond between two molecules resulting from an electrostatic attraction
between a proton in one molecule and an electronegative atom in the other.

• Hydrogen bonding, interaction involving a hydrogen atom located between a pair

of other atoms having a high affinity for electrons; such a bond is weaker than an
ionic bond or covalent bond.

• Hydrogen bonds can exist between atoms in different molecules or in parts of the
same molecule. One atom of the pair (the donor), generally a fluorine, nitrogen,
or oxygen atom.
For each letter A - E, identify the type of bond.

A: Ionic bond
B: Non-polar covalent bond
C: Polar covalent bond
D: Hydrogen bond
E: Covalent coordinate or dative bond
Lewis Symbols and Structures
• Lewis structures are very useful in chemistry because they give us a
relatively simple way to describe the structures of molecules.

• You will learn how to use Lewis structures to make reasonably accurate
predictions about the shapes of molecules.

• The Lewis dot notation is a way of describing the outer shell (valence shell)
of an atom’s electrons.

• Dots are drawn around the symbol of the element to represent the
electrons in the valence shell of the atom.
Lewis Symbols and Structures
• Lewis structures are molecular representations that show the
connectivity or bonding of the atoms.

• Unshared electrons (called lone pairs) as well as single, double or

triple bonds are indicated.

• Lewis structures also show any formal charges

Lewis Symbols
• Lewis symbols to describe valence electron configurations of atoms
and monatomic ions.

• E.g, calcium, atomic number 20, has the following electron

configuration: 1S2 2S2 2P6 3S2 3P6 4S2. So it has only two valence
electrons, represented by two dots,
Similarly as above, lewis symbols illustrating the number of valence
electrons for each element in the third period of the periodic table are:
 Lewis Structures
• Lewis symbols to indicate the formation of covalent bonds, which are
shown in Lewis structures, to describe the bonding in molecules and
polyatomic ions.

• E.g, when two chlorine atoms form a chlorine molecule, they share
one pair of electrons:

A dash (or line) is sometimes used to indicate a shared pair of electrons, in a single bond, as in:
 The Octet Rule
• The tendency of main group atoms to form enough bonds to obtain
eight valence electrons is known as the octet rule.

• The number of bonds that an atom can form can often be predicted
from the number of electrons needed to reach an octet (eight valence
electrons)

A main group atom is surrounded by either lone pairs and a bond (line) between the atoms
Exceptions to the Octet rule
• There are three exceptions to the Octet rule, namely:

- molecules with an odd number of electrons

- molecules in which an atom has less than 8 valence electrons
- molecules in which an atom has more than 8 valence electrons

When a molecule has more than 8 electrons in the valence shell, it is

known as an expanded octet.
 Double and Triple Bonds
• A double bond forms when two pairs of electrons are shared
between a pair of atoms.

• A triple bond forms when three electron pairs are shared by a pair of
atoms
Writing Lewis Structures with the Octet Rule
• Please follow carefully all steps 1-5 on page 356 – 358 of the text
book, chemistry 2e, on how to write the Lewis Structures with the
Octet Rule, on more complicated molecules and molecular ions, by
also studying ALL those examples provided, such as SiH4, CHO2−, NO+,
and OF2.
 follow the step-by-step procedure outlined here:

• 1. Determine the total number of valence (outer shell) electrons. For

cations, subtract one electron for each positive charge. For anions,
add one electron for each negative charge.
• 2. Draw a skeleton structure of the molecule or ion, arranging the
atoms around a central atom. (Generally, the least electronegative
element should be placed in the center.) Connect each atom to the
central atom with a single bond (one electron pair).
• 3. Distribute the remaining electrons as lone pairs on the terminal
atoms (except hydrogen), completing an octet around each atom.
• 4. Place all remaining electrons on the central atom.
• 5. Rearrange the electrons of the outer atoms to make multiple bonds
with the central atom in order to obtain octets wherever possible.
Titan also contains ethane (H3CCH3), acetylene (HCCH), and ammonia (NH3). What
are the Lewis structures of these molecules?
 FORMAL CHARGES
• The formal charge of any atom in a Lewis structure is a number
assigned to it according to the number of valence electrons of the
atom and the number of electrons around it.

