General Chemistry

1b
(MCHM012)

Chapter 01

Structure and Bonding

Adapted by Mr. Mutendela T Olivier

Sefako Makgatho Health Sciences
1
University
 Atomic Structure 1

The nucleus contains positively charged protons and

uncharged neutrons.

The electron cloud is composed of negatively charged

electrons.
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 Atomic Structure 2

The atomic number is the number of protons in the

nucleus and also the number of electrons surrounding (i.e.,
protons = electrons).
The mass number is the number of protons plus neutrons
in the nucleus (e.g., has six protons and six neutrons).
Carbon’s atomic number is 6; its mass number is 12.
In a neutral atom, the number of protons equals the
number of electrons.
The atomic weight of a particular element is the weighted
average of the mass of all its isotopes reported in atomic
mass unit (amu).
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 Ions
In addition to neutral atoms, we will also encounter
charged ions.
• A cation is positively charged and has fewer electrons
than protons.

• An anion is negatively charged and has more electrons

than protons.

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 Isotopes
Isotopes are two atoms of the same element
having a different number of neutrons.

Isotopes have different mass numbers.

Most isotope of carbon have 6 protons and 6

neutrons.

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 The Periodic Table
Elements in the same row are similar in size.
Elements in the same column have similar electronic and
chemical properties.

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 Atomic Orbitals
An s orbital has a sphere of electron density and is lower
in energy than the other orbitals of the same shell.

A p orbital has a dumbbell shape and contains a node (no

electron density) at the nucleus. It is higher in energy than
an s orbital.

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 Periodic Table 1

The First Row

• There is only one orbital in the first shell.
• Each shell can hold a maximum of two electrons.
• Therefore, there are two elements in the first row: H
and He.

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 Periodic Table 2

The Second Row

Each element in the second row of the periodic table also
has four orbitals available to accept additional electrons:
one 2s orbital, and three 2p orbitals.

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 Periodic Table 3

The Second Row

• Each of the four orbitals in the second shell hold two
electrons.
• There is a maximum capacity of eight valence
electrons for elements in the second row.
• The second row of the periodic table consists of eight
elements, obtained by adding electrons to the 2s and
three 2p orbitals.

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 Bonding
Bonding is the joining of two atoms in a stable
arrangement.
Through bonding, atoms gain, lose, or share electrons to
attain the electronic configuration of the noble gas closest
to them in the periodic table.
Atoms can form either ionic or covalent bonds to attain a
complete outer shell (octet rule for second row elements).
Ionic bonds result from the transfer of electrons from one
element to another.
Covalent bonds result from the sharing of electrons
between two nuclei.
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 Ionic Bonding
An ionic bond generally occurs when elements on the far
left side of the periodic table combine with elements on the
far right side, ignoring noble gases.
A positively charged cation formed from the element on the
left side attracts a negatively charged anion formed from
the element on the right side (e.g., sodium chloride, NaCl).

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 Covalent Bonding 1

Covalent bonding occurs with elements like carbon

in the middle of the table (e.g., ) with elements that
have similar electronegativity.

Covalent bonds also occur between two of the

same elements from the sides of the table (e.g., , ).

A covalent bond is a two-electron bond, and a

compound with covalent bonds is called a
molecule.

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 Covalent Bonding 2

Bonding in Molecular Hydrogen (H2)

• Hydrogen forms one covalent bond.

• When two hydrogen atoms are joined in a bond, each

has a filled valence shell of two electrons.

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 Valence Electrons
Second row elements can have no more than eight
electrons around them. For neutral molecules, this
has two consequences:
• Atoms with one, two, three, or four valence electrons
form one, two, three, or four bonds, respectively, in
neutral molecules (e.g., BF3, CH4).

• Atoms with five or more valence electrons form enough

bonds to give an octet (e.g., NH3). In this case,
predicted number of bonds = 8 − number of valence
electrons.

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 Nonbonded Electrons
When second-row elements form fewer than four
bonds their octets consist of both bonding (shared)
and nonbonding (unshared) electrons. Unshared
electrons are also called lone pairs.

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 Lewis Structures
Lewis structures are electron dot representations
for molecules.

General rules for drawing Lewis structures:

1. Draw only the valence electrons.
2. Give every second-row element no more than eight
electrons.
3. Give each hydrogen two electrons.

In a Lewis Structure, a solid line indicates a two-

electron covalent bond.

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 How to Draw a Lewis Structure 1

Step [1] Arrange atoms next to each other that you think
are bonded together.
• Always place hydrogen and halogens on the periphery
because they form only one bond each.

• Place no more atoms around an atom than the number of

bonds it usually forms.

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 How to Draw a Lewis Structure 2

Step [2] Count the electrons.

