Chapter 11: Chemical Bonding I- Basic Concepts

I. Lewis Theory
1Electrons, especially those of the outermost (valence) electronic shell, play fundamental
role in chemical bonding.
2 In some cases, electrons are transferred from one atom to another. Positive and negative
ions are formed and attracted each other through electrostatic forces called ionic bonds.
3 In other cases, one or more pairs of electrons are shared between atoms. A bond formed
by the sharing of electrons between atoms is called covalent bond.
4 Electrons are transferred or shared in such a way that each atom acquires an especially
stable electron configuration. Usually, this is a noble gas configuration, one with eight
outer-shell electrons, or an octet.

Lewis Symbols and Lewis Structure (formula)

Lewis developed a special set of symbols for his theory. A Lewis symbol consists of a
chemical symbol to represent the nucleus and core (inner-shell) electrons of an atom,
together with dots placed around the symbol to represent the valence electrons.
E.g. the Lewis symbol for Mg, Si, N and Se

Electron spin had not yet been proposed when Lewis framed his theory, and so he did not
show that two of the valence electrons (3s2) are paired and two (3p2) are unpaired.

A Lewis structure is a combination of Lewis symbols that represents either the transfer
or sharing of electrons in a chemical bond.
For ionic compound:
The formula unit of an ionic compound is the simplest electrically neutral collection of
cations and anions from which we can establish the chemical formula of the compound.
In the Lewis structure of an ionic compound of main-group elements
(1) the Lewis symbol of the metal ion has no dots if all the valence electrons are lost and
(2) the ionic charges of both ions are shown.
E.g. Write Lewis structures for the following compounds: (a) BaO (b)MgCl2
(a) Write the Lewis symbol, and determine how many electrons each atom must gain or
lose to acquire a noble gas electron configuration.

II Covalent Bonding :
A covalent bond can be described as a pair of electrons shared by two atoms.
E.g.
lone pair e- is the electron pairs that are not
.. .. .. .. .. .. involved in bonding.
Cl . + . Cl . Cl or
.. . ..
Cl Cl Cl
..

..

..
..

..

..

.. .. .. ..

Bond pair e-
is a pair of electrons shared between atoms in a covalent bond.
The sharing of a single pair of electrons between bonded atoms produces a single
covalent bond.
The sharing of two pairs of electrons between bonded atoms produces a double covalent
bond. E.g.
.. .. .. ..
. O . + .O O O
.. ..
.

.. ..
The sharing of three pairs of electrons between bonded atoms produces a triple covalent
bond. E.g.
.. .. .. ..
. N . + .N N N
. .
.
Coordinate Covalent Bonds
A covalent bond in which a single atom contributes both of the electrons to a shared pair
is called a coordinate covalent bond.
E.g.

III Polar Covalent Bonds

A polar covalent bond is a covalent bond in which electrons are not shared equally
between two atoms.
E.g.
+ .. δ−
δH Cl
..
..

.. δ +
= partial positive charge
In HCl molecule, Cl (more EN) attracted electrons more strongly than does H. The
electron charge density is greater near the Cl atom than H atom. The center of negative
charge lies closer to the Cl nucleus than the center of positive charge. We say that there
is a separation of charge in H-Cl bond and that the bond is polar.

Electronegativity (EN)
~ describe an atom’s ability of atoms to complete for electrons with other atoms to which
it is bonded. A widely used EN scale is one devised by Linus Pauling.
Linus Pauling defined EN as the power of an atom in a molecule to attract electrons to
itself.
Pauling’s EN, is based on thermochemical data and the scale is arbitray assigned
F = 4.0
EN is related to ionization energy, I, and electron affinity, EA. In general, EN decrease
from top to bottom in a group and increase from left to right in a period of elements.
If ∆ EN for two atoms is very small, the bond between them is essentially covalent.
If ∆ EN for two atoms is large, the bond is essentially ionic.
For intermediate values of ∆ EN, the bond is described as polar covalent bond.
E.g. Which bond is more polar, HCl or HI?