• formal charge results when we take the number of valence electrons

of a neutral atom, subtract the nonbonding electrons (lone pair
electrons), and then subtract the number of bonds connected to that
atom in the Lewis structure.

• Thus, we calculate formal charge as follows:

• formal charge = # valence shell electrons (free atom) − # lone pair
electrons − ½ (half) # bonding electrons.
 Calculating Formal Charge from Lewis Structures
• Assign formal charges to each atom in the interhalogen ion ICl4−, and
interhalogen molecule BrCl3.

• It is important to understand how to draw the Lewis stricture of

molecules in line with the Octet Rules leaned above.

• The Lewis structure for ion ICl4− is

formal charge = # valence shell electrons (free atom) − # lone pair
electrons − ½ (half) # bonding electrons.

• The valence electrons of Cl atom (free atom) is 7, each atom has 6 number of
lone pair electrons (unbounded electrons) around it, and each Cl atom has only
two bonded electrons (indicated by a line),

• So formal charge of Cl = 7 – 6 – ½(2) = 7 – 7 = 0

• The valence electrons of I atom (free atom) is 7, and has 4 number of lone pair
electrons (unbounded electrons) around it, and I atom has 8 bonded electrons
(indicated by a 4 lines),

• So formal charge of I = 7 – 4 – ½(8) = 7 – 8 = -1

• The sum of the formal charges of all the atoms equals –1, which is identical to the
charge of the ion (–1).
 For interhalogen molecule BrCl3.

• The Lewis structure is:

The valence electrons of Cl atom (free atom) is 7, each atom has 6 number of lone pair electrons
(unbounded electrons) around it, and each Cl atom has only two bonded electrons (indicated by a
line),

So formal charge of Cl = 7 – 6 – ½(2) = 7 – 7 = 0

The valence electrons of Br atom (free atom) is 7, and has 4 number of lone pair electrons
(unbounded electrons) around it, and Br atom has 6 bonded electrons (indicated by a 3 lines),

So formal charge of Br = 7 – 4 – ½(6) = 7 – 7 = 0

All atoms in BrCl3 have a formal charge of zero, and the sum of the formal charges totals zero, as it
must in a neutral molecule.
 Using Formal Charge to Predict Molecular Structure
• A few guidelines involving formal charge can be helpful in deciding
which of the possible structures is most likely for a particular
molecule or ion:
Resonance structures of molecules
• A given compound can have several valid Lewis formulae.
• For example, O3 (ozone) is a molecule that is said to have resonance,
as it can be represented by two different but valid Lewis structures
called resonance forms, or resonance structures, shown below:
• The only accurate way to describe the structure of ozone is to show
both Lewis structures (as shown below) and then indicate that the
true molecule is an average of the two resonance structures.
• Convention dictates that we use double-headed arrows to indicate
that several resonance structures contribute to the same hybrid. The
resonance structures of O3 should be written as follows:
 −
Other examples: NO2 and CO3 2−,
Draw the three Lewis structures for the ion SCN-. (Hint: the carbon atom is
in the middle). Assign the formal charge of each atom in all your
structures. Then decide which resonance structure would be most stable.
Give a short reason for your answer.
By using Formal Charge to Predict Molecular
Structure rules:
• The 3rd structure is out, since its Lewis structure has the highest
number of nonzero formal charges (two), rule 2

• Both the 1st and the 2nd structure has the same number of nonzero
formal charges (one), still rule two,

• but the negative formal charge is carried out by N (middle structure)

(electronegativity: 3.04) the most electronegative atom compared to
S (1st structure ) (electronegativity: 2.58), rule 4, so the middle
structure, is the most stable resonance Lewis structure
 Molecular Structure and Polarity / Valence-shell electron-pair
repulsion (VSEPR) theory

• The valence-shell electron-pair repulsion (VSEPR) model is a simple model

for predicting molecular geometries.

• Valence shell electron-pair repulsion theory (VSEPR theory) enables us to

predict the molecular structure, including approximate bond angles
around a central atom, of a molecule from an examination of the number
of bonds and lone electron pairs in its Lewis structure.

