Bonding: General

Concepts

13.1 Types of Chemical Bonds

13.2 Electronegativity

13.3 Bond Polarity and Dipole Moments

13.4 Ions: Electron Configurations and Sizes

13.5 Formation of Binary Ionic Compounds

13.6 Partial Ionic Character of covalent Bonds

13.7 The Covalent Chemical Bond: A Model

13.8 Covalent Bond Energies and Chemical Reactions

13.9 The Localized Electron Bonding Model

13.10 Lewis Structures

13.11 Resonance

13.12 Exceptions to the Octet Rule

13.13 Molecular Structure: The VSEPR Model

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A computer representation of K3C60, a

superconducting substance formed by reacting
potassium with buckminster fullerine (C60)

Source: Photo Researchers, Inc.

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Quartz grows in beautiful, regular crystals. (right)

Two forms of carbon: graphite and diamond.

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Two forms of carbon; graphite and diamond.

Source: Grant Hellman

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13.1 Types of Chemical Bonds

There are many types of experiments we can perform to
determine the fundamental nature of materials.
We can obtain information about the strength of a bonding
interaction by measuring the energy required to break the
bond, the bond energy.
When solid sodium chloride is melted, it conducts
electricity, a fact that convinces us that sodium chloride
contains Na+ and Cl- ions.
The best simple answer is that the system can achieve the
lowest possible energy by behaving in this way.

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 This is an example of ionic bonding. Ionic substances are

formed when an atom that loses electrons relatively easily
reacts with an atom that has a high affinity for electrons.
That is, an ionic compound results when a metal reacts
with a nonmetal.
The energy of interaction between a pair of ions can be
calculated by using Coulombs law:

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 The negative sign indicates an attractive force. That is, the

ion pair has lower energy than the separated ions. For a
mole of pairs of Na+ and Cl ions, the energy of
interaction is

Lets explore this situation from a very simple points of

view by considering the energy terms that result when two
hydrogen atoms are brought close together, as shown in
Fig. 13.1(a).

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 Under what conditions will the H2 molecule be favored

over the separated hydrogen atoms? That is, what
conditions will favor bond formation? The answer lies in
natures strong tendency to achieve the lowest possible
energy.
A bond will form-that is, the two hydrogen atoms will exist
as a molecular unit-if the system can lower its total energy
in the process.
The distance at which the energy is minimum is called the
equilibrium internuclear distance or, more commonly, the
bond length.
The total energy of this system as a function of distance
between the hydrogen nuclei is shown in Fig. 13.1(b).

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Figure 13.1: (a)The interaction of two hydrogen atoms.

(b) Energy profile as a function of the distance between
the nuclei of the hydrogen atoms. As the atoms
approach each other, the energy decreases until the
distance reaches 0.074 nm (0.74 A) and then begins to
increase again because of repulsions.

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Note four important features of this diagram:

The energy terms involved are the potential energy
that results from the attractions and repulsions among
the charged particles and the kinetic energy caused by
the motions of the electrons.
The zero reference point for energy rises steeply
because of the great importance of the internuclear
repulsive forces at these distances.
At very short distance the energy rises steeply because
of the great importance of the internuclear repulsive
forces at these distance.
The bond length is the distance at which the system
has minimum energy and the bond energy corresponds
to the depth of the well at this distance.
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 The type of bonding we encounter in the hydrogen

molecule and in many other molecules in which electrons
are shared by nuclei is called convalent bonding.
Between these extremes lie intermediate cases in which the
atoms are not so different that electrons are completely
transferred but are different enough so that unequal sharing
results. These are called polar covalent bonds.
When a sample of hydrogen fluoride gas is placed in an
lectric field, the molecules tend to orient themselves as
shown in fig. 13.2, with the fluoride end closest to the
positive pole and the hydrogen end closest to the negative
pole.

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FIGURE 13.2
The effect of an electric field on hydrogen fluoride molecules. (a) When no
electric field is present, the molecules are randomly oriented. (b) When
the field is turned on, the molecules tend to line up with their negative
ends toward the positive pole and their positive ends toward the negative
pole. (This illustration exaggerates the effect. Actually, only a small
fraction of the molecules are lined up with the field at a given instant.)

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13.2 Electronegativity
The different affinities of atoms for the electrons in a bond
are described by a property called electronegativity: the
ability of an atom in a molecule to attract shared electrons
to itself.
To understand Paulings model, consider a hypothetical
molecule HX.

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 Electronegativity values have been determined by this

process for virtually all the elements; the results are given
in Fig. 13.3.
The relationship between electronegativity and bond type
is shown in Table 13.1. for identical atoms
(electronegativity difference of zero) the electrons in the
bond are shared equally and no polarity occurs.

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Figure 13.3: The Pauling electronegativity

values as updated by A.L. Allred in 1961.

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Figure 13.3: The Pauling electronegativity values

as updated by A.L. Allred in 1961. (contd)

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 Example 13.1
Arrange the following bonds according to increasing
polarity: H-H, O-H, Cl-H, S-H, and F-H.
Solution
The polarity of the bond increases as the difference in
electronegativity increases. From the electronegativity
values in Fig. 13.3, the following variation in bond polarity
is expected (the Pauling electronegativity value appears in
parentheses below each element):

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 Although we will not consider the details of Allens

quantum mechanical analysis, it is useful to compare
Allens and Paulings values for some of the more
important representative elements (Table 13.2).

