CHAPTER SIX

Chemical Bonding and Molecular Geometry

Introduction
Ø Experimental evidence discovered the formula, C60, and then
scientists determined how 60 carbon atoms could form one
symmetric, stable molecule.
Ø They were guided by bonding theory-the topic of this
chapter-which explains how individual atoms connect to
form a bond.

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 6.1. Ionic Bonding

Ø Ions are atoms or molecules bearing an electrical charge.

• These are cation and anion
Ø A cation (a positive ion) forms when a neutral atom loses one
or more electrons from its valence shell.
Ø an anion (a negative ion) forms when a neutral atom gains one
or more electrons in its valence shell.
Ø Compounds composed of ions are called ionic compounds (or
salts), and their constituent ions are held together by ionic
bonds: electrostatic forces of attraction between oppositely
charged cations and anions.

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 Cont…..

Ø Ionic solids exhibit a crystalline structure and tend to be rigid

and brittle; they also tend to have high melting and boiling
points, which suggests that ionic bonds are very strong.
Ø Ionic solids are also poor conductors of electricity for the
same reason-the strength of ionic bonds prevents ions from
moving freely in the solid state.
Ø Most ionic solids, however, dissolve readily in water.
Ø Once dissolved or melted, ionic compounds are excellent
conductors of electricity and heat because the ions can move
about freely.
Q. Why ionic solids poor conductors of electricity than ionic
compound solution form?

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 Cont….
Ø Neutral atoms and their associated ions have very different
physical and chemical properties.
Sodium atoms
• form sodium metal,
• a soft, silvery-white metal that burns vigorously in air and
• reacts explosively with water.
Chlorine atoms
§ form chlorine gas, Cl2,
§ a yellow-green gas that is extremely corrosive to most metals
and
§ very poisonous to animals and plants.

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 Cont….

Ø The vigorous reaction between the elements sodium and

chlorine forms the white, crystalline compound sodium
chloride, common table salt, which contains sodium cations
and chloride anions.
Ø Chlorine is poisonous, but sodium chloride is essential to life;
sodium atoms react vigorously with water, but sodium chloride
simply dissolves in water.

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 6.1.1. The Formation of Ionic Compounds
Ø Binary ionic compounds are composed of just two elements: a
metal and nonmetal.
Ø Many metallic elements have relatively low ionization
potentials and lose electrons easily.
Ø These elements lie to the left in a period or near the bottom of
a group on the periodic table.
Ø Nonmetal atoms have relatively high electron affinities and
thus readily gain electrons lost by metal atoms, thereby
filling their valence shells.
Ø Nonmetallic elements are found in the upperright corner of the
periodic table.

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 Cont…..
.
Ø 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.
Ø This results in the ions arranging themselves into a tightly
bound, three-dimensional lattice structure.

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 Cont…
Ø The atoms in sodium chloride (common table salt) are
arranged to (a) maximize opposite charges interacting.
Ø In the expanded view (b), the geometry can be seen more
clearly.

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 6.1.2. Electronic Structures of Cations and Anions

Ø When a Ca atom loses both of its valence electrons, the result

is a cation with 18 electrons, a 2+ charge, and an electron,
configuration of 1s22s22p63s23p6.
Ø The Ca2+ ion is therefore isoelectronic with the noble gas Ar.
Example
Ø Two of these essential trace elements, chromium and zinc, are
required as Cr3+ and Zn2+ . Write the electron configurations of
these cations.

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 Cont….
Solution
Ø First, write the electron configuration for the neutral atoms:
Zn: [Ar]3d104s2
Cr: [Ar]3d54s1
Ø Next, remove electrons from the highest energy orbital.
Ø For the transition metals, electrons are removed from the s
orbital first and then from the d orbital.
Ø For the p-block elements, electrons are removed from the p
orbitals and then from the s orbital.
• Zn2+ : [Ar]3d10
• Cr3+ : [Ar]3d3

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Example
Determining the Electronic Structure of Anions
Ø Selenium and iodine are two essential trace elements that form
anions.
Ø Write the electron configurations of the anions.
Solution
Se2– : [Ar]3d104s24p6 I– : [Kr]4d105s25p6

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 6.2. Covalent Bonding
Ø A different type of bonding results from the mutual attraction
of atoms for a “shared” pair of electrons.
§ Such bonds are called covalent bonds.
Ø 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).
Ø Covalent compounds generally have much lower melting and
boiling points than ionic compounds, Because the attraction
between molecules, which electrically neautral, is weaker
than that between electrically charged ions.