• The VSEPR model assumes that electron pairs in the valence shell of a
central atom will adopt an arrangement that minimizes repulsions
between these electron pairs by maximizing the distance between them.
• The electrons in the valence shell of a central atom form either
bonding pairs of electrons, located primarily between bonded atoms,
or lone pairs.

• The electrostatic repulsion of these electrons is reduced when the

various regions of high electron density assume positions as far from
each other as possible.
 Steps in the prediction of molecular geometry using the VSEPR
model:

• Follow these steps to predict the geometry of an AXn molecule or ion using
the VSEPR method: (All X atoms of AXn need not be identical.)

• Step 1: Determine, from the Lewis structure, how many regions of electron
density are around the central atom. Count a multiple bond as a single
region.

• Step 2: Arrange the electron pairs as shown in the table below.

• Step 3: Obtain the molecular geometry from the directions of the bonding
pairs.
Predicting Electron Pair Geometry and Molecular Structure
• Careful study examples 7.11 – 7.15 of textbook chemistry 2e, which
the use of VSEPR theory to predict the molecular structure of
molecules or ions. Follow the explanations of all those examples
provided.

• Try the following activity from the study guide as an exercise:

 Molecular Polarity and Dipole Moment
• Polar covalent bonds connect two atoms with differing
electronegativities, leaving one atom with a partial positive charge
(δ+) and the other atom with a partial negative charge (δ–), as the
electrons are pulled toward the more electronegative atom. This
separation of charge gives rise to a bond dipole moment.

• Dipole vectors are shown as arrows pointing along the bond from the
less electronegative atom toward the more electronegative atom.
• A small plus sign is drawn on the less electronegative end to indicate
the partially positive end of the bond.
 Dipole Moment
Polar covalent bonds connect two atoms with differing electronegativities,
leaving one atom with a partial positive charge (δ+) and the other atom with a
partial negative charge (δ–), as the electrons are pulled toward the more
electronegative atom. This separation of charge gives rise to a bond dipole
moment.

A whole molecule may also have a separation of charge, depending on its

molecular structure and the polarity of each of its bonds. If such a charge
separation exists, the molecule is said to be a polar molecule (or dipole);
otherwise the molecule is said to be nonpolar. The dipole moment measures the
extent of net charge separation in the molecule as a whole. We determine the
dipole moment by adding the bond moments in three-dimensional space, taking
into account the molecular structure.
When a molecule contains more than one bond, the geometry (VSEPR
theory) must be taken into account. If the bonds in a molecule are arranged
such that their bond moments cancel (vector sum equals zero), then the
molecule is nonpolar (no dipole moment).

To summarize, to be polar (dipole), a molecule must:

1. Contain at least one polar covalent bond.

2. Have a molecular structure such that the sum of the vectors of each bond
dipole moment does not cancel.
 Example 1

Consider the molecule, SF4 , according to the geometry (VSEPR theory), it has a
Sawhorse or SeeSaw molecular geometry structure, AX4E, represented by the
skeleton structure below, where A = S atom, and X = F atom.
Electronegativity increases from left to right across a period, and it decreases down
a group, so Fluorine is more electronegative than S atom, so a Dipole vectors are
shown as arrows pointing along the bond from the less electronegative atom
toward the more electronegative atom

The bond moments of the two vertical X (F atoms) cancel because they are pointed
in opposite directions; however, the other two F atoms have pointed in different
directions, so therefore their bond dipole moment does not cancel. As a result, the
molecule has a dipole moment.
 Example 2
Consider the molecule, SF6 , according to the geometry (VSEPR theory), it has
an Octahedral molecular geometry structure, AX6, represented by the
skeleton structure below, where A = S atom, and X = F atom.
The bond moments of the two vertical X (F atoms) cancel because they are pointed
in opposite directions. In addition, there are also other two pairs of F atoms that are
pointing on opposite direction, which makes the bond moment cancel, so that the
overall bond moment is zero. The molecule therefore has no dipole moment.

For your exercise, try the following molecules and test that indeed they have no dipole moment

[1] PCl5
[2] BF3
[3] CCl4