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13.3 Bond Polarity and Dipole Moments

A molecule such as HF that has a center of positive charge
and a center of negative charge is said to be dipolar, or to
have a dipole moment.
A molecule that has a positive center of charge of
magnitude Q and a negative center of charge of magnitude
Q separated by a distance R has a dipole moment give by
the expression.

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 The dipolar character of a molecule is often represented by

an arrow pointing to the negative charge center, with the
tail of the arrow indicating the positive center of charge:

The dipole moment of a molecule gives useful

information about its bonding and electron distribution. For
example.

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 Using the measured dipole moment, we have

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 The dipole moments of some representative diatomic

molecules are listed in Table 13.3.
Polyatomic molecules can also exhibit dipolar behavior.

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 Because the oxygen atom in the water molecule has a

greater electronegativity than the hydrogen atoms, the
molecular charge distribution is that shown in fig. 13.4(a)

This charge distribution causes the water molecule to

behave in an electric field as if it had two centers of chargeone positive and one negative-as shown in fig. 13.4(b).

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Figure 13.4: (a) The charge distribution in the

water molecule. (b) The water molecule
in an electric field.

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 Thus the water molecule has a dipole moment. Similar

behavior is observed for the NH3 molecule (Fig. 13.5).

An example is the CO2 molecule, a linear molecule that has

the charge distribution shown in Fig. 13.6.

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Figure 13.5: (a) The structure and charge distribution

of the ammonia molecule. The polarity of the N-H bonds
occurs because nitrogen has a greater electronegativity than
hydrogen. (b) The dipole moment of the ammonia molecule
oriented in an electric field.

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Figure 13.6: (a) The carbon dioxide

molecule. The opposed bond polarities
cancel, and the carbon dioxide molecule
has no dipole moment.

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Linear molecules

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Planar molecules

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Tetrahedral molecules

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 There are many cases where the bond polarities in

molecules oppose and exactly cancel each other. Some
common types of molecules with polar bonds but without
dipole moments are shown in Table 13.4.

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 Example 13.2
For each of the following molecules, show the direction of
the bond polarities. Also indicate which ones have dipole
moments: HCl, Cl2, SO3 (planar), CH4 (tetrahedral), and
H2S (V-shaped).

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 Solution
The HCl molecule: Because the electronegativity of
chlorine (3.2) is greater than that of hydrogen (2.2), the
chlorine is partially negative, and the hydrogen is partially
negative, and the hydrogen is partially positive. The HCl
molecule has a dipole moment oriented as follows:

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 The Cl2 molecule: Because the two chlorine atoms share

the electrons equally, no bond polarity occurs. The Cl2
molecule has no dipole moment.
The SO3 molecule: Because the elctronegativity of oxygen
(3.4) is greater than that of sulfur (2.6), each oxygen has a
partial negative charge, and the sulfur has a partial positive
charge:

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 However, the bond polarities cancel, and the molecule has

no dipole moment. The CH4 molecule: Carbon has a
slightly higher electronegativity (2.6) than hydrogen (2.2).
This leads to small partial positive charges on the hydrogen
atoms and a small partial negative charge on the carbon:

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 This case is similar to the third type in Table 13.4. since the
bond polarities cancel, the molecule has no dipole moment.
The H2S molecule: Since the electronegativity of sulfur
(2.6) is greater than that of hydrogen (2.2), the sulfur has a
partial negative charge and the hydrogen atoms have a
partial positive charge, which can be represented as
follows:

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 This case is analogous to the water molecule. The polar

bonds result in a dipole moment oriented as shown.

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13.4 Ions: electron Configurations and Sizes

The description of the electron arrangements in atoms that

emerged from the quantum mechanical model has helped a
great deal in our understanding of what consititutes a stable
compound.

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 The following generalizations can be applied to the

electron configurations in most stable compounds:
When two nonmetals react to form a covalent bond,
they share electrons in a way that completes the valence
electron configurations of both atoms. That is, both
nonmetals attain noble gas electron configurations.
When a nonmetal and a representative group metal react
to form a binary ionic compound, the ions form so that
the valence electron configuration of the nonmetal is
completed and the valence orbitals of the metal are
emptied. In this way both ions achieve noble gas
electron configurations.

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 Predicting Formulas of Ionic Compounds

Solid ionic compounds contain a large collection of
positive and negative ions packed together in a way that
minimizes the and repulsions and maximizes the
.. and .. repulsions and maximizes the ..
attractions.
This situation is in contrast to the gas phase of an ionic
substance where discrete ion pairs exist.
We can predict what compound will form by considering
the valence electron configurations of the two atoms:

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 Note that oxygen needs two electrons to fill its 2s and 2p

valence orbitals and to achieve the configuration of neon
(1s22s22p6).
Two electrons are therefore transferred:

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 Table 13.5 shows common elements that form ions with

noble gas electron configurations in ionic compounds.
There are some important exceptions to the rules discussed
here.
For example, tin forms both Sn2+ and Sn4+ ions, and lead
forms both Pb2+ and Pb4+ ions.
Also, bismuth forms Bi3+ and Bi 5+ ions, and thallium forms
Tl + and Tl3+ ions.

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The HCl molecule

has a dipole moment

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Sulfur has a partial

positive charge

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Hydrogen atoms and a small partial negative

charge on the carbon

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Hydrogen atoms have a partial positive charge

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