Chapter 7

Chemical Bonding and Molecular Geometry

Ions

Ions are atoms or molecules bearing an electrical charge.

A cation (a positive ion) occurs when a neutral atom loses one or

more electrons from its valence shell.

An anion (a negative ion) occurs when a neutral atom gains one or

more electrons in its valence shell.
Ionic Bonding

Compounds formed by ions are called ionic compounds (or

salts).

Ions in ionic bonds are held together by electrostatic forces of

attraction between oppositely charged cations and anions.

Properties:

Solids are crystalline structures that are rigid and brittle

High melting and boiling points (suggest strong bonds)

Formation of Ionic Compounds

Binary compounds (composed of two elements): a metal and a

nonmetal

Metals lose electrons easily

Nonmetals gain electrons

In a binary compound, the overall charge of the ionic compound

must be zero (positives must equal negatives)

Formula is the simplest ratio of the numbers of ions necessary to

3-D Structure of Ionic Compound

● The formula for an ionic compound does not represent the

physical arrangement of its ions.

● It is incorrect to refer to a sodium chloride (NaCl) “molecule”

because there is not a single ionic bond, per se, between any
specific pair of sodium and chloride ions.

● The attractive forces between ions are isotropic—the same in all

directions—meaning that any particular ion is equally attracted to
all of the nearby ions of opposite charge. This results in the ions
arranging themselves into a tightly bound, three-dimensional
Electronic Structures of Cations

● When forming a cation, an atom of a main group element tends

to lose all of its valence electrons, thus assuming the electronic
structure of the noble gas that precedes it in the periodic table.

● For example, when calcium forms ions it becomes Ca2+ which is

isoelectronic with Ar.

● Transition metals and inner transition metals can have multiple

oxidation numbers, since they have the ability to lose both s
and d electrons, respectively.
Check Your Learning

1. Potassium and magnesium are required in our diet. Write the

electron configurations of the ions expected from these elements.
Electronic Structures of Anions

● Monatomic anions form when a nonmetal gains electrons to fill

its outer shell.

● The charge is equal to the number of electrons that must be

gained to fill the s and p orbitals of the parent atom.
Check Your Learning

2. Write the electron configurations of a phosphorus atom and its

negative ion. Give the charge on the anion.
Covalent Bonding

In covalent bonding the electrons are shared between the

elements.

Covalent bonds form when two atoms have similar tendencies to

attract electrons to themselves. For example, in the H 2 molecule.

Properties:

Low melting and boiling points (weaker forces of attraction)

Many compounds are liquids or gases, or soft solids

Formation of Covalent Bonds

Covalent bonds are generally formed between two or more

nonmetals.

Generally, covalent bonds occur because as the atoms get closer

together their sublevels overlap. This causes the electrons to
orbit both nuclei.

As the atoms get closer and closer the potential energy first
decreases, then begins to increase.

The bond length is determined by the distance at which the

Pure Covalent Bonds

When electrons are shared in a bond equally, the bond is said to be

a pure covalent bond.

Electrons shared in pure covalent bonds have an equal probability

of being near either nucleus.

Pure bonds occur when the elements are the same or the elements
have the same electronegativity value.
Polar Covalent Bonds

When covalent bonds exist between different elements, the

electrons are not shared equally.

In polar covalent bonding electrons are attracted to the atom that

has the highest affinity for electrons.

The unequal distribution of electrons is known as a polar covalent

bond.

With polar covalent bonds, there is a partial positive charge ( 𝛅+)

on one atom and a partial negative charge (𝛅-) on the other.
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
Electronegativity Trend

In general, electronegativity increases from left to right across a

period in the periodic table and decreases down a group.

Nonmetals tend to have the highest electronegativities, with

fluorine the most electronegative element of all (EN = 4.0).

Metals tend be less electronegative elements, and the group 1

metals have the lowest electronegativities.

Note that noble gases have no electronegativity values because

these atoms usually do not share electrons with others atoms
Electronegativity vs Electron Affinity

The electron affinity of an element is a measurable physical

quantity (the energy released or absorbed when an isolated gas-
phase atom acquires an electron, measured in kJ/mol).

Electronegativity, on the other hand, describes how tightly an

atom attracts electrons in a bond. It is a dimensionless quantity
that is calculated, not measured.
Electronegativity and Bond Type

The absolute value of the difference in electronegativity (ΔEN) of

two bonded atoms provides a rough measure of the polarity to be
expected in the bond and, thus, the bond type.

When the difference is very small or zero, the bond is covalent

and nonpolar.

When it is large, the bond is polar covalent or ionic.

Electronegativity and Bond Type
Check Your Understanding

3. Silicones are polymeric compounds containing, among others, the

following types of covalent bonds: Si–O, Si–C, C–H, and C–C. Using
the electronegativity values in Figure 7.6, arrange the bonds in order
of increasing polarity and designate the positive and negative atoms
using the symbols δ+ and δ–.
Figure 7.6
Lewis Symbols

Lewis symbols to describe

valence electron
configurations of atoms and
monatomic ions.

