CHEM 1042

General Chemistry I
Prof. A P L Tong
2024-2025
Semester 1

1
Course Information:
No. of credits: 6
Pre-requisite: Level 3 or above in HKDSE Chemistry or a pass in
CHEM1041 or equivalent
Duration: Semester 1, repeated in Semester 2
Teaching: 24 hours of lectures plus additional classes/tutorials to be
scheduled as necessary, and 24 hours of laboratory work
Course Coordinator/ Prof. A P L TONG (apltong@[Link]; Rm 602, 6/F, Chong Yuet
Teacher: Ming Chemistry Building)
Teacher: Dr. K K H NG (kkhn3@[Link]); Room 418C, 4/F, Chong Yuet
Ming Physics Building)

Teaching Assistants: Mr. Xiang LI (lxxx@[Link]),

Mr. Yunfeng LUO (luoyf@[Link])

Please refer to the Course Information Sheet (CIS) of CHEM1042 for

other details including course aims, learning outcomes, assessment,
lab matters, out-of-class support, tutorial schedule, etc.

2
Your Prior Knowledge in Chemistry
HKDSE Chemistry - Syllabus
[Link]

HKDSE Chemistry (Compulsory Part)

Topic I) Planet Earth Topic IV) Acids and Bases
a. The atmosphere a. Introduction to acids and alkalis
b. The ocean b. Indicators and pH
c. Rocks and minerals c. Strength of acids and alkalis
Topic II) Microscopic World I d. Salts and neutralisation
a. Atomic structure e. Concentration of solutions
b. The Periodic Table f. Volumetric analysis involving acids and alkalis
c. Metallic bonding Topic V) Fossil Fuels and Carbon
d. Structures and properties of metals Compounds
e. Ionic and covalent bond a. Hydrocarbons from fossil fuels
f. Structures and properties of giant ionic substances b. Homologous series, structural formulae and
naming of carbon compounds
g. Structures and properties of simple molecular c. Alkanes and alkenes
substances
d. Addition polymers
h. Structures and properties of giant covalent
substances Topic VI) Microscopic World II
i. Comparison of structures and properties of a. Polarity of bond and molecule
important types substances b. Intermolecular forces
Topic III) Metals c. Structures and properties of ice
a. Occurrence and extraction of metals d. Simple molecular substances with non-octet
b. Reactivity of metals structures
c. Reacting masses e. Shapes of simple molecules
d. Corrosion of metals and their protection
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(Con’t) Your Prior Knowledge in Chemistry

Topic VII) Redox Reactions, Chemical Topic X) Chemical Equilibrium

Cells and Electrolysis
a. Dynamic equilibrium
a. Chemical cells in daily life
b. Equilibrium constant
b. Reactions in simple chemical cells
c. The effect of changes in concentration and
c. Redox reactions
temperature on chemical equilibria
d. Redox reactions in chemical cells
Topic XI) Chemistry of Carbon Compounds
e. Electrolysis
a. Introduction to selected homologous series
Topic VIII) Chemical Reactions and
Energy b. Isomerism
a. Energy changes in chemical reactions c. Typical reactions of various functional groups
b. Standard enthalpy changes of reactions d. Inter-conversions of carbon compounds
c. Hess’s law e. Important organic substances
Topic IX) Rate of Reaction Topic XII) Patterns in the Chemical World
a. Rate of chemical reaction a. Periodic variation in physical properties of the
b. Factors affecting rate of reaction elements from Li to Ar
c. Molar volume of gases at room temperature b. Bonding, stoichiometric composition and acid-base
and pressure (r.t.p.) properties of the oxides of elements from Na to Cl
c. General properties of transition metals

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(Con’t) Your Prior Knowledge in Chemistry
HKDSE Chemistry (Elective part, 2 out of 3)
Topic XIII) Industrial Chemistry
a. Importance of industrial processes
b. Rate equation
c. Activation energy
d. Catalysis and industrial processes
e. Industrial processes
f. Green chemistry
Topic XIV) Materials Chemistry
a. Naturally occurring polymers
b. Synthetic polymers and plastics
c. Metals and alloys
d. Synthetic materials in modern life
e. Green chemistry
Topic XV) Analytical Chemistry
a. Detecting the presence of chemical species
b. Separation and purification methods
c. Quantitative methods of analysis
d. Instrumental analytical methods
e. Contribution of analytical chemistry to our society

5
Textbook & Reference Books:
Petrucci; Herring; Madura; Bissonnette:
General Chemistry: Principles and Modern Applications,
11th or 12th edition, Pearson

11th edition 12th edition

Other reference books:

1) Moore; Stanitski; Jurs: Chemistry: The Molecular Science, latest edition,
Brookes/Cole
2) Zumdahl; Zumdahl: Chemistry, latest edition, Brookes/Cole
3) Silberberg: Chemistry: The Molecular Nature of Matter and Change, latest edition,
McGraw Hill
4) Raymond Chang: Chemistry, latest edition, McGraw Hill
6
CHEM 1042 General Chemistry I