• Count the number of valence electrons from all atoms.
• Add one electron for each negative charge.
• Subtract one electron for each positive charge.
• This gives the total number of electrons that must be used in
drawing the Lewis structure.
Step [3] Arrange the electrons around the atoms.
• Place a bond between every two atoms, giving two electrons
to each H and no more than eight to any second-row atom.
• Use all remaining electrons to fill octets with lone pairs.
• If all valence electrons are used and an atoms does not have
an octet, form multiple bonds.
Step [4] Assign formal charges to all atoms.
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 Multiple Bonds
If all valence electrons are used and an atom does
not have an octet, form multiple bonds.

To give both C’s an octet, change one lone pair

into one bonding pair between the two C’s, forming
a double bond.
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Summary on Lewis structure

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 Formal Charge
Formal charge is the charge assigned to
individual atoms in a Lewis structure.
Formal charge is calculated as follows:

The number of electrons “owned” by an atom is

determined by its number of bonds and lone pairs.
An atom “owns” all of its unshared electrons and
half of its shared electrons.
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 Electron Ownership 1

The number of electrons “owned” by different

atoms is indicated in the following examples:

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 Electron Ownership 2

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Formal Charge & Lewis structures (Exercises)

25
 Isomers
Sometimes more than one arrangement of atoms (Lewis
structure) is possible for a given molecular formula.

These two compounds are called isomers.

Isomers are different molecules having the same
molecular formula. Ethanol and dimethyl ether are
constitutional isomers.
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 Exceptions to the Octet Rule
Elements in Groups 2A and 3A

Elements in the Third Row

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 Resonance
Some molecules cannot be adequately represented by a
single Lewis structure. For example:

These structures are called resonance structures or

resonance forms. A double-headed arrow is used to
separate the two resonance structures.
Resonance structures are two Lewis structures having the
same placement of atoms but a different arrangement of
electrons.
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 Resonance Forms

Neither resonance structure is an accurate representation for

(HCONH)−. The true structure is a composite of both
resonance forms and is called a resonance hybrid.
The hybrid shows characteristics of both structures.
Resonance allows certain electron pairs to be delocalized
over two or more atoms, and this delocalization adds stability.
A molecule with two or more resonance forms is said to be
resonance stabilized.
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 Basic Principles of Resonance
Theory
Resonance structures are not real. An individual
resonance structure does not accurately represent
the structure of a molecule or ion. Only the hybrid
does.
Resonance structures are not in equilibrium
with each other. There is no movement of
electrons from one form to another.
Resonance structures are not isomers. Two
isomers differ in the arrangement of both atoms
and electrons, whereas resonance structures differ
only in the arrangement of electrons.
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 Drawing Resonance Structures 1

Rule [1]: Two resonance structures differ in the

position of multiple bonds and nonbonded
electrons. The placement of atoms and single
bonds always stays the same.

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 Drawing Resonance Structures 2

Rule [2]: Two resonance structures must have the same

number of unpaired electrons.

Rule [3]: Resonance structures must be valid Lewis

structures. Hydrogen must have two electrons and no
second-row element can have more than eight electrons.

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 Curved Arrow Notation
Curved arrow notation is a convention that shows how electron
position differs between two resonance forms.
Curved arrow notation shows the movement of an electron
pair. The tail of the arrow always begins at the electron pair,
either in a bond or lone pair. The head points to where the
electron pair “moves.”

Example 1:

Example 2:

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 Atoms Without Octets
Resonance structures can have an atom with fewer than 8
electrons.

However, resonance structures can never have a second-

row element with more than 8 electrons.

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 Occurrence of Resonance
Two different resonance structures can be drawn
when a lone pair is located on an atom directly
bonded to a double bond.

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 The Resonance Hybrid
A resonance hybrid is a composite of all possible
resonance structures. In the resonance hybrid, the
electron pairs drawn in different locations in
individual resonance forms are delocalized.

When two resonance structures are different, the

hybrid looks more like the “better” resonance
structure.

The “better” resonance structure is called the

major contributor to the hybrid, and all others are
minor contributors.
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 Resonance Hybrids
A “better” resonance structure is one that has more
bonds and fewer charges.

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Major contributor

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Summary on Resonance

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 Determining Molecular Shape 1

Two variables define a molecule’s structure: bond

length and bond angle.
• Bond length decreases across a row of the periodic
table as the size of the atom decreases.

• Bond length increases down a column of the periodic

table as the size of an atom increases.