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 Cont….
Q. why covalent compounds are poor conductor of electricity at
any state?
6.2.1. Formation of Covalent Bonds
Ø Nonmetal atoms frequently form covalent bonds with other
nonmetal atoms.
Ø For H2, we have two separate hydrogen atoms with a particular
potential energy, indicated by the red line.
Ø As the two atoms approach each other (moving left along the
x-axis), their valence orbitals (1s) begin to overlap.

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 Cont….
Ø The single electrons on each hydrogen atom then interact with
both atomic nuclei, occupying the space around both atoms
Ø The strong attraction of each shared electron to both nuclei
stabilizes the system, and the potential energy decreases as the
bond distance decreases.
Ø If the atoms continue to approach each other, the positive
charges in the two nuclei begin to repel each other, and the
potential energy decreases.
Ø The bond length is determined by the distance at which the
lowest potential energy is achieved.

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 Cont….
Two atoms of hydrogen approaches,

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 Cont…..
Ø The covalent bond is very strong; a large amount of energy,
436 kJ, must be added to break the bonds in one mole of
hydrogen molecules and cause the atoms to separate:
Ø Chemical bond breaking is an endothermic process

Ø whereas forming chemical bonds an exothermic process).

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 6.2.2. Polarity of Covalent Bonds
Ø If the atoms that form a covalent bond are identical, as in H2, Cl2,
and other diatomic molecules, then the electrons in the bond must
be shared equally.
q We refer to this as a pure covalent bond.
Ø When the atoms linked by a covalent bond are different, the bonding
electrons are shared, but no longer equally.
Ø This unequal distribution of electrons is known as a polar
covalent bond
Ø Characterized by a partial positive charge on one atom and a partial
negative charge on the other.
Ø The atom that attracts the electrons more strongly acquires the partial
negative charge and vice versa.

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 6.3. Lewis Structures

Ø 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.
The Octet Rule
Ø The tendency of main group atoms to form enough bonds to
obtain eight valence electrons is known as the octet rule.

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 6.3.1. Writing Lewis Structures with the Octet Rule
Ø For very simple molecules and molecular ions, we can write
the Lewis structures by simply pairing up the un paired
electrons on the constituent atoms.

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 Rules
Helpful to 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.

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 Cont……
Ø Let us determine the Lewis structures of SiH4, CHO2−, NO+,
and OF2 as examples in following this procedure:
SiH4

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 CHO2−

It follows

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 Cont…..
OF2

Q. Write Lewis structure with the octet rule for NO+

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 Cont….
Writing Lewis Structures
Write the Lewis structure of the following molecules
HCN, H3CCH3, HCCH, NH3

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 6.3.2. Exceptions to the Octet Rule

Ø Many covalent molecules have central atoms that do not have

eight electrons in their Lewis structures.
Ø These molecules fall into three categories:
q Odd-electron molecules have an odd number of valence
electrons, and therefore have an unpaired electron.
q Electron-deficient molecules have a central atom that has
fewer electrons than needed for a noble gas configuration.
q Hypervalent molecules have a central atom that has more
electrons than needed for a noble gas configuration.

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 Odd-electron Molecules
Ø We call molecules that contain an odd number of electrons
free radicals.
Ø Nitric oxide, NO, is an example of an odd-electron molecule;
it is produced in internal combustion engines when oxygen
and nitrogen react at high temperatures.
Ø The sum of the valence electrons is 5 (from N) + 6 (from O) =
11.
Ø We can easily draw a skeleton with an N–O single bond.
Ø We give eight electrons to the more electronegative atom in
these situations; thus oxygen has the filled valence shell.
Ø We take one of the lone pairs from oxygen and use it to form a
NO double bond.

