CHEM1300 Chemistry

Semester A

Tutorial 2

Chapter 7: Periodic Properties of the Elements

Chapter 8: Basic Concept of Chemical Bonding
Chapter 9: Molecular Geometry and Bonding Theories

Yung-Kang Will Peng

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 Periodic Properties of the Elements

 Effective Nuclear Charge

 Property 1: Sizes of Atoms and Ions
Outline  Property 2: Ionization Energy
 Property 3: Electron Affinity
 Property 4: Metals, Metalloids and Nonmetals

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 Chapter 7: Periodic Properties of the Elements
Effective Nuclear Charge
Many properties of atoms depend on the effective nuclear charge, which is the portion of
the nuclear charge that an outer valence electron experiences. The core electrons are very
effective in screening the outer valence electrons from the full charge of the nucleus,
whereas electrons in the same shell do not screen each other as effectively.

Increase in Zeff

Zeff
Ar
Increase in Zeff

Ne

K
Na
Li

Atomic number, Z

How to explain this trend for elements in a period/group?

Why Zeff increases relatively slow in a group (cf. in a period)? 3
 Chapter 7: Periodic Properties of the Elements
Property 1: Sizes of Atoms and Ions
The size of an atom can be gauged by its bonding atomic radius, which is based on
measurements of the distances separating atoms in their chemical compounds. In general,
it increases as we go down a column in the periodic table and decrease as we proceed left
to right across a row.

Why atom/ion sizes increases down a group, while

decreases from left to right across a period?
How the size changes with gaining/losing an electron?

Periodic Trends in
Bonding Atomic Radius 4
 Chapter 7: Periodic Properties of the Elements
Property 1: Sizes of Atoms and Ions
• Cations are smaller than
their parent atoms because
the outermost electrons are
removed so that the
repulsions between
electrons are reduced.

• Anions are larger than their

parent atoms because
electrons are added so that
the repulsions between
electrons are increased.

• For ions carrying the same

charge, Ionic radius
increase in size as you go
down a group because of
the increasing value of n.
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 Chapter 7: Periodic Properties of the Elements
Property 2: Ionization Energy
The first ionization energies of the elements show periodic trends that are opposite those
seen for atomic size, with smaller atoms having higher first ionization energies. First
ionization energies slightly decrease as we go down a column and increase sharply as we
proceed left to right across a row.

Period 2
Why first ionization energy
increases sharply in a period
Period 3 while it decreases mildly down
Period 4 a group (Zeff/size)?
Period 5
Can you explain the cause of
the two discontinuities?

How ionization changes as we

remove electron successively?

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 Chapter 7: Periodic Properties of the Elements
Property 3: Electron Affinity
The electron affinity of an element is the energy change upon adding an electron to an
atom in the gas phase, forming an anion. In general, electron affinities become more
negative as we proceed from left to right across the periodic table. The halogens have the
most negative electron affinities, while for noble gases have positive electron affinities.

Why electron affinity becomes

very negative in a period while
not for elements in a group?

Can you explain the cause of

the three discontinuities?
1A & 2A/4A & 5A/7A & 8A

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 Chapter 7: Periodic Properties of the Elements
Property 4: Metals, Nonmetals, and Metalloids
The elements can be categorized as metals, nonmetals, and metalloids. The tendency of
an element to exhibit the properties of metals, called the metallic character, increases as
we proceed down a column and decreases as we proceed from left to right across a row.

Can you correlate this trend with ionization

energy/electron affinity trends above?
Why ?

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 Learning Outcomes for Chapter 7
• Explain the meaning of effective nuclear charge, Zeff, and how Zeff depends on nuclear
charge and electron configuration.
• Explain the general trends in properties (below) for elements in the periodic table.

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 Basic Concept of Chemical Bonding

 Chemical Bonding
 Bond Polarity & Electronegativity
Outline  Lewis Symbols & Octet Rule
 Drawing Lewis Structures
 Resonance Structures

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 Chapter 8: Basic Concept of Chemical Bonding

Chemical Bonding
We classify these bonds into three broad groups: ionic bonds,
which result from the electrostatic forces that exist between
ions of opposite charge; covalent bonds, which result from
the sharing of electrons by two atoms; and metallic bonds,
which result from a delocalized sharing of electrons in metals.
Bond Polarity & Electronegativity
In a nonpolar covalent bond the electrons in the bond are
shared equally by the two atoms; in a polar covalent bond
one of the atoms exerts a greater attraction for the electrons
than the other. Electronegativity is a numerical measure of
the ability of an atom to compete with other atoms for the
electrons shared between them.

