7.

Chemical Bonds
General Chemistry 1A
Dr. Rukman Hertadi

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Student learning outcomes
After following this material, students are expected to be able to:
• describe the conditions for bond formation
• describe the factors involved in the formation of ionic bonds
• write down Lewis symbols for atoms and ions
• applie the understanding of covalent bonds, the octet rule and the
double bond in describing molecular structures with Lewis symbols
complete with formal charges
• apply an understanding of electronegativity to identify bond polarity
and element reactivity.
• draw and explain resonance structures
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Types of chemical bonds

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Energetics of chemical bond formation

When two or more atoms form bonds, this process can cause an
increase or decrease in potential energy.
A stable molecule is a molecule that has a lower potential energy than
the individual atoms of which it is composed.
ΔHof is often used as a reference whether the formation of compounds
causes a decrease or increase in potential energy.
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Practice problem
Based on the ΔHof value, the most stable compound is ...

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Ionic Bonds

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Ionic bonds
Ionic bonds are bonds that occur as a result of the attractive forces between
particles with opposite charges.

Ionic bonds take place between ions from metal elements and ions from
non-metal elements, because:
• Metallic elements have a relatively low ionization energy so that they easily
remove electrons to form stable positive ions.
• Non-metal elements have a relatively exothermic electron affinity so they
tend to accept electrons to form stable negative ions
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Ionic compounds
Ionic crystal is a cation-anion arrangement in a 3-dimensional lattice
called a lattice structure.

The ionic compound formula is an empirical formula, which is the

simplest ratio of cations and anions
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Energetics for the formation of ionic bonds
A stable compound is formed from the elements if in its formation
there is a decrease in potential energy (ΔHof).
Lattice energy is the amount of potential energy drop in the system
when 1 mole of solid is formed from the ions in the gas phase.

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Determination of lattice energy
Example of determining the lattice energy of NaCl:
Elattice = ?

One approach to the determination of lattice energy is to divide the

thermochemical reaction of standard formation of NaCl into several steps:

IE (Na) = +495.4 kJ/mol

EA (Cl) = -348.8 kJ/mol
Elattice =

The multi-stage reaction above by Born-Haber is depicted in the form of a

diagram, known as the Born-Haber Diagram.
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Born-Haber diagram

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Lattice energy of ionic compounds
Apart from using the Born-Habber diagram, the energy of the lattice can also
be estimated in value by using Coulomb's law.
The lattice energy of two ions with a charge and that is separated by a
distance according to Coulomb's law can be estimated by the following
equation:

• k = 4πεo , where εo is the dielectric constant of the medium

• Based on the above equation, the lattice energy will be negatively charged
because q1 and q2 are opposite signs.
• The equation above states that the lattice energy will be greater if
• the charge of the interacting particles is greater. Example: Elattice NaCl < Elattice MgCl2
• the distance between the ions is closer. Example: Elattice NaCl < Elattice LiCl.

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Lattice energy of ionic compounds

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Practice problem
Assuming that the separation distance between cations and anions is
almost the same, which species will have the greatest lattice energy?
A. Sodium chloride
B. Calcium chloride
C. Calcium nitride
D. Sodium oxide
E. Calcium oxide

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Practice problem
The first ionization energy of cesium is +376 kJ / mol and the electron
affinity of bromine is -325 kJ / mol, determine ΔE for the reaction

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Practice problem
Lithium fluoride has a lattice energy of -1033 kJ / mol. Ionic solid AB,
ion A2+ has a radius nearly the same as Li+, and B2- has a radius almost
the same as F-. What is the approximate value of the lattice energy for
AB?
A. Around 3 x (-1033 kJ/mol)
B. Around -1033 kJ/mol
C. Around 4 x (-1033 kJ/mol)
D. Around 2 x (-1033 kJ/mol)
E. Around 6 x (-1033 kJ/mol)

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Practice problem
Which solid below has the most exothermic lattice energy?