A Lewis symbol consists of an

elemental symbol
surrounded by one dot for
each of its valence
electrons:
Lewis Structures

We also use Lewis symbols to indicate the formation of covalent

bonds, which are shown in Lewis structures, drawings that
describe the bonding in molecules and polyatomic ions.

In a Lewis structure, electrons that are not used in bonding are

called lone pairs.

A dash (or line) indicates when electrons are shared between

atoms.

When one pair of electrons is shared, a single bond is formed.

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 element hydrogen does not follow the octet rule (it only needs
two electrons to complete the first shell).

Also, transition elements and inner transition elements do not

follow the octet rule.
Multiple Bonds

Sometimes, more than one bond will be needed to get elements to

their octets.

When two pairs of electrons are shared a double bond is formed.

When three pairs of electrons are shared a triple bond is formed.

Writing Lewis Structures

To draw a Lewis Structure:

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
Check Your Learning

4. Both carbon monoxide, CO, and carbon dioxide, CO2, are products
of the combustion of fossil fuels. Both of these gases also cause
problems: CO is toxic and CO2 has been implicated in global climate
change. What are the Lewis structures of these two molecules?
Exceptions to the Octet Rule

There are three categories of exceptions to the octet rule:

1.Odd electron molecules

2.Electron-deficient molecules (less than eight)

3.Hypervalent molecules (more than eight)

Check Your Learning

5. The halogens form a class of compounds called the interhalogens,

in which halogen atoms covalently bond to each other. Write the
Lewis structures for the interhalogens BrCl3 and ICl4−.
Formal Charge

When more than one valid Lewis structure can be drawn formal
charges help us predict the most appropriate structure.

The formal charge of an atom in a molecule is the hypothetical

charge the atom would have if we could redistribute the electrons
in the bonds evenly between the atoms.

formal charge = # valence shell electrons (free atom) − # lone pair

electrons − ½ # bonding electrons

Sum of the formal charges of all atoms in a molecule must be zero;

Example

Draw the Lewis structures of:

1. BF3

2.CCl4

3.NO3-
Check Your Learning

6. Calculate the formal charge for each atom in the carbon monoxide
mole:

7. Determine the formal charge for each atom in NCl 3.

Formal Charge and Molecular Structure
The arrangement of atoms in a molecule or ion is called its
molecular structure.
Rules:
1. A molecular structure in which all formal charges are zero
is preferable to one in which some formal charges are not
zero.
2. If the Lewis structure must have nonzero formal charges,
the arrangement with the smallest nonzero formal charges is
preferable.
3. Lewis structures are preferable when adjacent formal
charges are zero or of the opposite sign.
4. When we must choose among several Lewis structures
Check Your Learning

8. Which is the most likely molecular structure for the nitrite (NO 2−)
ion?
Resonance

If two or more structures can be drawn where formal charge has

been minimized then we use a structure to summarize the
structures, called a resonance structure.

Resonance: if two or more Lewis structures with the same

arrangement of atoms can be written for a molecule or ion, the
actual distribution of electrons is an average of that shown by the
various Lewis structures.

Individuals are called resonance forms and the combination is

Bond Strength: Covalent Bonds

Stable molecules exist because covalent bonds hold the atoms

together.

The strength of a covalent bond is measured by measuring the

energy required to break it, that is, the energy necessary to
separate the bonded atoms.

Separating any pair of bonded atoms requires energy

The stronger a bond, the greater the energy required to break it.
Bond Strength and Length

The strength of a bond between two atoms increases as the

number of electron pairs in the bond increases.

Generally, as the bond strength increases, the bond length

decreases.

Triple bonds are stronger and shorter than double bonds

Double bonds are stronger and shorter than single bonds

Endothermic vs Exothermic Reactions

An exothermic reaction (ΔH negative, heat produced) results

when the bonds in the products are stronger than the bonds in
the reactants.

An endothermic reaction (ΔH positive, heat absorbed) results

when the bonds in the products are weaker than those in the
reactants.

The enthalpy change, ΔH, for a chemical reaction is approximately

equal to the sum of the energy required to break all bonds in the
Enthalpy Change for Reaction

The enthalpy change, ΔH, for a chemical reaction is approximately

equal to the sum of the energy required to break all bonds in the
reactants (energy “in”, positive sign) plus the energy released
when all bonds are formed in the products (energy “out,”
negative sign).

Equation: ΔH = ƩDbonds broken − ƩDbonds formed

Example

Consider the following reaction: H2(g) + Cl2(g)⟶2HCl(g) or H–H(g)

+ Cl–Cl(g)⟶2H–Cl(g)

ΔH = ƩDbonds broken − ƩDbonds formed

ΔH = [DH−H + DCl−Cl]− 2DH−Cl
= [436 + 243] − 2(432) = −185 kJ
Check Your Learning
7. Ethyl alcohol, CH3CH2OH, was one of the first organic chemicals
deliberately synthesized by humans. It has many uses in industry,
and it is the alcohol contained in alcoholic beverages. It can be
obtained by the fermentation of sugar or synthesized by the
hydration of ethylene in the following reaction:

Using the bond energies in Table 7.3, calculate an approximate

enthalpy change, ΔH, for this reaction.
 Bond Abond Length (Å) Bond Energy (kJ/mol)
C–C 1.54 345
C=C 1.34 611
C≡C 1.20 837
Table 7.3

C–N 1.43 290

C=N 1.38 615
C≡N 1.16 891
C–O 1.43 350
C=O 1.23 741
C≡O 1.13 1080
3D Molecules

Lewis structures are 2D drawings, but molecules that form are 3

dimensional and therefore the bond angles and orientation
around the central atom is extremely important.

