F23 Topic 1

Topic 1: The Quantum

Mechanical Model of the Atom (Ch. 7)
particleofmatter ismanest
Topics covered:
centernucleussurroundingbyelectrons E l
7.2 Theelements
nature of light
make up
7.3energy
just Atomic spectroscopy and the Bohr model
emptyspace
7.4 The wave nature of matter
hasorbitals
7.5 Quantum mechanics and electrons in atoms
atomicnumbertells uswhichelementit is
7.6 The shapes of atomic orbitals
7.7 Electron configurations
1
 F23 Topic 1

What do you know about the atom?

morbital

electrode
mode
nuclear
mmqif.de and
together

ygt
Bohr
model Quantum
model
ngg
onangemioanotner noticearayumen
atomosiindivisible aparticusmanertnan
aaromrerectrons

piumbpuaaingm.ae
uneg
c naraea
qgm.es
floating in

mum catnoaera

2
 F23 Topic 1

200 years of atomic theory

electrons

ἄτο
ἄτομος
μος

460-370 BCE 1804 1903 1911 1913 1926

Democritus Dalton Thomson Rutherford Bohr Schrödinger

3
 F23 Topic 1

Cathode Ray Tube – Discovery of the electron

Theoryisnotaguess rather
scientificmethod
theoryisanexplanationforagiven
phenomenalbasedonexperimental
measurements
atomictheory
stringtheory
theoryofrelativity
law's unexpectedoutcomegiven
ME previousobservations
principles
PKnRT gematriesthatexplain
law
newtons whatisouewang https://www.youtube.com/watch?v=7YHwMWcxeX8
tohappenwhen
4
whats
 g app F23 Topic 1

Theories vs. laws in science

• What is the difference
between a theory and a
law in science?

5
 F23 Topic 1

7.2 THE NATURE OF LIGHT

6
 F23 Topic 1

7.2 The nature of light

• Light is a type of energy called electromagnetic radiation
• Perpendicular oscillating electric and magnetic fields
Tah
Iamdat
A

Iwavelength
• Light moves at a speed of 2.998 x 108 m/s (given the symbol 𝑐)
7
 F23 Topic 1

7.2 The nature of light

• Electromagnetic waves exhibit peaks and troughs at regular intervals.

ni

to
causesame
wavelength
8
 F23 Topic 1

7.2 The nature of light

• Wavelength (𝜆) – Distance

between adjacent peaks
• Determines colour of the ummmm
light

• Amplitude – Height of the

wave higherfrequencybemorewavelengthpass
• Determines brightness of inverserelationshiphigh
frequency
shortfrequency
the light
9
 F23 Topic 1

7.2 The nature of light

• Frequency (𝜐) – The # of wavelengths
I pass
that a particular point in space over
C2.99811108ms
a period of time (Hz = cycles/second)
3 distancenm m
• What do you notice about the
relationship between wavelength and
6 frequency?

12
 F23 Topic 1

7.2 The nature of light

• Wavelength multiplied by frequency equals the speed of light 𝑐.

𝑐 = 𝜆𝜐

frequency.
71 5.09 𝑐
É
• This means there is an inverse relationship between wavelength and

𝑐
1014420
𝜐
𝜆= 𝜐 =
𝜆
– Larger wavelength → smaller frequency
– Smaller wavelength → larger frequency
11
 F23 Topic 1

7.2 The nature of light – Example #1

Sodium vapour street lamps emit light at a wavelength of 589 nm. What is
lowfrequency highfrequency
the frequency of this radiation?
rotations vibrations

0
wavelength Tshort
long wavelength

I shfrtesta
longestA
visible visible 12
 F23 Topic 1

7.2 The nature of light

• The range of all possible frequencies is known as the electromagnetic spectrum.

and shortest
wavelength

13
 F23 Topic 1

7.2 The nature of light – Example #2

Which wave has the higher frequency?

a) Wave 1

b) Wave 2
IR rlongerwavelength
14
 F23 Topic 1

7.2 The nature of light – Example #2

If one wave represents visible light and the other represents infrared
radiation, which wave is which?

a) Wave 1

b) Wave 2
Blackbody radiation thermal
radiation
15
 F23 Topic 1

7.2 The nature of light

• Prevailing theory in the early 1900’s: energy consisted of waves &

matter consisted of particles.

• But some things couldn’t be

explained!
É
• For example, why does matterenergy y
give off light when it gets hot?

g 16
 F23 Topic 1

7.2 The nature of light

• The ultraviolet catastrophe – infinite light intensity at short wavelengths!
specific
amount
• Max Planck (1900) proposed
ofthat energy can only be
energy
released or absorbed by
atoms in “chunks” called
quanta.

𝐸 = 𝑛ℎ𝜈
• Planck’s constant ℎ = 6.626 x 10-34 J s
• 𝑛 = 1, 2, 3 etc.
chunks 17
 F23 Topic 1

7.2 The nature of light

lightisshinedon
electronsgetrejectedatLathery
metaland th

Continuous energy Quantized energy

(classical physics) (quantum physics)
18
 F23 Topic 1

7.2 The nature of light

• The photoelectric effect – only light at certain wavelengths can eject
electrons from a metal surface.

photonsdepindingon n
frequency

MY immbworthnnenfhenergytoejectelectrons
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Ephotontoolow
19
toejectane haveenough haveenough F23 Topic 1

energytoeject energytoejectelectron
7.2 The nature of light electron
• Einstein (1905) explained that light must consist of particles
(photons), each with energy 𝐸 = ℎ𝜈.
– Wave-particle duality! ℎ𝑐
𝐸 = ℎ𝜈 =
𝜆

Keotejectedelectron

tworkfunctionenergyneededtoejectanelectron
20
 photon j
F23 Topic 1

7.2 The nature of light

• The amount of energy required to remove an electron is the work
function 𝜙 J

a Aasonm.epnoton
Emoteofphotons
Ephotonhey Esinglephotonxarogaarosnumber

3osaxoiajpnotonCG.ozzxiophotonim.ie
photon
6.626 1.810ilmoler
1,1t.gxioktim
1
9513121

epn.tn
• Kinetic energy isae
i
m of electron is equal to the “leftover” energy
zixo.at
Epnoton

𝐾𝐸 = ℎ𝜈 − 𝜙
21
 F23 Topic 1

7.2 The nature of light– Example #3

A red laser pointer emits light at a wavelength of 650 nm.
a) What is the energy of a single photon from the laser pointer?
b) What is the energy of one mole of photons from the laser pointer?
epnot.nra.am
1 19
m Ephoton6.534 1018 7
YEE 85 653
JIM
10
0
jJ 5.522 10 185
1812xyj 22
 F23 Topic 1

7.2 The nature of light– Example #4

Light with a wavelength of 30.4 nm was shone on a sample of platinum
metal. Electrons were ejected with a kinetic energy of 5.522 x 10-18 J. What
is the work function for platinum?

23
 F23 Topic 1

7.3 ATOMIC SPECTROSCOPY AND THE BOHR MODEL

whitight

24
 F23 Topic 1

7.3 Atomic spectroscopy and the Bohr model

• Light passed through a prism can be separated into a spectrum of its
component wavelengths.