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Practice problem
Calculation of lattice energy
For two ions with a charge and those separated by a distance, the
potential energy can be determined by Coulomb's law:

Calculate the energy released when 1 mole of NaCl is formed, if you

know:

with

- The shortest distance between Na+ and Cl- ions is 282 pm.
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The electron configuration of the sodium ion
First and second ionization of sodium:
IE1 = 496 kJ/mol
IE2 = 4563 kJ/mol

IE2 ≈ 10 × IE1 so Na2+ is difficult to form, because the energy released cannot be
compensated for by the lattice energy when forming salt.

Therefore, sodium ions are found in nature only up to Na+.

In addition, Na+ ions also have noble gas electron configurations.

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The electron configuration of the calcium ion
IE1 = 590 kJ/mol
IE2 = 1140 kJ/mol
IE3 = 4940 kJ/mol

IE3 ≈ 4 × IE2 and the energy obtained from the lattice energy is only about
2000 kJ / mol, so that Ca3 + ions are difficult to form
Therefore, calcium ions are found in nature only up to Ca2+.

In addition, Ca2+ ions also have noble gas electron configurations.

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The ionic electron configuration of the transition metal
• The electrons that are lost first come from the largest n (outer shell), then
l.
• Example:

• The formation of Fe3+ ions provides extra stability as the d subshell

becomes half full
• Since the released transition metals are electrons in the outer shell, the
common ionic charge in transition metals is +2.
• Ions with a charge greater than +2 result from the loss of d electrons
• Note that both Fe2+ and Fe3+ do not achieve the rare gas electron
configurations.
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The ionic electron configuration of the post
transition metal
Example:

Sn can become Sn2+ by emptying the electrons at 5p.

Sn can also become Sn4+ by emptying electrons at 5s and 5p.

Note that both Sn2+ and Sn4+ do not achieve the rare gas electron
configurations.
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Predicting the electron configuration of a cation
Question:
The electron configuration of Bi according to Aufbau: [Xe] 6s2 4f14 5d10 6p3. What Bi ions
can be formed?
Answer:
Change the writing of the electron configuration Bi based on the increment of the
principal quantum number:

Bi can form Bi3+ ions by vacating electrons at 6p.

Bi can form Bi5+ ions by vacating electrons at 6s and 6p.

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Anion electron configuration
Non-metallic elements tend to accept electrons to achieve the noble gas electron
configurations:

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Octet rule
• The octet rule only works for group
1A and 2A metals, Al, and the non-
metal elements
• H and He cannot fulfil the octet
rule due to the limited number of
electrons which only 2 electrons
are maximum for filling skin n = 1.
• The octet rule also does not apply
to transition and post-transition
metal groups.

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Practice problem
The ground-state electron configurations appropriate for Cu and Cu2+
are …

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Practice problem
The ion which has the noble gas electron configuration is …

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Lewis’s symbol

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Lewis symbol for ionic bonds

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Practice problem
The species that has 8 valence electrons in its Lewis symbol is …

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Covalent Bond

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Covalent bond
Covalent bonds are formed as a result of sharing electrons.
To understand covalent bonds, consider how the bonds between H and H form H2

a) The attraction of the valence electrons from the H atom by the nucleus of another H
atom makes the two atoms move closer to each other.
b) When the two H atoms are close together, the electron density moves to the center as
the attraction of the H atom's nucleus increases over the other valence electrons of
the H atom.
c) When the two electrons get closer, the probability of finding the electron in the
middle increases, thus shifting the position of the nucleus closer together.

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Covalent bond

• When the nucleus continues to get

closer, there will be repulsion because
the same charge of the nucleus causes
the potential energy of the interaction to
increase.
• The final interaction distance between
two atoms that are covalently bonded is
at an equilibrium distance, which is the
distance where the balance between
attraction and repulsion occurs.
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Covalent bond
There are two quantities that characterize covalent bonds:
1. Bond length = distance between two nuclei (rA + rB)
2. Bond energy = the amount of potential energy released when a bond is
formed, or the amount of energy required to break a bond.