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 Chapter 8: Basic Concept of Chemical Bonding
 Lewis Symbols & the Octet Rule
The valence electrons of an atom can be represented by electron-dot symbols, called
Lewis symbols. The tendencies of atoms to gain, lose, or share their valence electrons
often follow the octet rule, which says that the atoms in molecules or ions (usually)
have eight valence electrons.
 Drawing Lewis Structures
We learned steps for drawing Lewis structures for molecules/ions. Formal charge
calculation was introduced to determine the most important Lewis structure. In
general, the dominant Lewis structure will have low formal charges with any negative
formal charges residing on more electronegative atoms.
 Resonance Structures
In some cases, more than one equivalent Lewis structure can be drawn for a molecule
or polyatomic ion. The bonding description in such cases is a blend of two or more
resonance structures.

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 Chapter 8: Basic Concept of Chemical Bonding
 Steps for Drawing Lewis Structures

1. Sum the valence electrons from all atoms of the given molecule.
2. Write the symbols for the atoms and connect them with a single bond.
3. Complete the octets around all the atoms (not applicable to H/B/Be…).
4. If not enough electrons to give an atom an octet, try multiple bonds.

When a molecule have more than one possible Lewis structures….

Assigning formal charges to each atom in the molecule.
In general, best Lewis structure …
– … is the one with the (1) fewest formal charges.
– … puts a (2) negative formal charge on the most electronegative atom.

Still cannot decide after considering formal charge…

We call Lewis structures of this sort resonance structures.
(i.e. the delocalizing electron structure of the molecule.)
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1. Draw the best Lewis structure(s) for
(a) Phosphorus Trichloride (PCl3)_step 1-3
(b) Hydrogen Cyanide (HCN)_step 1-4 (multiple bond)
(c) Cyanate Ion (NCO–)_step 1-4 + formal charge

C: not octet
N: octet

C: octet Both C & N: octet

N: not octet

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2. Draw the best Lewis structure(s) for
(a) Ozone (O3)_step 1-4 + formal charge + resonance
(b) Boron Trifluoride (BF3)_step 1-4 + formal charge + resonance

Two possible Lewis structures

For the B=F double bond in each

structure, the F atom has a formal
charge of +1 while the less electro-
negative B atom has a formal charge
of -1…..Less important!
Boron here is an exception
to the Octet Rule! 15
You have learned how to obtain “the best Lewis structure of a molecule” above!

Theories introduced below can convert “the best Lewis structure of a molecule”
into 3D geometry and rationalize the obtained geometry by orbital hybridization
(allows us to identify the origin of sigma/pi bond)

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Molecular Geometry and Bonding Theories

 Shape of Molecules
Outline  VSEPR Theory
 Hybridization Theory
 Valence-bond Theory

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 Chapter 9: Molecular Geometry and Bonding Theories

 Shape of Molecules
The three-dimensional shapes and sizes of molecules are determined by their bond
angles and bond lengths.
 Theory 1: valence-shell electron-pair repulsion (VSEPR)
VSEPR model rationalizes molecular geometries based on the repulsions between
electron domains, which are regions about a central atom in which electrons are
likely to be found. The arrangement of electron domains around a central atom is
called the electron-domain geometry; the arrangement of atoms is called the
molecular geometry.
 Theory 2: Hybridization
To correlate the electron domain of central atom in terms of its atomic orbitals,
hybridization of atomic orbitals (e.g. s, p,..) is thus introduced. A particular mode of
hybridization can be associated with each of three common electron-domain
geometries (linear = sp; trigonal planar = sp2; tetrahedral = sp3).
 Theory 3: Valence-bond
Covalent bonds in which the electron density lies along the line connecting the atoms
(the internuclear axis) are called Sigma Bond (σ bond). Bonds can also be formed
from the sideways overlap of p orbitals. Such a bond is called a Pi Bond (π bond).
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 Chapter 9: Molecular Geometry and Bonding Theories
From the obtained electron-domain number of central atom to determine….
…electron-domain geometry and molecular geometry
(lone pairs are not considered!)

180°
AB2
180°

120° AB3

AB2
115°

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 Chapter 9: Molecular Geometry and Bonding Theories
From the obtained electron-domain number of central atom to determine….
…electron-domain geometry and molecular geometry
(lone pairs are not considered!)