• A white light source (like sunlight) produces a continuous spectrum.

a
25
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7.3 Atomic spectroscopy and the Bohr model

• When electric current is passed through H2 gas, it glows pink.
at t t t
• A prism separates this into a line spectrum.
H

He

Ba

26
 F23 Topic 1

7.3 Atomic spectroscopy and the Bohr model

• Each element has its own line spectrum. Why does this happen?

Hg He H
27
 F23 Topic 1

7.3 Atomic spectroscopy and the Bohr model

• Johann Balmer (1885) and Johannes Rydberg (1888) developed an
equation to reproduce the line spectrum of hydrogen.
𝑅𝐻 = 1.096776 x 107 m-1
(Rydberg constant)

1 1 1
= 𝑅𝐻 2
− 2
𝜆 𝑛1 𝑛2

Johann Balmer Johannes Rydberg

𝑛1 and 𝑛2 are positive integers,
with 𝑛1 < 𝑛2

• This equation explains what but not why!

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 F23 Topic 1

7.3 Atomic spectroscopy and the Bohr model

• Niels Bohr (1913) explained these observations with a new model of
the H atom
1. Electrons in an atom can only occupy certain orbits at fixed
distances from the nucleus.

Niels Bohr

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 F23 Topic 1

7.3 Atomic spectroscopy and the Bohr model

2. Electrons in orbits have specific, “allowed” energies.
∞ ∞ 0J
Nuclear charge
Excited states
𝑍2
𝐸𝑛 = −ℎ𝑐𝑅𝐻
𝑛2

𝑍2
𝐸𝑛 = −2.178 × 10−18 𝐽
𝑛2
Ground state
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7.3 Atomic spectroscopy and the Bohr model

3. Energy is only absorbed or emitted in such a way as to move an electron
from one “allowed” energy state to another.

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7.3 Atomic spectroscopy and the Bohr model

• The amount of energy absorbed or emitted is calculated by:

∆𝐸 = 𝐸𝑓𝑖𝑛𝑎𝑙 − 𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙

𝑍2 𝑍2
∆𝐸 = −2.178 × 10−18 𝐽 2
− 2
𝑛𝑓 𝑛𝑖

Final energy level Initial energy level 32

 F23 Topic 1

7.3 Atomic spectroscopy and the Bohr model

• The Bohr model explains why hydrogen exhibits a line spectrum.

33
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7.3 Atomic spectroscopy and the Bohr model

• A note on sign:
– If a photon is being emitted, it moves to a lower energy level and Δ𝐸
is negative.
– If a photon is being absorbed, it moves to a higher energy level and
Δ𝐸 is positive.

• The energy of an individual photon can only be positive.

𝐸𝑝ℎ𝑜𝑡𝑜𝑛 = Δ𝐸
Absolute value

34
 F23 Topic 1

7.3 Atomic spectroscopy and the Bohr model – Example #1

a) For a hydrogen atom, calculate the energy change (kJ/mole) when the
electron undergoes a transition from n = 5 to n = 2.
b) What is the frequency (Hz) and wavelength (nm) of the light emitted?

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 F23 Topic 1

7.3 Atomic spectroscopy and the Bohr model

• The emission spectrum of hydrogen is often split into series
∞
• Which series would produce the
Name 𝒏𝒇𝒊𝒏𝒂𝒍 highest energy photon?
Lyman 1
Balmer 2
Paschen 3
• Which series would produce the
Brackett 4
lowest energy photon?

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 F23 Topic 1

7.3 Atomic spectroscopy and the Bohr model

• Based on what you know about the EM spectrum, in what region would
you expect the Lyman and Brackett series to lie?
Name 𝒏𝒇𝒊𝒏𝒂𝒍 EM region
Lyman 1
Balmer 2 visible
Paschen 3 IR
Brackett 4

37
UV Visible Infrared
 F23 Topic 1

7.3 Atomic spectroscopy and the Bohr model– Example #2

The Brackett series contains an emission at 𝜆 = 2620 nm. Determine the

initial and final values of 𝑛 associated with this spectral line.

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 F23 Topic 1

7.3 Atomic spectroscopy and the Bohr model

• Recap:
– Nucleus has +ve charge and most of
the mass
– e- travel in fixed orbits around the
nucleus, like the solar system
– Orbits are fixed in energy and radius
– Electrons can transition from one
orbit to another by absorbing or
emitting photons of specific energies
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 F23 Topic 1

7.3 Atomic spectroscopy and the Bohr model

• Deficiencies of the Bohr model:
– Only works for one-electron systems
– Doesn’t explain why electrons don’t fall into the nucleus
– Doesn’t explain why orbits are fixed in energy

• A new model was needed to address these deficiencies!

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 F23 Topic 1

7.4 THE WAVE NATURE OF MATTER

41
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7.4 The wave nature of matter

• When waves meet each other in a pond, they cause interference.

42
 F23 Topic 1

7.4 The wave nature of matter

• Photons interfere with each other when a beam of light is passed
through two closely spaced slits.

• An interference
pattern is a
characteristic
property of waves

43
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7.4 The wave nature of matter

• What happens when we repeat this experiment with electrons?

44
 F23 Topic 1

7.4 The wave nature of matter

• Electrons build up an interference pattern, even if one electron is fired
through the slits at a time.
• What does this tell us?

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 F23 Topic 1

7.4 The wave nature of matter

• Electrons also exhibit wave-particle duality!

• There are 3 important consequences of this fact that address the

shortcomings of the Bohr model:
1. de Broglie wavelength
2. The Heisenberg uncertainty principle
3. Indeterminacy

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 F23 Topic 1

7.4 The wave nature of matter

1. The de Broglie wavelength (1924)
• Louis de Broglie realized that if light can have particle properties,
then matter should also have wave properties
• He proposed that matter in motion can be treated as a wave.

Planck’s constant

ℎ ℎ
𝜆= = momentum
𝑚𝑣 𝑝
mass velocity
Louis de Broglie
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 F23 Topic 1

7.4 The wave nature of matter

• Scanning electron
Electron Gun
microscope uses the
wave properties of
electrons to obtain
Magnetic extreme magnification
Lens

Mounting
Stage for
Sample 48
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 F23 Topic 1

7.4 The wave nature of matter – Example #1

What is the wavelength of an electron moving with a speed of 5.97 × 106
m/s? (The mass of an electron is 9.11 × 10-31 kg, 1 J = 1 kg●m2/s2)

49
 F23 Topic 1

7.4 The wave nature of matter

2. The Heisenberg Uncertainty Principle (1927)
• What happens when the
two-slit experiment is
modified so that we can
detect which slit an
electron goes through?

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 F23 Topic 1

7.4 The wave nature of matter

2. Heisenberg Uncertainty Principle (1927):
• It is impossible to know both the exact
momentum and location of an electron at the
same time.
Werner Heisenberg

ℎ
(Δ𝑥)(𝑚Δ𝑣) ≥
4𝜋
Uncertainty in position Uncertainty in
(particle property) momentum
(wave property)
51
https://xkcd.com/1473/
 F23 Topic 1

7.4 The wave nature of matter – Example #2

Calculate the uncertainty in position for an electron with a speed known
to ± 2.0 x 104 m/s (the mass of an electron is 9.11 ×10-31 kg) to the
uncertainty in the position of Usain Bolt (94 kg) moving at 10.45 m/s ±
0.10 m/s.