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 Determining Molecular Shape 2

Table 1.2 Average Bond Lengths

Bond Length(pm) Bond Length(pm) Bond Length(pm)

H-H 74 H-F 92 C-F 133

C-H 109 H-Cl 127 C-Cl 177

N-H 101 H-Br 141 C-Br 194

O=H 96 H-I 161 C-I 213

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 Molecular Geometry
The number of groups surrounding a particular
atom determines its geometry. A group is either an
atom or a lone pair of electrons.
The most stable arrangement keeps these groups
as far away from each other as possible. This is
exemplified by Valence Shell Electron Pair
Repulsion (VSEPR) theory.
Number of groups Geometry Bond angle

• two groups linear

• three groups trigonal planar

• four groups tetrahedral

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 Two Groups Around an Atom

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 Three Groups Around an Atom

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 Four Groups Around an Atom

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Summary of Geometry

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 Drawing Three-Dimensional
Structures
A solid line is used for a bond in the plane.
A wedge is used for a bond in front of the plane.
A dashed line is used for a bond behind the plane

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 Equivalent Representations
for Methane
The molecule can be turned in many different ways,
generating equivalent representations.
All of the following are acceptable drawings for CH4.
Each drawing has two solid lines, one wedge, and
one dashed wedge.

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 Wedges and Dashed Wedges
Note that wedges and dashed wedges are used for
groups that are really aligned one behind another.

It does not matter in the following two drawings

whether the wedge or dash is skewed to the left or
right.

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 A Nonbonded Pair of Electrons is
Counted as a “Group”
In ammonia (NH3), one of the four groups attached
to the central N atom is a lone pair.
The group geometry is a tetrahedron.
The molecular shape is referred to as trigonal
pyramidal.

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 The 3-D Structure of Water
In water (H2O), two of the four groups attached to
the central O atom are lone pairs.
The group geometry is a tetrahedron.
The molecular shape is referred to as bent.

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 Varying Bond Angles

In both NH3 and H2O the

Methane (CH4)
bond angle is smaller
than the theoretical
tetrahedral bond angle
because of repulsion of
the lone pairs of
Ammonia (NH3)
electrons.
The bonded atoms are
compressed into a
smaller space with a
Water (H2O) smaller bond angle.

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 Summary: Predicting Geometry
Based on Number of Groups

Table 1.3 Summary: Determining Geometry Based on

the Number of Groups

https://phet.colorado.edu/sims/html/molecule-shapes/latest/molecule-shapes_en.html

https://phet.colorado.edu/sims/html/molecule-shapes-basics/latest/molecule-shapes-
basics_en.html

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 Drawing Organic Molecules—
Condensed Structures
All atoms are drawn in, but the two-electron bond lines are
generally omitted.
Atoms are usually drawn next to the atoms to which they
are bonded.
Parentheses are used around similar groups bonded to the
same atom.
Lone pairs are omitted.

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 Examples of Condensed
Structures

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 Condensed Structures with
C=O

In these examples, the only way for all atoms to have

an octet is by having a carbon-oxygen double bond.

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 Skeletal Structures 1

Assume there is a carbon atom at the junction of

any two lines or at the end of any line.
Assume there are enough hydrogens around each
carbon to make it tetravalent.
Draw in all heteroatoms and the hydrogens directly
bonded to them.

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 Skeletal Structures 2

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 Interpreting Skeletal Structures

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 Skeletal Structures with Charged
Carbon Atoms
A charge on a carbon atom takes the place of one
hydrogen atom.
The charge determines the number of lone pairs.
Negatively charged carbon atoms have one lone pair
and positively charged carbon atoms have none.

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 Lone Pairs on Heteroatoms

Skeletal structures often leave out lone pairs on

heteroatoms, but don’t forget about them.
Use the formal charge to determine the number of
lone pairs.

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 Orbitals and Bonding: Hydrogen
When the 1s orbital of one H atom overlaps with the 1s
orbital of another H atom, a sigma (σ) bond that
concentrates electron density between the two nuclei is
formed. All single bonds are  bonds.
This bond is cylindrically symmetrical because the
electrons forming the bond are distributed symmetrically
about an imaginary line connecting the two nuclei.

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 Orbitals and Bonding: Methane
To account for the bonding patterns observed in more complex
molecules, we must take a closer look at how the 2s and 2p
orbitals of atoms in the second row are utilized.
In addition to its two core electrons, carbon has four valence
electrons.
In its ground state, carbon places two electrons in the 2s orbital
and one each in 2p orbitals.

Note: The lowest energy arrangement of electrons for an atom is called

its ground state.
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 Divalent Carbon
In this description, carbon should form only two
bonds because it has only two unpaired valence
electrons.
However, the resulting species, CH2, is very
unstable and cannot be isolated under typical
laboratory conditions.
Note that in CH2, carbon would not have an octet
of electrons.

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 Hybrid Orbitals
To solve this dilemma, chemists have proposed that atoms
like carbon do not use pure s and pure p orbitals in forming
bonds.
Instead, atoms use a set of new orbitals called hybrid
orbitals.
Hybridization is the combination of two or more atomic
orbitals to form the same number of hybrid orbitals, each
having the same shape and energy.