The bonding continuum from ionic to nonpolar covalent. Polar covalent bonds lie
between the two extremes. They are characterized by an unsymmetrical electron
distribution in which the bonding electrons are attracted somewhat more strongly by one
atom than the other. The symbol d (Greek delta) means partial charge, either partial
positive (δ +) or partial negative (δ -).

IV. Writing Lewis Structures: We always try to satisfy the octet rule when writing
Lewis formula
1 Determine the total number of valence electrons in the molecule by adding the numbers
of valence electrons for all the atoms in the molecule. If the species is an ion rather than a
molecule, then you must take the charge of the ion into account by adding or substracting
electrons.

Write a Lewis structure for OF2

2 Identify the central atoms and terminal atoms. A central atom is bonded to two or more
atoms, and a terminal atom is bonded to just one other atom. Sometime the correct
arrangement can only be found by trial and error.
* H atoms are always terminal atoms.
* Central atoms are generally those with lowest EN.
* Carbon atoms are always central atoms.
* Except for the very large number of chainlike organic molecules, molecules and
polyatomic ions generally have compact, symmetrical structures.
3 Write a plausible skeletal structure: Arrange the symbol of the atoms in the order in
which they are bonded to one another. Then, join the atoms in the skeletal structure by a
single bonds (two electrons), which can be represented by a single line between two
atoms that are assumed to bond to each other.

4 Counting the remaining electrons, subtract two e- for each bond from the total number
of valence electrons.

5 Now arrange remaining valence electrons as lone pairs about each atom so that octet
rule is satisfied for each one. First complete the octets of the terminal atoms. Then to the
extent possible, complete octets for all the atoms. Usually, each atom acquires an outer
shell octet of electrons. Hydrogen, however, is limited to two outer shell electrons.

6 Sometimes, multiple covalent bond, (double or triple bonds) are needed. Multiple
covalent bonds are formed most readily by C, N, O, P and S atoms.
If one or more central atoms is left with an incomplete octet after step 5, move lone-pair
electrons from terminal atoms to form multiple covalent bonds to central atoms. Do this
to the extent necessary to give all atoms complete octets.
 −
E.g. Write a plausible Lewis structure for CN

Formal Charge- as an aid to find the best Lewis structure that represent the molecule or
ions.
~ are apparent charges on certain atoms in Lewis structure that arise when atoms have not
contribute equal numbers of electrons to the covalent bonds joining them, and they are
assigned by a set of arbitrary rules and do not necessary represent the actual charges on
the atom. To assign formal charge we assume that each pair of e- is share equally
between the bonded atoms. Count lone-pair electrons as belonging to the atom on which
they are found
Therefore,

E.g. Consider OF2 again

V Resonance
For many molecules and ions, we can write two or more equally satisfactory Lewis
−
structures. E.g. NO2
One Lewis structure is

Another equally acceptable Lewis structure is

Both of these Lewis structure satisfy the octet rule. When it is possible to write two or
more satisfactory Lewis structure without altering the positions of the nuclei, the actual
structure is viewed as an average of the individual structure. Each of the individual
Lewis structure is said to be a resonance form. We indicate resonance forms by means
of a two-headed arrow. Neither of the individual Lewis structure taken separately
accurately reflects the actual bonding. The true structure is a resonance hybrid of
plausible contributing structure.
The resonance hybrid for the nitrite ion suggests that the –1 charge of the ion is shared equally by
the two oxygen atoms, rather than being completely on either one of two oxygen. In such case
we say that the charge is delocalized. Resonance hybrids with delocalized charges have lower
energies than their individual resonance forms.
Structures with different energy may also contribute to an overall resonance hybrid, but
in general the higher the energy of a Lewis structure, the smaller the contribution. For
Lewis structure: The lowest energy structure is the one with the smallest formal charges
on atoms.
E.g BF3

VI Exception to the Octet Rule

Odd-electron Species
In some case the octet rule cannot be satisfied by each atom in a species with an odd total
number of electrons. E.g. nitrogen oxide NO

A species with one or more unpaired electrons is called a free radical. The presence of
unpaired electrons causes odd-electron species to be paramagnetic.

