COLLEGE OF PHARMACY

5.1 THE COVALENT BOND MODEL

Several key differences between ionic and covalent bonding and the resulting ionic and molecular compounds.
1. Ionic bonds form between atoms of dissimilar elements (a metal and a nonmetal). Covalent bond formation
occurs between similar or even identical atoms. Most often two nonmetals are involved.
2. Electron transfer is the mechanism by which ionic bond formation occurs. Covalent bond formation involves
electron sharing.
3. Ionic compounds do not contain discrete molecules. Instead, such compounds consist of an extended array of
alternating positive and negative ions. In covalently bonded compounds, the basic structural unit is a molecule.
Indeed, such compounds are called molecular compounds.
4. All ionic compounds are solids at room temperature. Molecular compounds may be solids (glucose), liquids
(water), or gases (carbon dioxide) at room temperature.

Covalent Bond - is a chemical bond resulting from two nuclei attracting the same shared electrons
(eg.) hydrogen molecule (H₂), the simplest of all molecules.

In terms of Lewis notation, this sharing of electrons by the two hydrogen atoms is diagrammed as follows:

5.2 LEWIS STRUCTURE FOR MOLECULAR COMPOUNDS

Using the octet rule, which applies to electron transfer and electron sharing, and Lewis symbols, let
us now consider the formation of selected simple covalently bonded molecules containing the
element fluorine. Fluorine, located in Group VIIA of the periodic table, has seven valence electrons.
Its Lewis symbol is

The molecules HF, F₂, and BrF, whose Lewis structures follow, represent this situation.

Bonding electrons are pairs of valence electrons that are shared between atoms in a covalent bond.
Nonbonding electrons are pairs of valence electrons on an atom that are not involved in electron sharing.

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SYSTEMATIC PROCEDURES FOR DRAWING LEWIS STRUCTURES
Step 1: Calculate the total number of valence electrons available in the molecule by adding together the valence
electron counts for all atoms in the molecule. The periodic table is a useful guide for determining this number.

An SO2 molecule has 18 valence electrons available for bonding.

Sulfur (Group VIA) has 6 valence electrons, and each oxygen (also Group VIA) has 6 valence electrons.
The total number is therefore 6 + 2(6) = 18.

Step 2: Write the chemical symbols of the atoms in the molecule in the order in which they are bonded to one
another, and then place a single covalent bond, involving two electrons, between each pair of bonded atoms.
For SO2, the S atom is the central atom.
O: S : O
The central atom is the atom that appears only once in the formula; (lowest number of subscripts) for example,
S is the central atom in SO₃, O is the central atom in H₂O, and P is the central atom in PF₃.

In molecular compounds containing hydrogen, oxygen, and an additional element, that additional element is the
central atom; for example, N is the central atom in HNO₃, and S is the central atom in H₂SO₄.

Step 3: Add nonbonding electron pairs to the structure such that each atom bonded to the central atom has an
octet of electrons. Remember that for hydrogen, an “octet” is only 2 electrons.

For SO2, addition of the nonbonding electrons gives

At this point, 16 of the 18 available electrons have been used.

Step 4: Place any remaining electrons on the central atom of the structure. Placing the two remaining electrons
on the S atom gives

Step 5: If there are not enough electrons to give the central atom an octet, then use one or more pairs of
nonbonding electrons on the atoms bonded to the central atom to form double or triple bonds.
The S atom has only 6 electrons. Thus a nonbonding electron pair from an O atom is used to form a sulfur–oxygen
double bond.

This structure now obeys the octet rule.

Step 6: Count the total number of electrons in the completed Lewis structure to make sure it is equal to the total
number of valence electrons available for bonding, as calculated in Step 1. This step serves as a “double-check” on
the correctness of the Lewis structure.

The preceding four examples of Lewis structures involved diatomic molecules, the simplest type of molecule. The
“thinking pattern” used to draw these diatomic Lewis structures easily extends to triatomic and larger molecules.

1. H₂O, NH₃, and CH₄

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5.3 SINGLE, DOUBLE, AND TRIPLE COVALENT BONDS
1. SINGLE COVALENT BOND is a covalent bond in which two atoms share one pair of electrons.

2. DOUBLE COVALENT BOND is a covalent bond in which two atoms share two pairs of electrons.
A common molecule that contains a double covalent bond is CO₂ (carbon dioxide). In fact, there are two carbon–
oxygen double covalent bonds present in CO₂.

3. TRIPLE COVALENT BOND is a covalent bond in which two atoms share three pairs of electrons.
A. N₂

B. C₂H₂ (acetylene)

C. HCN (hydrogen cyanide) contains a heteroatomic triple covalent bond.

Examples:

5.4 VALENCE ELECTRON AND COVALENT BONDS FORMED

Not all elements can form double or triple covalent bonds. There must be at least two vacancies in an atom’s
valence electron shell prior to bond formation if it is to participate in a double bond, and at least three vacancies are
necessary for triple-bond formation. This requirement eliminates Group VIIA elements (fluorine, chlorine, bromine,
iodine) and hydrogen from participating in such bonds. Let us consider the possible “bonding behaviors” for O (six
valence electrons, two-octet vacancies), N (five valence electrons, three octet vacancies), and C (four valence
electrons, four octet vacancies).

1. Nitrogen is a very versatile element with

respect to bonding. It can form single,
double, or triple covalent bonds as
dictated by the other atoms present in a
molecule.
2. Carbon is an even more versatile
element than nitrogen with
respect to a variety of types of
bonding, as illustrated by the
following possibilities. In each
case, carbon forms four bonds.