52
 F23 Topic 1

7.4 The wave nature of matter

3. Indeterminacy
• The uncertainty in position of an electron is often larger than the
size of an atom. How do we know where it is?

• We only know where the electron is likely to be.

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 F23 Topic 1

7.4 The wave nature of matter

3. Indeterminacy
• The behaviour of an electron can only be described using a
probability distribution map.

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7.5 QUANTUM MECHANICS

7.6 THE SHAPES OF ATOMIC ORBITALS

55
 F23 Topic 1

7.5 Quantum mechanics

• Bohr: electrons are particles in quantized orbits.
• Quantum mechanics: electrons are standing waves.

• Quantization: Only specific wavelengths will

create a standing wave! 56
 F23 Topic 1

7.5 Quantum mechanics

• Erwin Schrödinger (1926) developed the quantum model of the atom
based on Bohr and de Broglie’s equations.

Schrödinger equation Energy

Hamiltonian operator
෡ = 𝐸𝜓
ℋ𝜓
Wave function Erwin Schrödinger

• Schrödinger realized the electron was a 3D standing wave

– Described by the wave function 𝜓
– No easy physical interpretation for 𝜓
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 F23 Topic 1

7.5 Quantum mechanics

• The square of the wave function 𝜓 2 is the
electron density
– The probability of finding an electron at a
given point

• An orbital is defined as a region where there is

a high (90%) probability of finding an electron
– The orbital is the probability distribution
map for the electron
The Orbitron - https://winter.group.shef.ac.uk/orbitron/
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7.6 The shapes of atomic orbitals

• Orbitals can be represented in different ways

3D surface Dot distribution Radial distribution Energy level diagram

• Each orbital can hold two electrons

• Orbitals exist in energy levels called shells
• Shells consist of subshells with orbitals of different shapes
• Orbitals denoted by letters: s, p, d, f 59
 F23 Topic 1

7.6 The shapes of atomic orbitals

• Orbitals can have nodes
• Regions of space where there is no electron density

• Orbitals also have a phase

• Represented by different colours

60
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7.6 The shapes of atomic orbitals

s orbitals:

Shape

Number of nodal planes

Possible orientations

• Nodal plane – region where the probability of finding

the electron is zero

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7.6 The shapes of atomic orbitals

p orbitals:
Shape
Number of nodal planes

Possible orientations

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7.6 The shapes of atomic orbitals

d orbitals:
Shape
Number of nodal planes

Possible orientations

63
 F23 Topic 1

7.6 The shapes of atomic orbitals

f orbitals:
Shape
Number of nodal planes

Possible orientations

64
 F23 Topic 1

7.6 The shapes of atomic orbitals

• Orbitals in higher energy
levels have radial nodes.

• Distances from the

nucleus where there is no
electron density.

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7.5 Quantum mechanics

Let’s review the Bohr and quantum models of the atom
Bohr Model Quantum Model

Electronic
Structure

Energy
Levels

Generality
66
 F23 Topic 1

7.5 Quantum mechanics

• Each electron in an atom has a unique set of 4 quantum numbers.
– Principal quantum number 𝑛
– Azimuthal quantum number ℓ Solution to the
Schrödinger equation
– Magnetic quantum number 𝑚ℓ
– Spin quantum number 𝑚𝑠
More about this later!
• This is the “address” of the electron
– e.g. (𝑛, ℓ, 𝑚ℓ , 𝑚𝑠 ) = (2, 1, -1, +½)

67
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7.5 Quantum mechanics

Principle quantum number 𝒏
• Designates the shell/energy level,
same as the Bohr model

• Positive integer (e.g. 1, 2, 3 etc)

• Larger 𝑛 values means higher energy

and a bigger orbital

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7.5 Quantum mechanics

Azimuthal quantum number ℓ
• Defines the shape of the orbital (the subshell)
• Integer ranging from 0 to 𝑛 − 1
ℓ= 0 1 2 3
subshell s d
shape dumbbell more complex shapes

69
 F23 Topic 1

7.5 Quantum mechanics

Magnetic quantum number 𝒎ℓ
• Describes the 3D orientation of the orbital
• Allowed values: Integers ranting from −ℓ to +ℓ

Example: What are the allowed 𝑚ℓ values for p orbitals?

70
 F23 Topic 1

7.5 Quantum mechanics – Example #3

What is the value of ℓ and the allowed values of 𝑚ℓ for these orbitals?

71
 F23 Topic 1

7.5 Quantum mechanics

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7.5 Quantum mechanics – Example #4

How many orbitals exist in the 𝑛 = 4 level?

73
 F23 Topic 1

7.5 Quantum mechanics

Spin quantum number 𝒎𝒔
• Describes the “spin” of the
electron

• The electron behaves like a

small spinning charge which
yields a magnetic field that
can point “up” or “down”

• Allowed values: +½ or -½

74
 F23 Topic 1

7.5 Quantum mechanics

Pauli exclusion principle:
• No two electrons can have the same set of quantum
numbers

• Since there are only two possible values of 𝑚𝑠 , this means

Wolfgang Pauli
that each orbital can hold only two electrons!

𝑛 ℓ 𝑚ℓ 𝑚𝑠
+ ½ or -½
Describes orbital
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7.5 Quantum mechanics– Example #5

Consider these 4 quantum numbers (𝑛, ℓ, 𝑚ℓ , 𝑚𝑠 ) = (5, 2, -1, +½)

a) How many electrons does this correspond to?

b) What shell is it in?
c) What is the shape of the orbital?

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 F23 Topic 1

7.5 Quantum mechanics – Example #6

When 𝑛 = 3, the allowed values of ℓ are:

a) 1, 2, and 3.
b) 1 and 2.
c) 0, 1, 2, and 3.
d) 0, 1, and 2.

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 F23 Topic 1

7.5 Quantum mechanics – Example #7

Which of the following is a valid set of four quantum numbers? (𝑛, ℓ, 𝑚ℓ , 𝑚𝑠 )

a) 2, 1, 0, +1/2
b) 2, 2, 1, -1/2
c) 1, 0, 1, +1/2
d) 2, 1, +2, +1/2
e) 1, 1, 0, -1/2

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 F23 Topic 1

7.5 Quantum mechanics

• A few important points:
– The general orbital shape is the
same regardless of the shell it
belongs to.
– The same orbital in a higher shell
is larger and has more radial
nodes.
– All orbitals are centered on the
nucleus and are superimposed
over each other.
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 F23 Topic 1

7.7 ELECTRON CONFIGURATIONS

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7.7 Electron configurations

• One-electron atoms (e.g. hydrogen):
• The orbital energy is determined
by the value of 𝑛.

Orbitals with the same energy are

called degenerate

81
 F23 Topic 1

7.7 Electron configurations

• For atoms with more than one
electron:
• The orbital energy is determined
by the value of 𝑛 and ℓ.

𝐸 𝑠 <𝐸 𝑝 <𝐸 𝑑 <𝐸 𝑓 < …

• This is known as sub-level splitting

• Orbitals with the same ℓ are still degenerate
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 F23 Topic 1

7.7 Electron configurations

• Why does this happen?
• Recall radial nodes

• 2𝑠 orbital has a radial node, 2𝑝 does not

• The 2𝑠 penetrates closer to the nucleus,
which lowers its energy relative to the 2𝑝
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 F23 Topic 1

7.7 Electron configurations

• Can you use this figure to explain the sub-level splitting of the 𝑛 = 3
orbitals?

