Chemistry

Fifth Edition

Julia Burdge

Lecture PowerPoints

Chapter 8

Chemical Bonding I: Basic

Concepts

©2020 McGraw-Hill Education. All rights reserved. Authorized only for instructor use in the classroom. No reproduction or further distribution permitted without the prior written consent of McGraw-Hill Education.
 8.1 Lewis Dot Symbols 2

Lewis Dot Symbols

When atoms interact to form compounds, it is their valence
electrons that actually interact.
Therefore, it is helpful to have a method for depicting the
valence electrons of the atoms involved.
This can be done using Lewis dot symbols.
A Lewis dot symbol consists of the element’s symbol
surrounded by dots, where each dot represents a valence
electron.

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 8.1 Lewis Dot Symbols 3

Lewis Dot Symbols

For the main group elements, the number of dots in the
Lewis dot symbol is the same as the group number.

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 SAMPLE PROBLEM 8.1 Strategy

Write Lewis dot symbols for (a) fluoride ion (F−), (b)
potassium ion (K+), and (c) sulfide ion (S2−).

Strategy
Starting with the Lewis dot symbol for each element, add
dots (for anions) or remove dots (for cations) as needed to
achieve the correct charge on each ion.

Don’t forget to include the appropriate charge on the

Lewis dot symbol.

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 SAMPLE PROBLEM 8.1 Setup

Setup
The Lewis dot symbols for F, K and S are as follows:

Solution

(b) K+

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 8.3 Covalent Bonding

Topics
Lewis Structures
Multiple Bonds
Comparison of Ionic and Covalent Compounds

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 8.3 Covalent Bonding 1

Lewis Structures
When compounds form between elements with more
similar properties, electrons are not transferred from one
element to another but instead are shared to give each
atom a noble gas electron configuration.

It was Gilbert Lewis who first suggested that a chemical

bond involves atoms sharing electrons, and this approach
is known as the Lewis theory of bonding.

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 8.3 Covalent Bonding 2

Lewis Structures

Two H atoms move close enough to each other to share

the electron pair.

This arrangement allows each H atom to “count” both

electrons as its own and to “feel” as though it has the
noble gas electron configuration of helium.

This type of arrangement, where two atoms share a pair of

electrons, is known as covalent bonding, and the shared
pair of electrons constitutes the covalent bond.
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 8.3 Covalent Bonding 3

Lewis Structures
Lewis summarized much of his theory of chemical bonding
with the octet rule.

According to the octet rule, atoms will lose, gain, or share

electrons to achieve a noble gas electron configuration.

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 8.3 Covalent Bonding 4

Lewis Structures
The structures used to represent molecules held together
by covalent bonds, such as H2 and F2, are called Lewis
structures.

A Lewis structure is a representation of covalent bonding

in which shared electron pairs are shown either as dashes
or as pairs of dots between two atoms, and lone pairs are
shown as pairs of dots on individual atoms.

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 8.3 Covalent Bonding 5

Lewis Structures

The octet rule works best for elements in the second

period of the periodic table. In Section 8.8, we will discuss
some important exceptions to the octet rule.
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 8.3 Covalent Bonding 6

Multiple Bonds
In a single bond, two atoms are held together by one
electron pair.

Multiple bonds form, on the other hand, when two atoms

share two or more pairs of electrons.

A multiple bond in which the atoms share two pairs of

electrons is called a double bond.

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 8.3 Covalent Bonding 7

Multiple Bonds

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 8.3 Covalent Bonding 8

Multiple Bonds
A triple bond arises when two atoms share three pairs of
electrons:

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 8.3 Covalent Bonding 10

Bond Type Bond Length (pm)

C–H 107
Multiple Bonds O–H 96
C–O 143
Multiple bonds are shorter C=O 121
than single bonds. C≡O
C–C
113
154
C=C 133
C≡C 120
C–N 143
C=N 138
C≡N 116
N–N 147
N=N 124
N≡N 110
N–O 136
N=O 122
O–O 148
O=O 121

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 8.3 Covalent Bonding 12

Comparison of Ionic and Covalent Compounds

Intermolecular forces are usually quite weak compared to
the forces holding atoms together within a molecule, so
molecules of a covalent compound are not held together
tightly.

As a result, covalent compounds are usually gases, liquids,

or low- melting solids.

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 8.3 Covalent Bonding 13

Comparison of Ionic and Covalent Compounds

On the other hand, the electrostatic forces holding ions
together in an ionic compound are usually very strong, so
ionic compounds are solids at room temperature and have
high melting points.