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Bond polarity
Nonpolar covalent bonds
A nonpolar covalent bond is formed
from the same two elements
sharing the same number of
electrons with each other
Polar covalent bond
Polar covalent bonds are formed
from two different elements, where
one atom attracts electrons more
strongly than the other.
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Polar covalent bond
A polar covalent bond is formed from two different elements, where one
atom attracts electrons more strongly than the other.

This condition creates an imbalance of electron density in the bond leading

to the concept of partial charge (δ).
for H − Cl: δ H+ = +0,17 and δ Cl− = −0,17
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Dipole moment
The dipole moment (µ) is a quantity for measuring the degree of
polarization in a covalent bond.

Where q = charge (Coulomb) and r is the distance between nuclei (meters) in

a chemical bond. The dipole moment (µ) uses the Debye (D) unit, provided
that 1 D = 3.34 x 10-30 Cm.

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Practice problem
Dipole moment calculation
In the chlorine monoxide molecule, chlorine (Cl−O) has a charge of
+0.167 e−. If the bond length is 154.6 pm, calculate the dipole moment
of this molecule in Debye units. Electron charge = 1.602 x 10-19 C.

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Electronegativity
Electronegativity (EN) is the relative attraction of an atom to the electrons
in the bond.

In one period EN increases from left to right as Zeff increases.

The difference in electronegativity (ΔEN) creates the polarity of the bond.

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Electronegativity difference = degree of ionic character
Non polar: ΔEN = 0
Bond ionic character level:
• ΔEN > 1.7 has a character> 50%
ionic, where atoms with high
electronegativity control electrons.
• ΔEN < 0.5 almost pure covalent
(nonpolar)
• 0.5 < ΔEN <1.7 polar covalent

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The relationship between elemental reactivity and electronegativity

Metal elements with low EN are easy to oxidize, while metals with high
EN are difficult to oxidize.
For non-metal elements, the oxidizing properties become stronger as
EN increases.
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Practice problem
The most polar bonds is …

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Practice problem
Based on its electronegativity, the strongest oxidizing species is …

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Drawing Lewis structures
• Not all molecules meet the octet rule
• The octet rule only applies to period 2 elements, such as C, N, O, and F.
• Be and B often have less electrons than an octet or incomplete octet, for example in
the molecules of BeCl2 and BCl3
• A second period element cannot possibly have more than 8 electrons, because at n =
2, there are only s and p subshells with a total of 8 electrons filling both subshells.
• The 3rd period element (n = 3) can contain more than 8 electrons, because
it has s, p, and d subshells.

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 Procedure for drawing Lewis structures
1. Determine how the atoms are SiF4 Framework:
bonded
• Outline the structure
Determine the central atom.
Usually selected
• of the atom with the lowest
electronegativity. 2. Count the total number of
valence electrons
• Example: SiF4
• Si is the atom with the lowest
electronegativity, so it is used
as the central atom
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 Procedure for drawing Lewis structures
3. Place two electrons in each pair 4. Complete the octet of the
of atoms that form a bond, then terminal atom by adding an
replace them with bond lines electron pair

valence electron = 32e- number of e- left = 24e-

single bond = -8e- non-bonding F e- pair = -24e-
number of e- left = 24e- number of e- left =0
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 Procedure for drawing Lewis structures
5. Place the remaining electrons on the central atom
In that case of SiF4 there are no electrons left after being placed on
the end atom.
6. If the central atom is not yet in an octet, a double bond forms and if
necessary, a triple bond.
In the case of SiF4, the center atom has an octet. So the Lewis
structure of SiF4 was solved in the 4th procedure.

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Lewis structure of H2CO3
The CO32- ion is an oxy ion, so the C atom is the central atom, and the O atom
surrounds it. The H+ ion is bonded to two O atoms.
Electron distribution: H2CO3 framework:

H2CO3 structure:

Single bond
e- remaining
Nonbonding e- pair But the central C atom only has 6 e- so it's
not an octet yet. While the electrons have
e- remaining been completely divided.
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Lewis structure of H2CO3
Since there are no electrons left, The result of O free electron
one of the lone pairs on the O atom transfer will produce a double
is converted to the second bond. bond between C and O.