84
 F23 Topic 1

7.7 Electron configurations

• Methods for showing how electrons are distributed in atomic orbitals:

Energy Level Diagram Orbital Diagram Condensed Electron Configuration

3p
1s 2s 2p 3s
Energy

↿ 3s
Expanded Electron Configuration
↿⇂ ↿⇂ ↿⇂ 2p

↿⇂ 2s

↿⇂ 1s

85
Na
 F23 Topic 1

7.7 Electron configurations

• Rules for filling orbitals:

1. Aufbau Principle: Orbitals are filled from lowest to highest energy.

86
 F23 Topic 1

7.7 Electron configurations

4p
2. Hund’s Rule: For degenerate orbitals, the
3d lowest energy is attained by having the
4s maximum number of electrons with the same
spin.
3p
Energy

3s
3. Pauli Exclusion Principle: Maximum of 2
2p electrons per orbital.
2s

1s
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 F23 Topic 1

7.7 Electron configurations – Example #1

Draw the orbital diagram and write the electron configuration for oxygen
(O, Z = 8)

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 F23 Topic 1

7.7 Electron configurations – Example #2

a) Write the condensed electron configuration for silicon (Si, Z = 14).
b) How many unpaired electrons are there?
c) How many electrons are in the valence (i.e .outermost) shell?

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 F23 Topic 1

7.7 Electron configurations – Example #3

4p a) Complete the energy level diagram for N.
3d

4s b) Circle the electrons with quantum numbers (𝑛,

ℓ,𝑚ℓ ) = (2, 1, 0) on the energy level diagram.
3p
Energy

3s c) What are the values of 𝑛 and ℓ for the valence

electrons?
2p

2s

1s
90
 F23 Topic 1

7.7 Electron configurations

• Electron configurations for transition metals are a little tricky!
• The 4s and 3d orbitals are very close in energy

• Generally, the 4𝑠 is filled before

the 3𝑑

• Higher penetration, lower repulsion

91
 F23 Topic 1

7.7 Electron configurations

• There are some important exceptions:

• Half-filled and completely filled subshells are more energetically favourable.

• Only seen in the transition metals and lanthanides/actinides 92
 F23 Topic 1

7.7 Electron configurations

• Ions are atoms that have lost (cations, +) or gained (anions, −) electrons

• For anions, add extra electrons following the usual rules

↿⇂ ↿⇂ ↿ 2p 2p
Energy

Energy
↿⇂ 2s 2s

↿⇂ 1s 1s

F: 1s22s22p5 F−:
93
 F23 Topic 1

7.7 Electron configurations

• For cations, remove the electrons with the highest 𝑛
• If there is a tie, remove electron with highest ℓ (reverse Aufbau)

V: Ar 4s2 3d3 ↿⇂ 4s ↿⇂ ↿ 3d

V + : Ar 4s1 3d3 ↿ 4s ↿⇂ ↿ 3d

V 2+ : Ar 3d3 4s ↿⇂ ↿ 3d

V 3+ : Ar 3d2 4s ↿⇂ 3d
94
 F23 Topic 1

7.7 Electron configurations

• Why do we remove the 4𝑠 before the 3𝑑?

• The 4𝑠 is actually higher energy!

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 F23 Topic 1

7.7 Electron configurations – Example #4

Draw the orbital diagram and write the condensed electron configuration for:
a) S2- (Z = 16)
b) Fe3+ (Z = 26)

96
 F23 Topic 2

Topic 2: Periodic Properties of the Elements (Ch. 8)

Topics covered:
8.2 The development of the periodic table
8.3 Electron configurations, valence electrons and the periodic table
8.5 Periodic trends in the sizes of atoms and effective nuclear charge
8.6 Ionic radii
8.7 Ionization energy
8.8 Electron affinities and metallic character
8.9 Some examples of periodic chemical behaviour
1
 F23 Topic 2

What do you know about the periodic table?

2
 F23 Topic 2

8.2 THE DEVELOPMENT OF THE PERIODIC TABLE

8.3 ELECTRON CONFIGURATIONS, VALENCE ELECTRONS
AND THE PERIODIC TABLE

3
 F23 Topic 2

8.2 The development of the periodic table

• Dmitri Mendeleev (1871) observed that when the known elements were
arranged by mass, elements with similar properties fell into columns.

4
 F23 Topic 2

8.2 The development of the periodic table

• The table allowed Mendeleev to predict the existence and properties of
gallium and germanium

5
 F23 Topic 2

8.2 The development of the periodic table

• The modern
periodic table is
arranged by atomic
number, not mass

• Why does the

periodic table
work?
• Quantum theory!
6
 F23 Topic 2

8.3 Electron configurations and valence electrons

• Let’s look more closely at the first 18 elements of the periodic table.
• What do you notice about their electron configurations?

7
 F23 Topic 2

8.3 Electron configurations and valence electrons

• Elements in the same column have the same number of electrons in the
outermost principal energy level (highest 𝑛)
• These are called valence electrons
• Electrons in lower energy levels are called core electrons

8
 F23 Topic 2

8.3 Valence electrons – Example #1

Write the electron configuration for magnesium and determine how many
valence electrons it has.

9
 F23 Topic 2

8.3 Electron configurations and valence electrons

• The periodic table can be separated into 4 blocks (𝑠, 𝑝, 𝑑, 𝑓)

• Provides an easy
shortcut for
determining
electron
configurations!

10
 F23 Topic 2

8.3 Valence electrons – Example #2

Use the periodic table to write the condensed electron configuration for chlorine

11
 F23 Topic 2

8.3 Valence electrons

• The periodic table can also be used to predict formation of certain ions
• Recall: Noble gas electron configurations are very stable!

12
 F23 Topic 2

8.5 – 8.9 PERIODIC TRENDS

13
 F23 Topic 2

8.5 Periodic trends in atomic size

• Not only does the periodic table help with electron configurations, we
can also determine properties of elements based on their position in
the table.

• This includes:
– Atomic radius
– Ionization energy
– Electron affinity
– Metallic character
14
 F23 Topic 2

8.5 Periodic trends in atomic size

• These properties are due to the effective nuclear charge (𝑍𝑒𝑓𝑓 )
• This is the amount of positive charge “felt” by the valence electrons

Core electrons Valence electrons

e-
e- e-
e- e-
e- e-

• Core electrons repel the valence electrons, so 𝑍𝑒𝑓𝑓 < 𝑍

• Larger 𝑍𝑒𝑓𝑓 means larger nuclear-electron attraction 15
 F23 Topic 2

8.5 Periodic trends in atomic size

• 𝑍𝑒𝑓𝑓 is calculated as:

𝑍𝑒𝑓𝑓 = 𝑍 − 𝑆
Number of core electrons

Nuclear charge

• Practice: What is 𝑍𝑒𝑓𝑓 for Na?

16
 F23 Topic 2

8.5 Periodic trends in atomic size

𝑍𝑒𝑓𝑓 increases - Why?

Small
increase in
𝑍𝑒𝑓𝑓 - Why?