Topic 1 Atoms:
The Quantum World
Prof. A P L Tong

7
 All matter is made of atoms!

Silicon
8
What to learn in this topic?
Atoms: the quantum world:
✓ modern view of atomic structure 1

✓ electromagnetic radiation and matter

✓ Planck's quantum theory
2
✓ the Bohr model of the hydrogen atom
Electronic
✓ the quantum mechanical model of the atom
structure
✓ quantum numbers
✓ energy levels and shapes of atomic orbitals
✓ electron configurations
✓ periodic trends (atomic radii, ionic radii, ionization
3
energies, and electron affinities)

9
 Your reading:

Petrucci; Herring; Madura; Bissonnette:

General Chemistry: Principles and Modern Applications, 11th or 12th
edition, Pearson
Chapter 2) Atoms & the Atomic Theory
Chapter 8) Electrons in Atoms
9-3, 9-4 & 9-5, Chapter 9) The Period Table & Some Atomic Properties

11th edition 12th edition

10
 Part One:
Modern View of Atomic Structure

What are inside an atom?

11
What are inside an atom?

Protons are positively charged.

Thomson’s plum-pudding model
• Assumed the positive charge spread
over the entire sphere (‘pudding’) and
the negative charges (‘plums’) are
embedded in this diffused cloud of
positive charge.
Neutrons are neutral.

Electrons are negatively charged.

This is wrong!
(The plum-
pudding model
was disproved).
Raymond Chang, Chemistry, 9e, McGraw Hill

12
The Modern View of Atom - The Nuclear Atom

• The positively charged particle, the protons,

together with any neutrons, are contained in
the nucleus (small and dense), and
• the electrons, the negatively charged
particles, occupy the empty space outside
the nucleus.
atomic radius ~ 100 pm = 1 x 10−10 m
nuclear radius ~ 5 x 10−3 pm = 5 x 10−15 m

Properties of Protons, Neutrons, and Electrons

13
 Part Two:
Electronic Structure
(How are the electrons in atoms?)

• Why are some elements or compounds more stable than the others?

• In a chemical reaction (except nuclear reactions), only electrons take

part but the nuclei do not!

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Electromagnetic Radiation
• Our understanding of the electronic structures of atoms is
based on the studies of the interaction of electromagnetic
radiation with matter.

➢ Electromagnetic Radiation

➢ Its connections with atomic

structure

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Electromagnetic Radiation
• EM radiation is a form of energy transmission in which electric
and magnetic fields are propagated as waves through a vacuum
or through a medium (e.g. glass).

• A wave is a disturbance that transmits

energy through space or a material
medium.
The simplest wave motion –
traveling wave in a rope
The waves pass along the rope
from left to right. crest

The distance between two

identical points is called the
wavelength of the wave, .
trough
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Electromagnetic Radiation
Properties of wave:
• Wavelength,  (m)
• Frequency,  (s-1, Hz)
• Amplitude, A
• Velocity of light, c (3.00 x 108 ms-1)
A distinctive feature of EM radiation is its
constant speed in a vacuum.

Wavelength () is the distance between identical

points on successive waves.

Frequency () is the number of waves that pass

through a particular point in 1 second (Hz = 1 cycle/s).

Amplitude (A) is the vertical distance from the

midline of a wave to the peak or trough.

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Electromagnetic Radiation

Longer ;
Lower 

Shorter ;
Higher 

Electromagnetic waves
Electric and magnetic fields propagate as waves
through empty space or through a medium. A
wave transmits energy.
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Frequency, Wavelength and Speed of
Electromagnetic Radiation
• Frequency () in Hertz, Hz or s−1.

• Wavelength () in meters, m.

cm m nm Å pm
(10−2 m) (10−6 m) (10−9 m) (10−10 m) (10−12 m)

• Velocity (c), 2.997925  108 ms−1 (or 3.00  108 ms−1).

c =   = c /  = c /

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 The electromagnetic spectrum

Increasing energy
The visible region, which extends from violet at the shortest wavelength to red at the longest
wavelength, is only a small portion of the entire spectrum. The approximate wavelength and
frequency ranges of some other forms of electromagnetic radiation are also indicated.
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 Electromagnetic Radiation
Class Practice 1

Solution:

21
Diffraction – A Property of Waves
Electromagnetic Radiation

Example of interference
When two waves intersect → some places where
the waves disappear (destructive interference,
waves are out of phase) and some places where
the waves persist (constructive interference,
waves are in phase).

Interference in two overlapping light waves

crest crest

crest
trough

(a) In constructive interference, (b) In destructive interference,

the crests and troughs are in phase, the crests and troughs are out of phase,
leading to addition of the two waves. leading to cancellation of the two waves.
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Diffraction is the bending of a wave around an object or
through an aperture.

Interference is the combination of two or more waves to form

a composite wave.
Bands of alternating intensity
are observed

 Bands in the middle are the most

intense because the two waves are
perfectly in phase at that point and
thus constructively interfere.
 The dark bands are caused by out
of phase waves which result in
destructive interference.