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 Electron-deficient Molecules
Ø We will also encounter a few molecules that contain central
atoms that do not have a filled valence shell.
Ø Generally, these are molecules with central atoms from groups
2 and 13, outer atoms that are hydrogen, or other atoms that do
not form multiple bonds.
Ø For example, in the Lewis structures of beryllium dihydride,
BeH2, and boron trifluoride, BF3, the beryllium and boron
atoms each have only four and six electrons, respectively

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 Cont…
Ø An atom like the boron atom in BF3, which does not have
eight electrons, is very reactive.
Ø It readily combines with a molecule containing an atom with a
lone pair of electrons.
Ø For example, NH3 reacts with BF3 because the lone pair on
nitrogen can be shared with the boron atom:

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 Example

Writing Lewis Structures:

Ø Octet Rule Violations Xenon is a noble gas, but it forms a
number of stable compounds.
Ø What are the Lewis structures of XeF2 and XeF6?

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 6.4. Formal Charges and Resonances
6.4.1. Calculating Formal Charge
Ø We can use the concept of formal charges to help us predict the
most appropriate Lewis structure when more than one is
reasonable.
Ø Formal charge results when we take the number of valence
electrons of a neutral atom, subtract the nonbonding electrons,
and then subtract the number of bonds connected to that atom
in the Lewis structure.
Ø Thus, we calculate formal charge as follows:

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 Cont…..
Ø The sum of the formal charges of all atoms in a molecule must
be zero;
• the sum of the formal charges in an ion should equal the
charge of the ion.
Ø We must remember that the formal charge calculated for an
atom is not the actual charge of the atom in the molecule.
Ø Formal charge is only a useful book keeping procedure; it does
not indicate the presence of actual charges.
Example
Calculating Formal Charge from Lewis Structures
Assign formal charges to each atom in the interhalogen ion ICl4−.

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 Cont…..
Solution
Step 1: We divide the bonding electron pairs equally for all I-Cl
bonds:

Step 2: We assign lone pairs of electrons to their atoms.

Each Cl atom now has seven electrons Assigned to it, and
the I atom has eight.
Step 3: Subtract this number from the number of valence
electrons for the neutral atom:
I: 7 – 8 = –1
Cl: 7 – 7 = 0

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 Cont…
Calculating Formal Charge from Lewis Structures
Ø Assign formal charges to each atom in the interhalogen
molecule BrCl3.
Solution
Step 1: Assign one of the electrons in each Br–Cl bond to the Br
atom and one to the Cl atom in that bond:

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 Cont…
Step 2: Assign the lone pairs to their atom. Now each Cl atom
has seven electrons and the Br atom has seven electrons.
Step 3: Subtract this number from the number of valence
electrons for the neutral atom.
Ø This gives the formal charge:
Br: 7 – 7 = 0 Cl: 7 – 7 = 0
Ø 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.

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 6.4.2. Predicting molecular structure using formal charge
Ø The arrangement of atoms in a molecule or ion is called its
molecular structure.
Ø 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:
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.

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 Cont……
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 with
similar distributions of formal charges, the structure with the
negative formal charges on the more electronegative atoms is
preferable.
Ø let us consider some possible structures for carbon dioxide,
CO2.
We can draw three possibilities for the structure: carbon in the
center and double bonds, carbon in the center with a single and
triple bond, and oxygen in the center with double bonds:

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 Cont….
Ø Comparing the three formal charges, we can definitively
identify the structure on the left as preferable because it has
only formal charges of zero (Guideline 1).

Ø As another example, the thiocyanate ion, an ion formed from a

carbon atom, a nitrogen atom, and a sulfur atom.
Ø have three different molecular structures: NCS–, CNS–, or
CSN–.

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 Cont….

Ø The formal charges present in each of these molecular

structures can help us pick the most likely arrangement of
atoms.

Ø Note that the sum of the formal charges in each case is equal to
the charge of the ion (–1).

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 Cont……
Ø However, the first arrangement of atoms is preferred because it
has the lowest number of atoms with nonzero formal charges
(Guideline 2).
Ø Also, it places the least electronegative atom in the center, and
the negative charge on the more electronegative element
(Guideline 4).
Using Formal Charge to Determine Molecular Structure
Ø Nitrous oxide, N2O, commonly known as laughing gas, is used
as an anesthetic in minor surgeries, such as the routine
extraction of wisdom teeth.
Ø Which is the likely structure for nitrous oxide?

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 Cont….
Solution
Ø Determining formal charge yields the following:

Ø The structure with a terminal oxygen atom best satisfies the

criteria for the most stable distribution of formal charge:

Ø The number of atoms with formal charges are minimized

(Guideline 2), and there is no formal charge larger than one
(Guideline 2).
Ø This is again consistent with the preference for having the less
electronegative atom in the central position.