17
 F23 Topic 2

8.5 Periodic trends in atomic size

Atomic radius:
• The covalent radius 𝑟 is a convenient way to determine the radius of an
atom.

• Equal to half the bond length 𝑑 when two identical

atoms are covalently bonded.
– F2, O2, H2 etc.

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 F23 Topic 2

8.5 Periodic trends in atomic size

Discussion:
Based on your understanding of 𝑍𝑒𝑓𝑓 , determine the trend in atomic
radius as you progress from left to right across the second period (Li, Be, B,
C, N, O, F, Ne).

Based on your understanding of 𝑍𝑒𝑓𝑓 and quantum numbers, determine

the trend in atomic radius as you progress from top to bottom in group
one (H, Li, Na, K, Rb, Cs, Fr).

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 F23 Topic 2

8.5 Periodic trends in atomic size

• Atomic radius
decreases from
left to right across
a period

• Atomic radius
increases down a
column

20
 F23 Topic 2

8.5 Periodic trends in atomic size – Example #1

• Which element has a

larger radius?
a) P vs. S

b) Mg vs. Ca

c) F vs. Be

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 F23 Topic 2

8.5 Periodic trends in atomic size – Example #2

Arrange the following in order of smallest to largest atomic radii:
Na, Rb, Mg, K

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 F23 Topic 2

8.6 Ionic radii

• Recall: Ions are atoms that have gained or lost electrons
– Cation: positively charged (lost electrons)
– Anion: negatively charged (gained electrons)

• Cations are smaller than their parent atoms

– Less electron-electron repulsion, higher 𝑍𝑒𝑓𝑓

• Anions are larger than their parent atoms

– More electron-electron repulsion, lower 𝑍𝑒𝑓𝑓
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 F23 Topic 2

8.6 Ionic radii – Example #1

Which of the following statements about ionic radii is false?

a) Br – is larger than Cl –
b) Se2– is larger than Br –
c) K + is larger than Ca2+
d) Na+ is larger than K+

24
 F23 Topic 2

8.6 Ionic radii

• An isoelectronic series is a group of ions that have the same number of
electrons, and therefore the same electron configuration.

• What cations are isoelectronic with O2- and F-?

• What trend do you predict for ionic radii of isoelectronic ions?

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 F23 Topic 2

8.7 Ionization energy

Ionization energy:
• Ionization energy (IE) is the minimum amount of energy needed to
remove an electron from an atom or ion in the gas phase.
Na (𝑔) → Na+ (𝑔) + e‾ IE1 = + 496 kJ/mol
Na+ (𝑔) → Na2+ (𝑔) + e‾ IE2 = + 4560 kJ/mol

• The same factors that influence atomic radii also influence the first
ionization energies (IE1).

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 F23 Topic 2

8.7 Ionization energy

Discussion:
Based on your understanding of 𝑍𝑒𝑓𝑓 , determine the trend in first
ionization energy as you progress from left to right across the second
period (Li, Be, B, C, N, O, F, Ne).

Based on your understanding of 𝑍𝑒𝑓𝑓 and quantum numbers, determine

the trend in first ionization energy as you progress from top to bottom in
group one (H, Li, Na, K, Rb, Cs, Fr).

27
 F23 Topic 2

8.7 Ionization energy

• IE1 increases from left to

right across a period

• IE1 decreases down a

column

• Some exceptions to the

trend can be seen.

28
 F23 Topic 2

8.7 Ionization energy

• Exceptions to the IE trend:
Be → Be+ + e- vs. B → B + + e-

29
 F23 Topic 2

8.7 Ionization energy

• Exceptions to the IE trend:
N → N+ + e- vs. O → O+ + e-

30
 F23 Topic 2

8.7 Ionization energy

• Each successive IE is larger than the previous one.
• When all valence electrons have been removed, IE takes a big jump.
– Recall: Filled shells are very stable!
kJ/mol IE1 IE2 IE3 IE4 IE5 IE6 IE7
Na 496 4562
Mg 738 1451 7733
Al 578 1817 2745 11,577
Si 786 1577 3232 4356 16,091
P 1012 1907 2914 4964 6274 21,267
S 1000 2252 3357 4556 7004 8496 27,107
Cl 1251 2298 3822 5159 6542 9362 11,018
Ar 1521 2666 3931 5771 7238 8781 11,995 31
 F23 Topic 2

8.7 Ionization energy – Example #4

Rank increasing IE1 (smallest → largest) for P, Zr, Cs, and F.

32
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8.8 Electron affinities and metallic character

Electron affinity:
• Electron affinity (EA) is the amount of energy released when an electron
is added to an atom or ion in the gas phase.
e.g. Cl (𝑔) + e- → Cl- (𝑔) EA = | -349 kJ/mol |

• The greater the attraction between an atom and an electron, the more
positive the value.
• Trends in EA can be rationalized using 𝑍𝑒𝑓𝑓 .

33
 F23 Topic 2

8.8 Electron affinities and metallic character

• EA tends to increase left

to right across a period.

• EA tends to remain
constant down a column

• Can you spot any exceptions?

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 F23 Topic 2

8.8 Electron affinities and metallic character

Metallic character:
• Metals are good conductors of heat and electricity, and tend to lose
electrons in chemical reactions

• Based on what you have learned about ionization energy and electron
affinity, would you expect elements on the left or right side of the
periodic table to be metallic?

35
 F23 Topic 2

8.8 Electron affinities and metallic character

• Metallic character
decreases from left to
right across a period

• Metallic character
increases as you move
down a column

36
 F23 Topic 2

8.9 Periodic chemical behaviour

Let’s review what you know about periodic trends!
a) Which group will have the valence electron configuration ns2np3?

b) Which element in group 15 would have the smallest IE1?

c) Put these elements, Mg, Na, P, Si and Ar, in order in terms of atomic
radius from smallest to largest.

d) Which group has negative electron affinities?

e) Which group is likely to form +1 ions?

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 F23 Topic 3

Topic 3: Chemical Bonding I – Lewis Theory (Ch. 9)

Topics covered:
9.2 Types of chemical bonds
9.5 The ionic bonding model
9.3 Representing valence electrons with dots
9.4 Lewis structures
9.7 Electronegativity and bond polarity
9.6 Covalent bond energies, lengths and vibrations
9.8 Resonance and formal charge
1
 F23 Topic 3

What do you know about chemical bonding?

2
 F23 Topic 3

9.2 Types of chemical bonding

• There are three major types of chemical bonding:

Type of bond Description of interaction Example

Metallic

Ionic

Covalent

3
 F23 Topic 3

9.2 Types of chemical bonding

• Knowing the type of chemical bonding lets us predict structure and
properties of molecular systems.

Metallic Compounds Ionic Compounds Covalent Compounds

Metals Crystalline Solids Gases, liquids or solids
Extremely high MP/BP High MP/BP Low MP/BP
Conductors (melted or
Good Conductors Poor Conductors
aqueous)
Not water soluble Water soluble (many) Not water soluble (many)

4
 F23 Topic 3

9.5 THE IONIC BONDING MODEL

5
 F23 Topic 3

9.5 The ionic bonding model

• Made of cations and anions in a repeating pattern (crystal lattice)

• Usually results from the interaction of a metal with a non-metal.