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 Shape and Orientation of sp3
Hybrid Orbitals
The mixing of a spherical 2s orbital and three dumbbell shaped
2p orbitals together produces four hybrid orbitals, each having
one large lobe and one small lobe.

The four hybrid orbitals are oriented towards the corners of a

tetrahedron, and form four equivalent bonds.

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 Bonding Using sp3 Hybrid
Orbitals
Each bond in CH4 is formed by overlap of an sp3 hybrid
orbital of carbon with a 1s orbital of hydrogen.
These four bonds point to the corners of a tetrahedron.

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 Other Hybridization Patterns

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 Determining Hybridization
Count the number of groups (atoms and
nonbonded electron pairs) around the atom.
The number of groups corresponds to the number
of atomic orbitals that must be hybridized to form
the hybrid orbitals.
Table 1.4 Three types of Hybrid Orbitals
Number of groups Number of orbitals Type of hybrid orbital

2 2 two sp hybrid orbitals

3 3 three
4 4 four

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 Hybrid orbitals of NH3 and H2O

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 Hybridization and Bonding in
Ethane

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 Ethane, CH3—CH3
Making a model of ethane illustrates one additional
feature about its structure.

Rotation occurs around the central C—C  bond.

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 Hybrid Orbitals in Ethylene
Each carbon is trigonal planar.

Each carbon is sp2 hybridized.

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 σ and π Bonds in Ethylene

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 No Free Rotation in Ethylene

Unlike the C—C bond in ethane, rotation about the C—C

double bond in ethylene is restricted.
It can only occur if the π bond first breaks and then reforms,
a process that requires considerable energy.

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 sp Hybrid Orbitals

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 Acetylene (Ethyne)

Each carbon atom has two unhybridized 2p orbitals that are

perpendicular to each other and to the sp hybrid orbitals.
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 Triple Bonds
The side-by-side overlap of two 2p orbitals on one carbon with
two 2p orbitals on the other carbon creates the second and
third bonds of the triple bond.
All triple bonds are composed of one sigma and two pi bonds.
Figure 1.11

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 Summary of Bonding in
Acetylene 1

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 Summary of Bonding in
Acetylene

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 Bond Length and Bond
Strength
As the number of electrons between two nuclei
increases, bonds become shorter and stronger.

Triple bonds are shorter and stronger than double

bonds, which are shorter and stronger than single
bonds.

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 Carbon-Hydrogen Bonds 1

The length and strength of C—H bonds vary

depending on the hybridization of the carbon atom.

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 Carbon-Hydrogen Bonds 2

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 Percent s-Character

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 Electronegativity
Electronegativity is a measure of an atom’s
attraction for electrons in a bond.
Electronegativity values for some common elements:

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 Bond Polarity
Electronegativity values are used to indicate whether the
electrons in a bond are equally shared or unequally shared
between two atoms.

When electrons are equally shared, the bond is nonpolar.

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 Nonpolar Bonds
A carbon—carbon bond is nonpolar.

C—H bonds are considered to be nonpolar

because the electronegativity difference between
C and H is small.

Whenever two different atoms having similar

electronegativities are bonded together, the bond
is nonpolar.

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 Polar Bonds
Bonding between atoms of different electronegativity
values results in unequal sharing of electrons.
Example: In the C—O bond, the electrons are pulled away
from C (2.5) toward O (3.4), the element of higher
electronegativity. The bond is polar, or polar covalent. The
bond is said to have dipole; that is, partial separation of
charge.

A C—O bond is a polar bond.

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 Depicting Polarity

The δ+ means the indicated atom is electron deficient.

The δ− means the indicated atom is electron rich.
The direction of polarity in a bond is indicated by an arrow
with the head of the arrow pointing towards the more
electronegative element.
The tail of the arrow is drawn at the less electronegative
element.
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 Polarity of Molecules
Use the following procedure to determine if a molecule has
a net dipole:
• Use electronegativity differences to identify all of the polar
bonds and the directions of the bond dipoles.
• Determine the geometry around individual atoms by counting
groups, and decide if individual dipoles cancel or reinforce
each other in space.
Figure 1.13 Electrostatic potential plot of CH3Cl

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 Polar Molecules
A polar molecule has either one polar bond, or two
or more bond dipoles that reinforce each other. An
example is water:
• It is a bent molecule
• Two dipoles reinforce
• It has a net dipole, making it a polar molecule

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 Nonpolar Molecules
A nonpolar molecule has either no polar bonds, or
two or more bond dipoles that cancel. An example
is carbon dioxide:
• It is a linear molecule
• Two dipoles are equal and opposite in direction
• Two dipoles cancel
• It is a nonpolar molecule with no net dipole

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 Electrostatic Potential for Polar
and Nonpolar Molecules

The dipoles of H2O and CO2 can also be visualized

using electrostatic potential plots.

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