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 Cont…..
Q. Which is the most likely molecular structure for the nitrite
(NO2−) ion?

6.4.3. Resonance
Ø The more likely structure for the nitrite anion may actually be
drawn in two different ways, distinguished by the locations of
the N-O and N=O bonds:

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 Cont…..
Ø A double bond between two atoms is shorter (and stronger)
than a single bond between the same two atoms.
Ø Experiments show, however, that both N–O bonds in NO 2 −
have the same strength and length, and are identical in all other
properties.
Ø It is not possible to write a single Lewis structure for NO2− in
which nitrogen has an octet and both bonds are equivalent.

Ø Instead, we use the concept of 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.

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 Cont…..
Ø The actual distribution of electrons in each of the nitrogen-
oxygen bonds in NO2− is the average of a double bond and a
single bond.
• We call the individual Lewis structures resonance forms.
Ø The actual electronic structure of the molecule (the average of
the resonance forms) is called a resonance hybrid of the
individual resonance forms.
Ø A double-headed arrow between Lewis structures indicates
that they are resonance forms.

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 Cont….
Ø The carbonate anion, CO32−, provides a second example of
resonance:

Ø One oxygen atom must have a double bond to carbon to

complete the octet on the central atom.
Ø All oxygen atoms, however, are equivalent, and the double
bond could form from any one of the three atoms.
Ø This gives rise to three resonance forms of the carbonate ion.

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 6.5. Strengths of ionic and covalent bonds
Ø A bond’s strength describes how strongly each atom is joined
to another atom, and therefore how much energy is required to
break the bond between the two atoms.
6.5.1. Ionic bond strength and lattice energy
Ø An ionic compound is stable because of the electrostatic
attraction between its positive and negative ions.
Ø The lattice energy of a compound is a measure of the strength
of this attraction.
Ø The lattice energy (∆� �������) of an ionic compound is defined
as the energy required to separate one mole of the solid into its
component gaseous ions.

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 Cont…….
Ø For the ionic solid MX, the lattice energy is the enthalpy
change of the process:

Ø Note that we are using the convention where the ionic solid is
separated into ions, so our lattice energies will be endothermic
(positive values).
Ø Some texts use the equivalent but opposite convention,
defining lattice energy as the energy released when separate
ions combine to form a lattice and giving negative
(exothermic) values.

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 Cont…….
Ø For sodium chloride

Ø Thus, it requires 769 kJ to separate one mole of solid NaCl

into gaseous Na+ and Cl– ions.
Ø When one mole each of gaseous Na+ and Cl– ions form solid
NaCl, 769 kJ of heat is released.
Ø The lattice energy of an ionic crystal can be expressed by the
following equation (derived from Coulomb’s law, governing
the forces between electric charges):
C Z+ Z–
∆� ������� =
��

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 Cont…….
Ø In which C is a constant that depends on the type of crystal
structure; Z+ and Z– are the charges on the ions; and Ro is the
interionic distance (the sum of the radii of the positive and
negative ions).
Ø Thus, the lattice energy of an ionic crystal increases rapidly as
the charges of the ions increase and the sizes of the ions
decrease.
Ø When all other parameters are kept constant, doubling the
charge of both the cation and anion quadruples the lattice
energy.

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 Cont…….
Ø For example, the lattice energy of LiF (Z+ and Z– = 1) is 1023
kJ/mol, whereas that of MgO (Z+ and Z– = 2) is 3900 kJ/mol
(Ro is nearly the same-about 200 pm for both compounds).
Ø Different interatomic distances produce different lattice
energies.
For example,
Ø we can comparethe lattice energy of MgF2 (2957 kJ/mol) to
that of MgI 2 (2327 kJ/mol) to observe the effect on lattice
energy of the smaller ionic size of F– as compared to I–.
Q. Zinc oxide, ZnO, is a very effective sunscreen. How would the
lattice energy of ZnO compare to that of NaCl?

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 The Born-Haber Cycle
Ø It is not possible to measure lattice energies directly.

Ø However, the lattice energy can be calculated using the

equation given in the previous section or by using a
thermochemical cycle.