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5.5 ELECTRONEGATIVITY

Electronegativity is a measure of the relative attraction that an atom has for the shared electrons in a bond.

Linus Pauling, whose contributions to

chemical bonding theory earned him a
Nobel Prize in chemistry, was the first
chemist to develop a numerical scale of
electronegativity.

The table gives Pauling electronegativity

values for the more frequently
encountered representative elements.
The higher the electronegativity value for
an element, the greater the attraction of atoms of that element
for the shared electrons in bonds.

Predicting Electronegativity Relationships Using General Periodic Table Trends

Predict which member of each of the following pairs of elements the greater electronegativity value has based on
periodic table electronegativity relationships.

a. Cl or Br
Solution: Cl and Br are in the same periodic table group, with Cl being above Br. Therefore Cl is the more
electronegative element, as electronegativity decreases going down a group.
b. C or O
Solution: C and O are in the same periodic table period, with O being farther to the right. Therefore O has the
greater electronegativity, as electronegativity increases going across a period.
c. Li or K
Solution: Li and K are in the same group, with Li being two positions above K. Therefore Li is the more
electronegative element, as electronegativity decreases going down a group.
d. Al or N
Solution: Al is in Period 3 and N is in Period 2. The element P can be used as a “link” between the two elements. It
is in the same period as Al and the same group as N. The periodic table period trend predicts that P is more
electronegative than Al and the periodic table group trend predicts that N is more electronegative than P.
Therefore, N is more electronegative than Al.

5.6 BOND POLARITY

A nonpolar covalent bond is a covalent bond in which there is equal sharing of electrons between two atoms.
symmetrical e-density, and usually identical atoms.
Example: H-H

A polar covalent bond is a covalent bond in which there is unequal sharing of electrons between two atoms,
asymmetrical e- density.

Ionic Bond - e- are NOT shared, e- are transferred from the least electronegative atom to the most electronegative
atom, The most electronegative atom gains an e- and becomes negatively charged and The least electronegative
atom loses and e- and becomes positively charged.

***A notation that involves the lower-case Greek letter delta (δ) is used to denote fractional charge. The symbol:

δ ⁻meaning “fractional negative charge,” is placed above the more electronegative atom of the bond, and the symbol
δ⁺, meaning “fractional positive charge,” is placed above the less electronegative atom of the bond.

With delta notation, the direction of polarity of the bond in hydrogen chloride (HCl) is depicted as:

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The direction of polarity of a polar covalent bond can also be designated by

using an arrow with a cross at one end (6). The cross is near the end of the bond
that is “positive,” and the arrowhead is near the “negative” end of the bond.
Using this notation, we would denote the bond in the molecule HCl as

Bond polarity is a measure of the degree of inequality in the sharing of electrons between two atoms in a chemical
bond.

***Guidelines, which relate to the electronegativity difference between bonded atoms.

1. Bonds that involve atoms with the same or very similar electronegativities are called nonpolar covalent bonds.
“Similar” here means an electronegativity difference of 0.4 or less.
2. Bonds with an electronegativity difference greater that 0.4 but less than 1.5 are called polar covalent bonds.
3. Bonds with an electronegativity difference greater than 2.0 are called ionic bonds.
4. Bonds with an electronegativity difference between 1.5 and 2.0 are considered ionic if the bond involves a
metal and a nonmetal, and polar covalent if the bond involves two nonmetals.

Using Electronegativity Difference to Predict Bond Polarity and Bond Type

Consider the following bonds:

N−Cl Ca−F C−O B−H N−O

a. Rank the bonds in order of increasing polarity.

b. Determine the direction of polarity for each bond.
c. Classify each bond as nonpolar covalent, polar covalent, or ionic.

Solution
First, the electronegativity difference for each of the bonds is calculated using the electronegativity values.

a. Bond polarity increases as the electronegativity difference increases. Using the mathematical symbol <, which
means “is less than,” we can rank the bonds in terms of increasing bond polarity as follows:

b. The direction of bond polarity is from the least electronegative atom to the most electronegative atom. The
more electronegative atom bears the fractional negative charge (δ ⁻)

c. Nonpolar covalent bonds require a difference in electronegativity of 0.4 or less

An electronegativity difference of 2.0 or greater corresponds to ionic bonds.
Bonds with an electronegativity difference greater than 0.4 but less than 1.5 are polar covalent.

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If the electronegativity difference is between 1.5 and 2.0, the bond is polar covalent if it involves two nonmetals,
but is considered ionic if the bond involves a metal and a nonmetal. Using these guidelines the bond
classifications are:

5.7 NAMING BINARY MOLECULAR COMPOUNDS

A binary molecular compound is a molecular compound in which only two nonmetallic elements are present.

Here is the basic rule to use when constructing the name of a binary molecular compound:

The full name of the nonmetal of lower electronegativity is given first, followed by a separate word containing the
stem of the name of the more electronegative nonmetal and the suffix -ide. Numerical prefixes, giving numbers of
atoms, precede the names of both nonmetals.

Naming Binary Molecular Compounds

Name the following binary molecular compounds.

Solution
The names of each of these compounds will consist of two words. These words will have the following general
formats:

a. The elements present are sulfur and chlorine. The two portions of the name (including prefixes) are disulfur
and dichloride, which are combined to give the name disulfur dichloride.
b. b. When only one atom of the first nonmetal is present, it is customary to omit the initial prefix mono-. Thus
the name of this compound is carbon disulfide.
c. The prefix for four atoms is tetra- and for ten atoms is deca-. This compound has the name
tetraphosphorus decoxide.
d. Omitting the initial mono- (see part b), we name this compound carbon tetrabromide.

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