A bond angle is the angle between any two bonds that include a
common atom, usually measured in degrees.

A bond distance (or bond length) is the distance between the

nuclei of two bonded atoms along the straight line joining the
nuclei.
VSEPR Theory

Valence shell electron-pair repulsion theory (VSEPR theory)

helps predict the molecular structure,and bond angles around a
central atom, of a molecule from a Lewis structure.

VSEPR model minimizes repulsions between electron pairs by

maximizing the distance between them.

The types of electrons in the valence shell are either bonding

pairs of electrons, located primarily between bonded atoms, or
lone pairs.
VSEPR Theory (cont’d)
Repulsion of electrons is reduced when areas of high electron
density assume positions as far from each other as possible.

VSEPR theory predicts the arrangement of electron pairs around

each central atom and, usually, the correct arrangement of
atoms in a molecule.

We should understand, however, that the theory only considers

electron-pair repulsions.

Other interactions, such as nuclear-nuclear repulsions and nuclear-

Electron Pair Geometries

Two regions of electron density

around a central atom in a
molecule form a linear
geometry; three regions form a
trigonal planar geometry; four
regions form a tetrahedral
geometry; five regions form a
trigonal bipyramidal
geometry; and six regions form
an octahedral geometry.
Geometry vs Molecular Structure

The electron-pair geometries shown in Figure 7.16 describe all

regions where electrons are located, bonds as well as lone pairs.

Molecular structure describes the location of the atoms, not the

electrons.

The geometry that includes all electron pairs the electron-pair

geometry.

The structure that includes only the placement of the atoms in the
molecule is called the molecular structure.
Electron Repulsion

VSEPR theory predicts these distortions by establishing an order of

repulsions and an order of the amount of space occupied by
different kinds of electron pairs.

The order of electron-pair repulsions from greatest to least

repulsion is:
lone pair-lone pair > lone pair-bonding pair > bonding pair-
bonding pair
This order of repulsions determines the amount of space occupied
by different regions of electrons as follows:
lone pair > triple bond > double bond > single bond
Electron-Pair
Geometry
Positions in Geometries

Two positions in which constituent atoms can be

placed (the one occupied is the more that gives
the most space for the electrons)
axial position (top and bottom)

equatorial position (the ones in the same plane with the central
atom)
 Predicting Electron Pair Geometry and
Molecular Structure

The following procedure uses VSEPR theory to determine the electron pair
geometries and the molecular structures:
1. Write the Lewis structure of the molecule or polyatomic ion.
2. Count the number of regions of electron density (lone pairs and bonds)
around the central atom. A single, double, or triple bond counts as one
region of electron density.
3. Identify the electron-pair geometry based on the number of regions of
electron density: linear, trigonal planar, tetrahedral, trigonal bipyramidal,
or octahedral.
Prediction

4. Use the number of lone pairs to determine the molecular

structure. If more than one arrangement of lone pairs and chemical
bonds is possible, choose the one that will minimize repulsions,
remembering that lone pairs occupy more space than multiple bonds,
which occupy more space than single bonds. In trigonal bipyramidal
arrangements, repulsion is minimized when every lone pair is in an
equatorial position. In an octahedral arrangement with two lone
pairs, repulsion is minimized when the lone pairs are on opposite
sides of the central atom.
Check Your Learning

8. Carbonate, CO32−, is a common polyatomic ion found in various

materials from eggshells to antacids. What are the electron-pair
geometry and molecular structure of this polyatomic ion?

9. Identify a molecule with trigonal bipyramidal molecular structure.

10. The hydronium ion, H3O+ , forms when acids are dissolved in
water. Predict the electron-pair geometry and molecular structure of
this cation.
Check Your Learning

11. Predict the electron pair geometry and molecular structure for
molecules of XeF2 .

12. In a certain molecule, the central atom has three lone pairs and
two bonds. What will the electron pair geometry and molecular
structure be?
Bond Dipole Moment

When electrons are unevenly shared in a bond, the partial charges

resulting can lead to a bond dipole moment .

The magnitude of a bond dipole moment is represented by the

Greek letter mu (μ ) and is given by the formula shown here,
where Q is the magnitude of the partial charges (determined by
the electronegativity difference) and r is the distance between
the charges: μ = Qr.

The bond moment can be expressed as a vector (having both

Polarity

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.
Dipole

When a molecule contains more than one bond, the geometry

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.

If not, then the molecule is polar as in H2O.

Polarity of Molecules

To be polar, 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.