Many ionic compounds are soluble in water, and the

resulting aqueous solutions conduct electricity because
the compounds are strong electrolytes.

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 8.3 Covalent Bonding 15

Comparison of Ionic and Covalent Compounds

TABLE 8. 4 Comparison of Some Properties of an Ionic
Compound (NaCl) and a Covalent Compound
(CCl 4)
Property NaCI CCI4
Appearance White solid Colorless liquid
Melting point (°C) 801 −23
Molar heat of fusion∗ (kJ/mol) 30.2 2.5
Boiling point (°C) 1,413 76.5
Molar heat of vaporization* (kJ/mol) 600
Density (g/cm3) 2.17 1.59
Solubility in water High Very low
Electrical conductivity
Solid Poor Poor
Liquid Good Poor
Aqueous Good Poor
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 8.4 Electronegativity and Polarity

Topics
Electronegativity
Dipole Moment, Partial Charges, and Percent Ionic
Character

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 8.4 Electronegativity and Polarity 1

Electronegativity

So far, we have described chemical bonds as either ionic,

when they occur between a metal and a nonmetal, or
covalent, when they occur between nonmetals.

In fact, ionic and covalent bonds are simply the extremes

in a spectrum of bonding.

Bonds that fall between these two extremes are polar,

meaning that electrons are shared but are not shared
equally. Such bonds are referred to as polar covalent
bonds.
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 8.4 Electronegativity and Polarity 2

Electronegativity

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 8.4 Electronegativity and Polarity 3

Electronegativity
Electronegativity is the ability of an atom in a compound
to draw electrons to itself.
Elements with high electronegativity have a greater
tendency to attract electrons than do elements with low
electronegativity.
Electronegativity is related to electron affinity and
ionization energy. An atom such as fluorine, which has a
high electron affinity (tends to accept electrons) and a high
ionization energy (does not lose electrons easily), has a
high electronegativity. 22
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 8.4 Electronegativity and Polarity 4

Electronegativity

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 8.4 Electronegativity and Polarity 5

Electronegativity

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 8.4 Electronegativity and Polarity 6

Electronegativity
There is no sharp distinction between nonpolar covalent
and polar covalent or between polar covalent and ionic,
but the following guidelines can help distinguish among
them:
• A bond between atoms whose electronegativities differ by less
than 0.5 is generally considered purely covalent or nonpolar.
• A bond between atoms whose electronegativities differ by the
range of 0.5 to 2.0 is generally considered polar covalent.
• A bond between atoms whose electronegativities differ by 2.0 or
more is generally considered ionic.
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 SAMPLE PROBLEM 8.4 Setup

Classify the following bonds as nonpolar, polar, or ionic:

(a) the bond in ClF.
(b) the bond in CsBr.
(c) the carbon-carbon double bond in C2H4.

Setup
Electronegativity values are:
Cl (3.0), F (4.0), Cs (0.7), Br (2.8), C (2.5).

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 SAMPLE PROBLEM 8.4 Solution

Solution
(a) The difference between the electronegativities of F and
Cl is 4.0 − 3.0 = 1.0, making the bond in ClF polar.

(b) In CsBr, 2.8 − 0.7 = 2.1, making the bond ionic.

(c)In C2H4, the two atoms are identical.

(Not only are they the same element, but each C atom
is bonded to two H atoms.)

The carbon-carbon double bond in C2H4 is nonpolar. 27

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 8.4 Electronegativity and Polarity 7

Dipole Moment, Partial Charges, and Percent Ionic

Character
The shift of electron density in a polar bond is symbolized
by a crossed arrow (a dipole arrow).

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 8.5 Drawing Lewis Structures 1

Drawing Lewis Structures

1. From the molecular formula, draw the skeletal
structure of the compound, using chemical symbols
and placing bonded atoms next to one another.

In general, the least electronegative atom will be the

central atom. (H cannot be a central atom because it
only forms one covalent bond.)

Draw a single covalent bond (dash) between the

central atom and each of the surrounding atoms.

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 8.5 Drawing Lewis Structures 2

Drawing Lewis Structures

2. Count the total number of valence electrons present.

For polyatomic ions, add electrons to the total number

to account for negative charges; sub tract electrons
from the total number to account for positive charges.

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 8.5 Drawing Lewis Structures 3

Drawing Lewis Structures

3. For each bond (dash) in the skeletal structure, subtract
two electrons from the total valence electrons to
determine the number of remaining electrons.