– e.g. NaCl

• Na has low ionization energy.

• Cl has high electron affinity.

• Positive and negative charges are balanced.

6
 F23 Topic 3

9.5 The ionic bonding model

• Recall: Naming conventions for ionic compunds
– The cation is named first followed by the anion with the suffix –ide.
– There is more than one possibility for the charge of elements in the d-block. In
this case, we explicitly state the charge. e.g. CuCl2 is copper(II) chloride.

• Practice: Determine the charge of each ion and name each of the
compounds below.
a) KCl
b) Na3N
c) FeCl3
7
 F23 Topic 3

9.5 The ionic bonding model

Lattice energy:
• The amount of energy released when one mole of a solid ionic
compound is formed from gaseous ions

Higher lattice energy

Stronger ionic bond

8
 F23 Topic 3

9.5 The ionic bonding model

• Lattice energy is based on Coulomb’s Law
A constant (depends on the
type of lattice)

+ − Charges on ions
𝐶𝑞 𝑞
Δ𝐻𝑙𝑎𝑡𝑡𝑖𝑐𝑒 =
𝑅0

Distance between ions

• We will not be calculating lattice energies. However, you can use this
equation to predict trends in ionic bond strength.
9
 F23 Topic 3

9.5 The ionic bonding model

• If charges are the same, the lattice energy decreases (becomes less
negative) with increasing ionic radius

10
 F23 Topic 3

9.5 The ionic bonding model

• If ionic radius is similar, the lattice energy increases (becomes more
negative) with increasing ionic charge

• Charge is typically the more important factor

11
 F23 Topic 3

9.5 The ionic bonding model - Example

Which ionic compound has the higher lattice energy? Assume 𝐶 is the
same for all compounds.

a) NaCl or CaS

b) LiF or CsI

12
 F23 Topic 3

9.3 REPRESENTING VALENCE ELECTRONS

9.4 LEWIS STRUCTURES

13
 F23 Topic 3

9.3 Representing valence electrons

• Covalent bonds involve the sharing of valence electrons between two
atoms

• Usually occurs between non-metals

• e.g. H2O

• Non-metals have high ionization

energy and low electron affinity

• How do we represent covalent

bonding in a molecule?
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 F23 Topic 3

9.3 Representing valence electrons

• Lewis symbols and structures are convenient ways to represent the
valence shell electrons and chemical bonds in a molecule.

PROS
– Shows how atoms are connected in a molecule
– Shows non-bonding electrons
– Can identify resonance structures
– Simple and works well for most molecules
involving atoms from the 𝑠- and 𝑝-block

15
 F23 Topic 3

9.3 Representing valence electrons

• Lewis symbols and structures are convenient ways to represent the
valence shell electrons and chemical bonds in a molecule.

LIMITATIONS
– Does not give 3-D shape of overall molecule
– Does not give overall polarity
– Does not indicate the strength of the bonds

16
 F23 Topic 3

9.3 Representing valence electrons

Lewis symbols:
– Represents atoms
– Valence electrons are written as dots around the element symbol
– Only include electrons in 𝑠 and 𝑝 orbitals

• Practice: Write the Lewis symbols for H, N, Cl and Te.

17
 F23 Topic 3

9.4 Lewis structures

Lewis structures:
• Put Lewis symbols together to make molecules
• Covalent bonds (shared electron pairs) are represented as lines

Octet rule:

Atoms in the 𝑠- and 𝑝-block tend to gain, lose, or

share electrons until they are surrounded by eight
electrons.
18
 F23 Topic 3

9.4 Lewis structures

Method for writing Lewis structures:
1. Determine the total number of valence electrons
– For anions, add one electron for each negative charge
– For cations, subtract one electron for each positive charge

# valence electrons:
PCl3
5 + 3(7) = 26

19
 F23 Topic 3

9.4 Lewis structures

Method for writing Lewis structures:
2. Determine the central atom (usually the least electronegative) and
connect attached atoms with a single bond (2 electrons each). Subtract
these electrons from the total.

Cl P Cl # valence electrons remaining:

26 – (3×2) = 20
Cl
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 F23 Topic 3

9.4 Lewis structures

Method for writing Lewis structures:
3. Complete the octets on the outer atoms. Subtract these electrons from
the total.

Cl P Cl # valence electrons remaining:

20 – (3×6)= 2
Cl
21
 F23 Topic 3

9.4 Lewis structures

Method for writing Lewis structures:
4. Complete the octet of the central atom. Subtract these electrons from
the total.

Cl P Cl # valence electrons remaining:

2 –2 = 0
Cl
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 F23 Topic 3

9.4 Lewis structures

Method for writing Lewis structures:
5. If you run out of electrons before the central atom has an octet, use
lone pairs from the outer atoms to form multiple bonds.

H C N

H C N H C N
23
 F23 Topic 3

9.4 Lewis structures

Method for writing Lewis structures:
6. If you are drawing a Lewis structure for an ion, add square brackets
around the structure with the charge in the upper right-hand corner.

−
Cl O

24
 F23 Topic 3

9.4 Lewis structures – Example

• Draw Lewis structures for the following molecules:
a) HF

b) N2

c) NO+

d) H2O

25
 F23 Topic 3

9.7 ELECTRONEGATIVITY AND BOND POLARITY

26
 F23 Topic 3

9.7 Electronegativity and bond polarity

• Atoms do not always share electrons equally!

• HF molecules will align with

an external electric field

• This means there is some

electric charge in the
molecule!

27
 F23 Topic 3

9.7 Electronegativity and bond polarity

• Bond polarity: Measure of the unequal sharing of electrons in a bond

• Polar covalent bond: A bond with unequally shared electrons

28
 F23 Topic 3

9.7 Electronegativity and bond polarity

• Electronegativity (EN): How
strongly an atom attracts
shared electrons in a
covalent bond.
• Calculated from
thermochemical
data and ranges
from 0 (low) to 4
(high).

29
 F23 Topic 3

9.7 Electronegativity and bond polarity

• How is electronegativity different from electron affinity?

30
 F23 Topic 3

9.7 Electronegativity and bond polarity

• The greater the electronegativity difference (ΔEN), the more polar the
bond.
Covalent (ΔEN < 0.5) Polar covalent (ΔEN = 0.5 – 1.8) Ionic (ΔEN > 1.8)
C–C C–H N–H C–O Li – C Li – N Na – Cl Na – O

• The atom with the larger EN gains a

partial negative charge (𝛿 −).
𝛿− 𝛿+
• The atom with the smaller EN gains a Cl – H
partial positive charge (𝛿 +).
31
 F23 Topic 3

9.7 Electronegativity and bond polarity – Example

1. Which choice below correctly lists the elements in order of increasing
electronegativity (least → most) ?
a) N < C < O < F
b) N < C < F < O
c) C < N < O < F
d) C < N < F < O

2. Which bond is most polar?

a) P-F or P-Cl
b) Se-Cl or Se-Br

32
 F23 Topic 3

9.6 COVALENT BOND ENERGIES, LENGTHS AND

VIBRATIONS

33
 F23 Topic 3

9.6 Covalent bond energies, lengths and vibrations

• Bond energy is the energy required to break a bond
• Shorter bonds tend to be stronger bonds

• Multiple bonds are stronger than single bonds

34
 F23 Topic 3

9.6 Covalent bond energies, lengths and vibrations – Example

CCl4 is a banned substance because it wreaks havoc on the ozone layer

through the following sequence of reactions:
CCl4 → ∙CCl3 + Cl∙
Cl∙ + O3 → ClO∙ + O2
ClO∙ + O∙ → Cl∙ + O2
A 366 nm photon has just enough energy to break the C-Cl bond and
generate the Cl∙ radical needed to initiate this reaction sequence.
What is the bond energy, in kJ/mol, for the C-Cl bond?