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Lewis structure of N2F2

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Lewis structure of N2F2
• The number of valence electrons is insufficient to complete the nitrogen
octet.
• The formation of a double bond in the two nitrogen will complete the
second octet state of the nitrogen in the central atom.

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A structure with a central atom of expanded octet
• Elements on third period and more in the periodic table:
• has a larger atomic size
• has a d orbital
• can accept 18 electrons
• The Lewis structures for these group elements still follow the same procedure
only that the central atom can have additional bonds
• Example:

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A structure with incomplete octet central atom
Boron and Beryllium are two atoms when acting as the central atom cannot
reach the octet.

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Practice problem
Drawing Lewis structures
Draw Lewis structures for the following molecules:

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Selection of Lewis structures
When a molecule can be described by more than one possible Lewis
structure, how to determine the correct structure?
Examples on the structure of H2SO4 Experimental evidence:
there are two possibilities to The bond length (without H) < S-O
describe its structure binds H, indicating that S-O
without H is in the double bond
state S=O.

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Formal charges
Formal charge (FC) is the charge applied to an
atom regardless of its electronegativity.
Hence, charge
formal is not a real charge.

Where V = number of valence electrons for an

atom, N = number of nonbonding electrons,
and B = number of bonding electrons.

Stable structure:
1. The structure with the least formal charge.
2. The negative formal charge is carried by the
most electronegative atom
The lower structure has the
lowest formal charge, so it is
selected as the most plausible
structure.
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CO2 structure
There are 3 possible CO2 structures:

Among the three structures, the middle structure carries the least formal
charge, so that the second structure is the most stable of.

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Boron's formal and chemical charge
In the BCl3 structure, why are double bonds not formed to complete the octet?

When the formal charge (FC) is

calculated for B and Cl, we get:

All FC values are 0 so the molecules

are in the best structural condition,
so there is no need to form double
bonds.
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Practice problem
Based on the best Lewis structure for CH3NO2, the formal charge for
nitrogen on the molecule is ...

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Resonances

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Resonances
The Lewis structure of NO3- has one double bond (N= O) and two single bonds
(N-O):

The experimental results show that the three N-O bond lengths are the same,
namely the average of two single bonds and 1 double bond.
To explain the above problem, it is necessary to construct a resonance
structure, which is an equivalent structure that can explain the average bond
lengths of the three N-O:

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Resonance structure
• The Lewis structure assumes that the
electrons are localized between two
atoms
• In the resonance structure the
electrons are delocalized so that they
can move throughout the molecule
to give the equivalent bond length
• Another way of describing a
resonance structure is to create a
resonance hybrid structure

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Other examples of a resonance structures
CO32- resonance structure:

PO43- resonance structure:

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Resonance structures are not always equivalent
Two or more Lewis structures for the same compound do not always have
the same electron distribution.
How to determine the best e.g.: NCO- resonance
structure?
1. The octet must be filled
2. FC < 1
3. All negative charges are carried
by the more electronegative
atom.

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Resonance stabilization
The actual structure has better stability than one of the resonant structures.
As an example for benzene:

The resonance effect on benzene provides extra stability of 146 kJ / mol.

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Practice problem
Resonance structure
Draw all the resonance structures for SO3.

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Coordination Covalent Bonds

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Coordination covalent bonds
Normal covalent
For example in ammonia, one electron from each
atom shares to form a covalent bond.
Covalent coordination
For example in the ammonium ion, the N atom has a
pair of free electrons which are used to form a
covalent bond with the H+ ion which has no
electrons.
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Coordination covalent bonds
Boron which lacks electrons, readily accepts electron pairs to form
coordination covalent bonds.

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Practice problem
Coordination covalent bonds
1. When it is sublimated into gas at 180o C, solid AlCl3 forms Al2Cl6.
Draw the Lewis structure for Al2Cl6. Show that this molecule is
formed by covalent AlCl3 coordination of two molecules
2. Show the coordination covalent contribution of CO and HNO3
molecules.

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