Ø The Born-Haber cycle is an application of Hess’s law that

breaks down the formation of an ionic solid into a series of
individual steps:
∆�o = ∆�os + D + IE - EA - ∆� �������

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 Cont…..
Where

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 6.5.2. Bond strength of covalent bond
Ø Stable molecules exist because covalent bonds hold the atoms
together.
Ø Stronger a bond, the greater the energy required to break it.
Ø The energy required to break a specific covalent bond in one
mole of gaseous molecules is called the bond energy or the
bond dissociation energy.
Ø The bond energy for a diatomic molecule, DX–Y, is defined as
the standard enthalpy change for the endothermic reaction.

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 Cont…..
Ø For example, the bond energy of the pure covalent H–H bond,
DH–H, is 436 kJ per mole of H–H bonds broken:

Ø Molecules with three or more atoms have two or more bonds.

Ø The sum of all bond energies in such a molecule is equal to the
standard enthalpy change for the endothermic reaction that
breaks all the bonds in the molecule.
Ø For example, the sum of the four C–H bond energies in CH4,
1660 kJ, is equal to the standard enthalpy change of the
reaction:

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 Cont….
Ø The strength of a bond between two atoms increases as the
number of electron pairs in the bond increases.
Ø Generally, as the bond strength increases, the bond length
decreases.
Ø Triple bonds are stronger and shorter than double bonds
between the same two atoms;
§ likewise, double bonds are stronger and shorter than single
bonds between the same two atoms.
Ø An exothermic reaction (ΔH negative, heat produced) results
when the bonds in the products are stronger than the bonds in
the reactants.
Ø An endothermic reaction (ΔH positive, heat absorbed) results
when the bonds in the products are weaker than those in the
reactants.

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 Example
Ø Using Bond Energies to Calculate Approximate Enthalpy
Changes Methanol, CH3OH, may be an excellent alternative
fuel.
Ø The high-temperature reaction of steam and carbon produces a
mixture of the gases carbon monoxide, CO, and hydrogen, H2,
from which methanol can be produced.
CO + 2 H2 → CH3OH
Solution
First, we need to write the Lewis structures of the reactants and
the products:

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 Cont….

Ø we see that ΔH for this reaction involves the energy required to

break a C–O triple bond and two H–H single bonds, as well as
the energy produced by the formation of three C–H single
bonds, a C–O single bond, and an O–H single bond.

• Using the bond energy values in Table 6.3, we obtain:

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 6.6. Molecular structure and polarity
6.6.1. VSEPR Theory
Ø 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.
Ø 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.
Ø The electrons in the valence shell of a central atom form either
bonding pairs of electrons, located primarily between bonded
atoms, or lone pairs.

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 Cont…….
Ø As a simple example of VSEPR theory, let us predict the
structure of a gaseous BeF2 molecule.
Ø The Lewis structure of BeF2 shows only two electron pairs
around the central beryllium atom.
Ø With two bonds and no lone pairs of electrons on the central
atom, the bonds are as far apart as possible, and the
electrostatic repulsion between these regions of high electron
density is reduced to a minimum when they are on opposite
sides of the central atom.
Ø The bond angle is 180°

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3/18/2021 General Chemistry-6 59
 Electron-pair Geometry versus Molecular Structure
Ø It is important to note that electron-pair geometry around a
central atom is not the same thing as its molecular structure.
Ø We differentiate between these two situations by naming the
geometry that includes all electron pairs the electron-pair
geometry.
Ø The structure that includes only the placement of the atoms in
the molecule is called the molecular structure.
Ø The electron-pair geometries will be the same as the molecular
structures when there are no lone electron pairs around the
central atom, but they will be different when there are lone
pairs present on the central atom.

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 For example, the methane molecule, CH4
Ø Has four bonding pairs of electrons around the central carbon
atom; the electron-pair geometry is tetrahedral, as is the
molecular structure.

Ø VSEPR structures like this one are often drawn using the
wedge and dash notation, in which solid lines represent bonds
in the plane of the page, solid wedges represent bonds coming
up out of the plane, and dashed lines represent bonds going
down into the plane.

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 Cont……
Ø the ammonia molecule, NH3, also has four electron pairs
associated with the nitrogen atom, and thus has a tetrahedral
electron-pair geometry.
Ø One of these regions, however, is a lone pair, which is not
included in the molecular structure, and this lone pair
influences the shape of the molecule.