35
 F23 Topic 3

9.6 Covalent bond energies, lengths and vibrations

Recall: Visible and UV light causes
electronic excitation in atoms and
molecules
• Infrared radiation causes vibrational
excitation

36
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 F23 Topic 3

9.6 Covalent bond energies, lengths and vibrations

• Absorbance of infrared light causes the vibrations to become excited
(vibrate with a larger amplitude).
• Lower energy than an electronic excitation.

37
 F23 Topic 3

9.6 Covalent bond energies, lengths and vibrations

• In order for a vibrational mode to be IR active, the vibration must cause
a change in the dipole moment of the molecule.

• Consider the vibrations of CO2:

38
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 F23 Topic 3

9.6 Covalent bond energies, lengths and vibrations

• Different vibrations occur at characteristic frequencies.

• An IR spectrum can tell you what types of bonds are in a molecule

39
 F23 Topic 3

9.6 Covalent bond energies, lengths and vibrations

• The greenhouse effect is due to absorption and re-emission of infrared
energy by CO2 and other greenhouse gases in the atmosphere.

40
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 F23 Topic 3

9.8 RESONANCE AND FORMAL CHARGE

41
 F23 Topic 3

9.8 Resonance and formal charge

• Sometimes you can draw more than one possible Lewis structure for the
same molecule.
– For example: CO2

O C O O C O O O C
• Which structure is the best?
• Assigning formal charges can help us pick the most appropriate Lewis
structure.
42
 F23 Topic 3

9.8 Resonance and formal charge

• Formal charge is the hypothetical charge an atom would have if the
bonding electrons were distributed evenly amongst the atoms.

• The most appropriate Lewis structure:

– Has the fewest nonzero formal charges.
– Has adjacent formal charges with opposite signs.
– Puts a negative charge on the most electronegative atom.

Formal charge =
(# of valence e- in free atom) – (# of lone pair e-) – ½ (# of bonding e-)
43
 F23 Topic 3

9.8 Resonance and formal charge

• Let’s assign formal charges to the 3 possible Lewis structures for CO2.

O C O O C O O O C

• Based on the formal charges, which Lewis structure is the best? Why?

44
 F23 Topic 3

9.8 Resonance and formal charge

• Lewis structures are useful but simplistic.
• Ozone (O3) has two possible Lewis structures with equal formal charges.

O O O O O O
0 +1 -1 -1 +1 0

• Actual structure of O3 has O – O bonds that are the same length.

• We cannot accurately depict the structure of O3 using one Lewis
structure!
45
 F23 Topic 3

9.8 Resonance and formal charge

Resonance structures:
• Multiple Lewis structures used to better represent the properties of
a molecule.

• Actual structure is an average of the resonance structures.

46
 F23 Topic 3

9.8 Resonance and formal charge

• Double-headed arrow indicates resonance structures.

• In ozone, the O – O bond is between a single and double bond.

− Average of the two resonance structures

• Electrons that participate in resonance bonds are delocalized.

47
 F23 Topic 3

9.8 Resonance and formal charge

• The major (best) resonance structures have
– The fewest non-zero formal charges
– Formal charges as close to zero as possible
– The negative charge(s) on the most electronegative atom

Equivalent resonance structures!

48
 F23 Topic 3

9.8 Resonance and formal charge

• The major (best) resonance structures have
– The fewest non-zero formal charges
– Formal charges as close to zero as possible
– The negative charge(s) on the most electronegative atom

- 0 - - -
O O O O O
- + - - 0 - 0 0 - - 0 - - 0 0
O P O O P O O P O O P O O P O
- - - 0 -
O O O O O

Minor
Minor Major
Major
49
 F23 Topic 3

9.8 Resonance and formal charge – Example #1

• Draw the two equivalent resonance structures for the nitrite anion, NO2-

50
 F23 Topic 3

9.8 Resonance and formal charge

Rules for drawing resonance structures:
• Do NOT move electrons in single bonds. Move only electrons from:
– Lone pairs
– Double or triple bonds
– Free radical electron (more on this later)
• Octet rule still applies to C, N, O and F
• H is limited to two electrons
• Calculate formal charge using the same rules and ask
– Is this a reasonable structure?
– Is the formal charge distribution better, worse or similar?
51
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9.8 Resonance and formal charge

Curved arrow notation:
• ↷ notation is used to indicate the movement of a pair of electrons
• Useful to help develop different resonance structures
• Used extensively in organic chemistry to show reaction mechanisms
Double-headed arrow indicates
two electrons are moving

Source of electrons Destination

(lone pair, double/triple bond)

52
 F23 Topic 3

9.8 Resonance and formal charge

• In order to maintain an octet, you typically need to use two curved
arrows to generate resonance structures.

O O O O O O

O O O O O O
53
 F23 Topic 3

9.8 Resonance and formal charge – Example #2

Using the curved arrow notation, develop the resonance structures for
NCO- and HCONH2.

54
 F23 Topic 3

9.9 & 9.10 EXCEPTIONS TO THE OCTET RULE

55
 F23 Topic 3

9.9 & 9.10 Exceptions to the octet rule

• Molecules do not always follow the octet rule!

https://tenor.com/view/pirates-caribbean-code-guidlines-rules-gif-10164767

• Exceptions to the octet rule include:

1. Free radicals
2. Incomplete octets
3. Hypercoordinate molecules
56
 F23 Topic 3

9.9 & 9.10 Exceptions to the octet rule

1. Free radicals
• Impossible to have a full octet with an odd number of electrons.
• Many free radicals contain nitrogen.
• Let’s draw the Lewis structure for NO

57
 F23 Topic 3

9.9 & 9.10 Exceptions to the octet rule

1. Free radicals
• Impossible to have a full octet with an odd number of electrons.
• Many free radicals contain nitrogen.
• e.g. NO
N O
2. Incomplete octets
• These molecules have less than an octet on the central atom.
• Typically atoms from group 2 and group 13.
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 F23 Topic 3

9.9 & 9.10 Exceptions to the octet rule

• Let’s look at the resonance structures for BF3.

59
 F23 Topic 3

9.9 & 9.10 Exceptions to the octet rule

3. Hypercoordinate molecules
• These molecules have more than an octet on the central atom.

• Elements in the 3rd row and lower have 𝑑-orbitals that can
participate in bonding (more than 8 valence electrons).

• Remember that the best resonance structures have the lowest

formal charge on the central atom!

60
 F23 Topic 3

9.9 & 9.10 Exceptions to the octet rule

• Let’s determine the best Lewis structure for PF5.

61
 F23 Topic 3

9.9 & 9.10 Exceptions to the octet rule – Practice

Draw the best Lewis structure for PO43-. Remember to minimize formal
charge.