Incomplete octets
Some compounds, called electron-deficient compounds, have an even number of outer
electrons but do not have enough electrons to form octets about each atom. E.g. beryllium
hydride, BeH2.
Expanded Valence Shells
There are some Lewis structures that break octet rule by having 10 or 12 valence
electrons around the central atoms, creating what is called expanded valence shell.
Atoms of the third periodic elements and beyond can expand their valence shells.
E.g. sulfur tetraflouride, SF4.

Sulfur lies in the third row of the periodic table, so we added the remaining two electrons
as a lone pair to the sulfur atom. Thus the Lewis structure is
..
F
..
..

.. ..
..

F S F..
..

..

..

..F
..
..

VII The Shapes of Molecules

Lewis structure show the bonding relationships among atoms in a molecule but do not
indicate the molecule’s actual shape. A simple theory enable us to predict the shapes
(geometry) of molecules which based on total # of bonds and lone electron pairs in the
valence shell of the central atom in the molecule is the valence-shell electronic pair
repulsion theory.

Valence –Shell Electron-Pair Repulsion (VSEPR) Theory

Electron pairs repel each other whether they are in chemical bonds (bond pair) or
unshared (lone pairs). Electron pairs assume orientations about an atom to minimize
repulsions.
E.g. Consider BeCl2
Although the central Be atom has no lone pair, it does have two covalent bonds and thus
have two bonding electron pairs in its valence shell. These valence shell electrons pairs
repel each other and can minimize their mutual repulsion by being as far apart as
possible. The two bonds minimize their mutual repulsion by being at opposite sides of
the central Be atom, and the Cl-Be-Cl bond angle is 180°. The shape of the molecule is
determined by the location of the atomic nuclei in the molecule, so we say that BeCl2 is a
linear molecule.
Bond angle is the angle between adjacent lines representing bonds.

180o
.. ..
Cl Be Cl
..
..

.. ..
 →Bond length is the distance between the nuclei of bonded atoms.

E.g. CH4 , NH3 and H2O

* The closer together two groups of electrons are forced, the stronger the repulsion
between them. The repulsion between two electron groups is much stronger at small
angle than at large angle.

Apply VSEPR theory

1) Draw a plausible Lewis structure
2) Determine the number of electron groups around central atom.
3) Establish the electron-group geometry around the central atom
4) determine the molecular geometry from the position around the central atom occupied
by the other atomic nuclei.

Structure with multiple covalent bonds

In predicting the shape of molecules by VSEPR theory, we count double or triple bond s
one group of electrons connecting the ligand X to the central atom A. We use this rule
because all the bonding electrons between two atoms must be shared between those same
two atoms.
E.g. H2CO
1) the Lewis structure is
Molecule Shape and Dipole Moment
E.g. In HCl, the Cl atom is more electronegative than H and electron are displace toward
the Cl atom. The HCl is a polar molecule with a dipole moment which is indicated by a
cross-base arrow that point to the atom attract electron more strongly.

The extend of the charge displace in a polar covalent bond is given by the dipole
moment, µ .
Molecular geometry determines whether or mot a molecule has a net dipole moment.
E.g CO2 a nonpolar molecule.
Bond Order and Bond Length
The term bond order describe whether the a covalent bond is single, double or triple etc.
For a covalent bond, bond length between two atom can be approximated as the sum of
the covalent radii of the two atoms.

Bond Energy (BE)

Energy is release when isolated atoms join to form a covalent bond, and energy must be
absorbed to break a bond.
Bond-dissociation energy, D, is the quantity of energy required to break one mole of
covalent bonds in a gaseous species.
Bond breaking H2(g) →2H(g) ∆ H = ∆ (H-H) = +436 kJ/mol
An average bond energy is the average of bond dissocation energies for a number of
different species containing the particular bond.
In a reaction, the enthalpy change of a reaction is