Ø (a) The electron-pair geometry for the ammonia molecule is

tetrahedral with one lone pair and three single bonds.
Ø (b) The trigonal pyramidal molecular structure is determined
from the electron-pair geometry.

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 Cont……..
(c) The actual bond angles deviate slightly from the idealized
angles because the lone pair takes up a larger region of space than
do the single bonds, causing the HNH angle to be slightly smaller
than 109.5°.
Ø As seen in CH4, small distortions from the ideal angles in
NH3 can result from differences in repulsion between various
regions of electron density.
Ø 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.
Ø The order of electron-pair repulsions from greatest to least
repulsion is:
Lone pair-lone pair>lone pair-bonding pair>bonding pair-
bonding pair

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 Cont……
Ø A lone pair of electrons occupies a larger region of space than
the electrons in a triple bond; in turn, electrons in a triple bond
occupy more space than those in a double bond, and so on.
Ø The order of sizes from largest to smallest is:
Lone pair>triple bond>double bond>single bond
Predicting Electron Pair Geometry and Molecular Structure
Ø 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.

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 Cont…….
Ø Identify the electron-pair geometry based on the number of regions
of electron density: linear, trigonal planar, tetrahedral, trigonal
bipyramidal, or octahedral.
4. Use the number of lone pairs to determine the molecular structure
Ø 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.
Ø In trigonal bipyramidal arrangements, repulsion is minimized when
every lone pair is in an equatorial position.
Ø In an octahedral arrangement with two lone pairs, repulsion is
minimized when the lone pairs are on opposite sides of the central
atom.

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 Cont…..
Ø The following examples illustrate the use of VSEPR theory to
predict the molecular structure of molecules or ions that have
no lone pairs of electrons.
Ø In this case, the molecular structure is identical to the electron
pair geometry.
Example
Ø Predict the electron-pair geometry and molecular structure for
each of the following:
(a) carbon dioxide, CO2, a molecule produced by the combustion
of fossil fuels
(b) boron trichloride, BCl3, an important industrial chemical

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 Cont…
Solution
(a) We write the Lewis structure of CO2 as:

Ø This shows us two regions of high electron density around the

carbon atom-each double bond counts as one region, and there
are no lone pairs on the carbon atom.
Ø Using VSEPR theory, we predict that the two regions of
electron density arrange themselves on opposite sides of the
central atom with a bond angle of 180°.
Ø The electron-pair geometry and molecular structure are
identical, and CO2 molecules are linear.

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 Cont….
(b) We write the Lewis structure of BCl3 as:

Ø The electron-pair geometry and molecular structure of BCl3

are both trigonal planar.
Ø Note that the VSEPR geometry indicates the correct bond
angles (120°), unlike the Lewis structure shown above.

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 6.6.2. Molecular structure and dipole moment
Ø p o l a r c o v a l e n t b o n d s c o n n e c t t w o a t o m s w i t h d i ff e r i n g
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.
Ø This separation of charge gives rise to a bond dipole moment.
Ø The magnitude of a bond dipole moment is represented by the Greek
letter mu (μ) and is given by the formula shown here,

Ø where Q is the magnitude of the partial charges (determined by the

electronegativity difference) and r is the distance between the
charges:

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 Cont…
Ø Dipole vectors are shown as arrows pointing along the bond
from the less electronegative atom toward the more
electronegative atom.
Ø A small plus sign is drawn on the less electronegative end to
indicate the partially positive end of the bond.
Ø The length of the arrow is proportional to the magnitude of the
electronegativity difference between the two atoms.

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 Cont….

Ø nonpolar molecules dipole moment is zero.

To summarize, 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.
Properties of Polar Molecules
Ø Polar molecules tend to align when placed in an electric field
with the positive end of the molecule oriented toward the
negative plate and the negative end toward the positive plate.
Ø We can use an electrically charged object to attract polar
molecules, but nonpolar molecules are not attracted.

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 Cont...
Ø Also, polar solvents are better at dissolving polar substances, and
nonpolar solvents are better at dissolving nonpolar substances.

Ø (a) Molecules are always randomly distributed in the liquid state in

the absence of an electric field.
Ø (b) When an electric field is applied, polar molecules like HF will
align to the dipoles with the field direction.

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