4. Use the remaining electrons to complete the octets of

the terminal atoms (those bonded to the central atom)
by placing pairs of electrons on each atom.

If there is more than one type of terminal atom,

complete the octets of the most electronegative atoms
first.
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 8.5 Drawing Lewis Structures 4

Drawing Lewis Structures

5. If any electrons remain after step 4, place them in pairs
on the central atom.

6. If the central atom has fewer than eight electrons after

completing steps 1 to 5, move one or more pairs from
the terminal atoms to form multiple bonds between
the central atom and the terminal atoms. (Unless the
central atom is a Group 3A element.)

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 SAMPLE PROBLEM 8.7 Setup 1

Draw the Lewis structure for carbon disulfide (CS2).

Setup
Step 1: C and S have identical electronegativities. We will
draw the skeletal structure with the unique
atom, C, at the center.
S—C—S
Step 2: The total number of valence electrons:
2(6) + 4 = 16.
Step 3: Subtract four electrons to account for the bonds
in the skeletal structure, leaving us 12 electrons
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 SAMPLE PROBLEM 8.7 Setup 2

Setup
Step 4: Distribute the 12 remaining electrons as three lone
pairs on each S atom.

Step 5: There are no electrons remaining after step 4, so step

5 does not apply.
Step 6: To complete carbon’s octet, use one lone pair from
each S atom to make a double bond to the C atom.

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 8.6 Lewis Structures and Formal Charge 1

Lewis Structures and Formal Charge

Formal charge can be used to determine the most
plausible Lewis structures when more than one possibility
exists for a compound.
• All the atom’s nonbonding electrons are associated
with the atom.
• Half of the atom’s bonding electrons are associated
with the atom.

formal charge = valence electrons − associated electrons

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 8.6 Lewis Structures and Formal Charge 2

Lewis Structures and Formal Charge

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 8.6 Lewis Structures and Formal Charge 3

Lewis Structures and Formal Charge

For molecules, the formal charges must sum to zero.
For ions, the formal charges must sum to the overall charge
on the ion.

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 SAMPLE PROBLEM 8.8 Setup

Determine the formal charges on each atom in the nitrate

ion (NO3−).
Setup

Solution
The formal charges are as follows: +1 (N atom), –1 (singly
bonded O atoms), and 0 (doubly bonded O atom).

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 8.6 Lewis Structures and Formal Charge 4

Lewis Structures and Formal Charge

When there is more than one possible skeletal arrangement
of atoms, we often can select the best skeletal arrangement
by using formal charges and the following guidelines:
• For molecules, a Lewis structure in which all formal
charges are zero is preferred to one in which there are
nonzero formal charges.
• Lewis structures with small formal charges (0 and 1)
are preferred to those with large formal charges (2, 3,
and so on).

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 8.6 Lewis Structures and Formal Charge 5

Lewis Structures and Formal Charge

When there is more than one possible skeletal
arrangement of atoms, we often can select the best
skeletal arrangement by using formal charges and the
following guidelines:
• The best skeletal arrangement of atoms will give rise to
Lewis structures in which the formal charges are
consistent with electronegativities.

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 SAMPLE PROBLEM 8.9

Formaldehyde(CH2O), which can be used to preserve

biological specimens, is commonly sold as a 37% aqueous
solution. Use formal charges to determine which skeletal
arrangement of atoms shown here is the best choice for
the Lewis structure of CH2O.

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 SAMPLE PROBLEM 8.9 Strategy

Strategy
Complete the Lewis structures for each of the CH2O
skeletons shown and determine the formal charges on the
atoms in each one.
Setup

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 SAMPLE PROBLEM 8.9 Solution

Solution

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 8.7 Resonance

Topics
Resonance

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 8.7 Resonance 1

Resonance
A resonance structure is one of two or more Lewis
structures for a single molecule that cannot be
represented accurately by only one Lewis structure.

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 SAMPLE PROBLEM 8.10 Setup

Draw all possible resonance structures of sulfur trioxide,

SO3.
Setup

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 SAMPLE PROBLEM 8.10 Solution

Solution

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 8.8 Exceptions to the Octet Rule

Topics
Incomplete Octets
Odd Numbers of Electrons
Expanded Octets

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 8.8 Exceptions to the Octet Rule 1

Incomplete Octets
In some compounds the number of electrons surrounding
the central atom in a stable molecule is fewer than eight.

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 8.8 Exceptions to the Octet Rule 2

Odd Numbers of Electrons

Some molecules contain an odd number of electrons. The
octet rule cannot be obeyed for all the atoms in these
molecules.