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 F23 Topic 7A

Topic 7: Organic Chemistry I – Structures (Ch. 20 & 3)

Topics covered:
20.3 Hydrocarbons
20.4 Functional groups Part One

20.5 Constitutional isomerism Part Two

20.7 Configurational isomerism

Part Three
3.5 Naming organic compounds

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 F23 Topic 7A

Intro to organic chemistry

• In chemistry, “organic” refers to molecules that contain carbon.

• Organic compounds include:

✓ Proteins ✓ Rubbers
✓ Sugars ✓ Plastics
✓ DNA ✓ Soaps
✓ Vitamins ✓ Gasoline
✓ Alcohols ✓ Explosives
✓ Pharmaceuticals ✓ Artificial flavourings

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 F23 Topic 7A

Traditional chemistry disciplines – 1900s

Organic

Physical Chemistry Inorganic

Analytical

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 F23 Topic 7A

Modern chemistry disciplines

Polymer
Supra-
Medicinal molecular

Materials Organic

Organo-
Biochem Chemistry metallic

Comput-
Inorganic
ational

Physical Analytical
Enviro

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 F23 Topic 7A

Disciplines related to organic chemistry

Enviro

Biochem Medicinal

Organic

Pharma Polymer

Materials
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The chemistry of carbon

• Carbon can form a diverse array of molecules because:
– It can form long chains
– It can form single, double and triple bonds
– C-C and C-H bonds are very stable

• Organic molecules are composed primarily of C, H, O, N, S.

• Functional groups add character and different properties to
hydrocarbons

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Types of organic molecules

Organic
Molecules

Other stuff we’re

Hydrocarbons not talking
about. e.g.
carbohydrates

Aromatic Aliphatic

Alkane Alkene Alkyne

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20.3 HYDROCARBONS

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20.3 Hydrocarbons
• Greek prefixes are used to indicate the number of carbon atoms in an
organic molecule.

# of C Greek prefix # of C Greek prefix

1 meth 6 hex
2 eth 7 hept
3 prop 8 oct
4 but 9 non
5 pent 10 dec
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20.3 Hydrocarbons
• There are different ways to represent an organic molecule:

• If you were representing a large molecule, which structure would be most time
consuming to draw?

• Which structures give you the most information about the structure?
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20.3 Hydrocarbons
• For very large molecules, Lewis structures are too cumbersome.
– e.g. Amoxycillin

Lewis structure Bond-line structure

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20.3 Hydrocarbons
• What features do you notice about bond-line structures?

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20.3 Hydrocarbons
• Line-dash-wedge notation can be used to make bond-line structures
three dimensional.
• Line – Same plane as the page
• Dash – Goes into the page (away from you)
• Wedge – Comes out of the page (towards you)

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20.3 Hydrocarbons
Molecular Formula C3H6O C2H3N C3H7NO2
Name acetone acetonitrile L-alanine

Lewis Structure

Condensed Structural
Formula

Bond-Line Structure
• Realistic bond angles
• Usually omits H atoms
• Can use wedges/hash
bonds to show spatial
relationships
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20.3 Hydrocarbons – Example #1

Draw the line structures for the following:
a) hexane: CH3CH2CH2CH2CH2CH3
b) diethylether: CH3CH2OCH2CH3
c) cyclopentanone:

d) 4-ethyl-2-methylhexane:

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20.3 Hydrocarbons
• Two basic categories of organic molecules:
1. Aromatic
– Consisting of benzene ring-like
structures
2. Aliphatic
– Everything else!

• Both types of molecules are modified with functional groups.

• Functional groups give “character” to organic molecules and are
generally the site of chemical reactivity.
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20.3 Hydrocarbons
Alkanes:
• Alkanes are saturated hydrocarbons.
• All bonds are single bonds and all carbons are sp3-hybridized.
• Alkanes can be straight chain, branched or cyclic.
• Non-cyclic alkane: CnH2n+2
• Cyclic alkanes: CnH2n
H H H H
H C C C C H
H H H H

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20.3 Hydrocarbons
Alkenes and alkynes:
• Alkynes and alkenes are unsaturated hydrocarbon
– alkene have double carbon-carbon bonds
– alkynes have triple carbon-carbon bonds

Which are the alkenes and which are the alkynes?

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20.3 Hydrocarbons
Aromatic molecules:
• Aromatic molecules have benzene-like structures.

2-chlorophenol 3-phenylpentanoic acid

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20.4 FUNCTIONAL GROUPS

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20.4 Functional groups

• You should be able to identify and draw the following functional groups.
Functional Structural Condensed Functional Structural Condensed
group formula formula group formula formula
Carboxylic Alcohol ROH
Highest priority

RCOOH
acid
Amine RNR1R2
Ester RCOOR1
Alkene RC=CR1
Amide RCONR1R2 Alkyne RC≡CR1

Aromatic C6H5R

Lowest priority
Aldehyde RCHO
Ether ROR1
Ketone RCOR1 Alkyl halide RX
Alkyl RH 21
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20.4 Functional groups

Alkyl halides:
• Alkanes with a halogen
attached: R-X
• X = F, Cl, Br, I

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20.4 Functional groups

Alcohols and thiols:
• Alcohols have an –OH group
• Thiols have an -SH group
• Can be categorized as 1o, 2o, or 3o depending on their substitution at
the carbon
Functional group Primary Secondary Tertiary

Alcohol

Thiol
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20.4 Functional groups

Ethers and thioethers:
• Ethers have the R-O-R’ structure
• Thioethers have the R-S-R’ structure
• These will be bent molecules around the O or S

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20.4 Functional groups

Ketones and aldehydes:
• Both contain carbonyls (C=O).
• C=O bond is strongly polar.
• Commonly found in biomolecules. Aldehyde Ketone

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20.4 Functional groups

Esters and carboxylic acids:
• Both contain a carbonyl (C=O) next to an
oxygen. Carboxylic Ester
• Carboxylic acids are acidic (low pH). acid

• Esters are commonly used as artificial

flavourings.

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20.4 Functional groups

Amines and amides:
• Amines are N analogue of alcohols
• Amides are N analogue of carboxylic acids
• Amines and amides can be categorized as 1o, 2o, or 3o depending on
their substitution at the N
Functional group Primary Secondary Tertiary

Amine

Amide
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20.4 Functional groups – Example #1

Identify the all the amines as primary, secondary or tertiary in the
antimalarial drugs below. F
F F F
F
Cl N
NH2
F
N

H2 N N OH
N
Pyrimethanamine or Daraprim H
Mefloquine or Lariam
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20.4 Functional groups – Example #2

Identify the functional group on each aromatic molecule:
OO HH OH OO OH H
O
OH O OOOH NH
NH22 O NH
OH
OH NH22
NH NH2
RR R

enzene
enzene phenylbenzene toluene
phenyl phenyl
toluene phenoltoluene
phenol phenolbenzoic
benzaldehyde
benzaldehyde benzaldehyde
benzoic benzoic
acid aniline
acid aniline acid aniline
benzamide
benzamide benzamid
(whenititisisthe
(when the (when it is the
substitutent)
substitutent) substitutent)

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20.4 Functional groups – Example #3

Identify all functional groups in the molecules below:

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20.4 Functional groups – Example #4

Identify all functional groups in melatonin:

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