AB4

109.5°

AB3
107°

AB2
104.5° 20
 Chapter 9: Molecular Geometry and Bonding Theories
From the obtained electron-domain geometry of central atom to determine….
atomic orbitals used for constructing hybrid orbital set.
electron-domain

BCH1100 Chemistry 19/20 Sem B - Lec 4 21

 Learning Outcomes for Chapter 8 & 9
1. Determine the best Lewis structure of a given molecule
2. Predict corresponding three-dimensional shapes using the VSEPR model.
3. Identify the atomic orbitals of central atom used for such hybridization.
4. Explain what orbitals are overlapped to form each σ and π bonds in a molecule.

One center case 4 e-domain

for central C

VSEPR
Molecular geometry e-domain geometry
(tetrahedral)
Lewis structure Hybridization

sp3 hybridization for central C

sp3-s Each sigma bond

sp3-s is formed by the
sp3-s overlapping of
1*sp3 from C and
sp3-s s from H

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 Learning Outcomes for Chapter 8 & 9
Two center case

3 e-domain H1 H2
H H
for each C

C1
H H e-domain geometry for each C sp2 p
Lewis structure (trigonal planar) C2

sp2 hybridization for each C H3 H4

Molecular geometry

sp2-sp2
sp2-s sp2-s
Five sigma bond
p-p sp -s
2
sp2-s
4*C-H σ bond: sp2-s
1*C-C σ bond: sp2-sp2
One pi bond
1*C-C π bond: p-p

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sp2 resonance structure
Valence-bond Theory
Resonance Structure, Delocalization and  Bonding_Benzene (C6H6)
Resonance structures can be
more fundamentally viewed with
the valence-bond theory.

Three e-domain for each C atoms (sp2)!

The C=C double bond:
1* bond: sp2-sp2 between C atoms.
1* bond: p-p between C atoms.

• A benzene molecule has six C–C/C-

H  bonds and one unhybridized p
orbital on each C atom.

• The  electrons in benzene are not

localized, they are delocalized.

• The even distribution of the

electrons in benzene makes the
molecule very stable.
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 Practice 1
(a) Draw the best Lewis structure(s) for BF3.
(b) Determine the corresponding formal charge of each atom.
(c) Determine the molecular geometry of BF3.
(d) Determine the hybridization scheme of the central atom of BF3.
(e) Determine orbitals used for forming each σ (or π) bonds in BF3.
0

0
0 0

best Lewis structure

sp2 hybridization for central B
Central B has
3 e-domains
F
promote

B
F F
Molecular geometry e-domain geometry
(trigonal planar)
sp2-p Each sigma bond is formed
sp2-p by the overlapping of 1*sp2
sp2-p from B and p from F 25
 Practice 2
(a) Draw the best Lewis structure(s) for nitrate anion (NO3−).
(b) Determine the corresponding formal charge of each atom.
(c) Determine the molecular geometry of NO3−.
(d) Determine the hybridization scheme of the central atom of NO3− .
(e) Determine orbitals used for forming each σ (or π) bonds in NO3−.
0

0
0

The central N has 3 electron domains

& no nonbonding electrons Trigonal planar

Three sigma bond p-p sp2-sp2

3*N-O σ bond sp2 hybridization for central
p-sp2 sp2-p
One pi bond N to provide this geography.
1*N-O π bond

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 Practice 3
(a) Determine the hybridization scheme of each central atom in the
following molecule (glycine).
(b) How many σ and π bonds in this molecule?

4 4 3 4

sp3 sp3 sp2 sp3

9 σ bonds and 1 π bond

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 Practice 4
(a) Determine the hybridization scheme of each central atom in the
following molecule (phenylalanine).
(b) How many σ and π bonds in this molecule?

O H H O H
sp3 sp3 sp2
NH2 CH C OH H N C C O sp3
sp3
H C H
CH2
sp2
H C sp2 H
C C
sp2

C C sp2

sp2
H C sp2 H

H
23 σ bonds and 4 π bonds
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 Practice 5
(a) Determine the hybridization scheme of each central atom in the
following molecule (cumulene).
(b) How many σ and π bonds in this molecule?
(c) Can you visualize the orbitals forming σ and π bonds? (challenging!)

sp2 sp sp sp2

7 σ bonds and 3 π bonds

sp2

sp
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 For inner two sp carbons

1 2 3 4
For outer two sp2 carbons

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 Cumulene in 3D

https://www.youtube.com/watch?v=W0BS45HranA&ab_channel=Edmerls
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 The End
&
Thanks For Your Attention !