Molecules with an odd number of electrons are sometimes

referred to as free radicals (or just radicals).

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 8.8 Exceptions to the Octet Rule 3

Odd Numbers of Electrons

Many radicals are highly reactive, because there is a
tendency for the unpaired electron to form a covalent
bond with an unpaired electron on another molecule.

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 8.8 Exceptions to the Octet Rule 4

Expanded Octets
Atoms of the second-period elements cannot have more than
eight valence electrons around them, but atoms of elements
in and beyond the third period of the periodic table can.
In addition to the 3s and 3p orbitals, elements in the third
period also have 3d orbitals that can be used in bonding.
These orbitals enable an atom to form an expanded octet.

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 SAMPLE PROBLEM 8.12 Strategy

Draw the Lewis structures of

(a) boron triiodide (Bl3).
(b) arsenic pentafluoride (AsF5).
(c) xenon tetrafluoride (XeF4).

Strategy

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 SAMPLE PROBLEM 8.12 Setup

Setup
(a) 24 valence electrons, 18 to distribute.
(b) 40 valence electrons, 30 to distribute.
(c) 36 valence electrons , 28 to distribute.

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 SAMPLE PROBLEM 8.12 Solution

Solution

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 8.9 Bond Enthalpy

Topics
Bond Enthalpy

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 8.9 Bond Enthalpy 1

Bond Enthalpy
One measure of the stability of a molecule is its bond
enthalpy, which is the enthalpy change associated with
breaking a particular bond in 1 mole of gaseous molecules.

H2(g) → H(g) + H(g) ∆H° = 436.4 kJ/mol

Cl2(g) → Cl(g) + Cl(g) ∆H° = 242.7 kJ/mol

HCl(g) → H(g) + Cl(g) ∆H° = 431.9 kJ/mol

N2(g) → N(g) + N(g) ∆H° = 941.4 kJ/mol

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 8.9 Bond Enthalpy 2

Bond Enthalpy
Measuring the strength of covalent bonds in polyatomic
molecules is more complicated than for diatomic
molecules.
H2O(g) → H(g) + OH(g) ∆H° = 502 kJ/mol

OH(g) → H(g) + O(g) ∆H° = 427 kJ/mol

For polyatomic molecules, therefore, we speak of the
average bond enthalpy of a particular bond.

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 8.9 Bond Enthalpy 3

Bond Enthalpy
The approximate enthalpy of a reaction can be calculated
by using the average bond enthalpies.

∆H = ∑BE(reactants) − ∑BE(products)

= total energy input(to break bonds)

− total energy released(by bond formation)

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 8.9 Bond Enthalpy 4

Bond Enthalpy

TABLE 8.6 Bond Enthalpies

Bond Enthalpy Bond Enthalpy Bond Enthalpy
Bond Bond Bond
(kJ/mol) (kJ/mol) (kJ/mol)
H-H* 436.4 C≡O 1070 O-O 142
H-N 393 c-p 263 O=O 498.7
H-0 460 c-s 255 O-P 502
H-S 368 C=S 477 O=S 469
H-P 326 C-F 453 O-F 190
H-F 568.2 C-Cl 339 O-cl 203
H Cl 431.9 C-Br 276 O-Br 234
H—Br 366.1 C-I 216 O-I 234
H-I 298.3 N-N 193 P-P 197

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 8.9 Bond Enthalpy 5

Bond Enthalpy
Bond Enthalpy Bond Enthalpy Bond Enthalpy
Bond Bond Bond
(kJ/mol) (kJ/mol) (kJ/mol)
C-H 414 N≡N 418 P=P 489
C-C 347 N=N 941.4 S-S 268
C=C 620 N-O 176 S=S 352
C≡C 812 N=O 607 F-F 156.9
C-N 276 N-F 272 Cl-Cl 242.7
C=N 615 N-Cl 200 Cl-F 193
C≡N 891 N-Br 243 Br-Br 192.5
C-O 351 N-I 159 I-I 151.0
C=O† 745

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 8.9 Bond Enthalpy 6

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 SAMPLE PROBLEM 8.13 Setup

Use bond enthalpies from Table 8.6 to estimate the

enthalpy of reaction for the combustion of methane:
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
Setup

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 SAMPLE PROBLEM 8.13 Solution

Solution
[4(414 kJ/mol) + 2(498.7 kJ/mol)] − [2(799 kJ/mol) + 4(460kJ/mol)]
= −785 kJ/mol

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