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Diffraction – A Property of Waves
Electromagnetic Radiation

More examples:
The diffraction of light from a diffraction grating is
shown in the picture on the right. The colours result
because the various wavelengths of visible light
are not all scattered in the same way. The colours
are ‘separated’, giving the same effect as light
passing through a prism.

When X rays are directed onto a

crystal of a compound with its regular
array of atoms/ions, the scattered
radiation produces a diffraction pattern
of bright areas and dark spots on a
photographic plate. This pattern occurs
because the scattered light can
interfere constructively or destructively.

• Diffraction is a phenomenon that can be explained only as a

property of waves.
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 Electromagnetic Radiation
The Visible Spectrum
• The speed of light in: vacuum > any medium (different speeds
c = 2.998  108 ms−1 in different media)
• When light passes from one medium to another, it is refracted or
bent.

• EM waves of different  have slightly different speeds in air and

other media. When a beam of white light is passed through a
transparent medium (e.g. a glass prism), the wavelength
components are refracted differently, giving rise to a band of
colours, a spectrum .

Dispersion of light through a prism

to give the spectrum of white light:
Red light is refracted the least and
violet light the most.

25
Prelude to Quantum Theory
• There are several experiments for which the results obtained
cannot be explained by the physical laws that govern the behavior
of particles at macroscopic scale. Classical physics

Some phenomena that classical physics cannot

explain are:

Photoelectric Atomic (line)

effect spectra

26
 Prelude to Quantum Theory

Planck proposed: Energy, like matter, is discontinuous.

Classical Physics Quantum Physics

A set of physical laws & their A set of physical laws & their
corresponding equations that corresponding equations that
describe/govern the motion describe/govern the motion
and interactions of and interactions of
big bodies. small bodies.

Classical physics places no Quantum theory limits this energy

limitations on the amount of energy a to a discrete set of specific values.
system may possess. It failed to The difference between any two
explain some phenomena, e.g. allowed energies of a system has a
photoelectric effect and line emission specific value, called a quantum of
spectra. energy. This means when the
energy increases from one allowed
value to another, it increases by a
tiny jump, or quantum.

27
Prelude to Quantum Theory

Classical physics Quantum physics

(Continuous) (Discontinuous)

28
 Prelude to Quantum Theory
(1) The Photoelectric Effect
• Heinrich Hertz (1887) discovered that when light strikes the surface of
certain metals, electrons are ejected (photoelectric effect).

• This electron emission only occurs when incident > 0 a particular

threshold value

A photon of energy h strikes a bound electron,

which absorbs the photon energy.
If this energy > the energy binding the e- to the
surface (work function),
a photoelectron is liberated. And any energy in
excess of the work function appears as KE in the
photoelectron.

• When this condition is met,

➢ The no. of e- emitted depends on the intensity of the incident light, but

➢ The KE of the emitted e- depend on the frequency of the light.

29
(1) The Photoelectric Effect
• Recall that all forms of EM radiation transport energy. Imagine this energy
being used to push tiny particles of negative charge free from the surface
of a metal where they are not all that strongly confined in the first place.

• Subsequent investigations into the photoelectric effect yielded results that

did not fit with the classical theory of EM radiation. When it interacted with
electrons, light just didn't behave like it was supposed to. See the next
slide for details.

30
 The Photoelectric Effect

• According to classical model of light (EM wave), the photoelectrons

should pop out even when red light is used as long as its intensity is
high enough. That means if energy is continuous in a system, it
should take awhile for any one electron to capture enough of the
diffuse energy to free itself. But the results are NOT like this!

31
 The Photoelectric Effect
• The photoelectric effect could not be explained by
classical physics.

• Albert Einstein showed that they are exactly what

would be expected with a particle interpretation of
radiation.

• In 1905, he proposed that EM radiation has particle-

like qualities and that “particles of light’, called
photons, have a characteristic energy given by
Albert Einstein
Planck's equation. (1879-1955)

Photoelectric effect:
Showed particle
properties of light

32
 Prelude to Quantum Theory

We now see that dual nature of light:

Electromagnetic radiation exhibits
• wave properties and
• particle properties.

33
 Prelude to Quantum Theory
Max Planck – Quantization of Energy

• In 1900, Max Planck proposed that

Energy, like matter, is discontinuous.

• Energy can only be absorbed or released from

atoms in certain amounts called quanta.

Max Planck E = h -- Planck’s equation

(1858 – 1947)
where 𝐸 is the energy, 𝜈 is the frequency, and h is a constant
called Planck’s constant (h = 6.62607  10-34 J s molecule-1).

From Planck’s equation, we see that the energy of a quantum of EM

radiation is proportional to the frequency of the radiation – the higher the
frequency, the greater the energy. Energy is not continuous, but
quantized
34
 Prelude to Quantum Theory
Class Practice 2

Solution:

35
 Prelude to Quantum Theory
(2) Atomic Emission Spectra
• The visible spectrum is a continuous spectrum which contains
many wavelength components.

• If the light source is a gas flame into which an ionic compound is

introduced, the flame may acquire a distinctive colour indicative of
the metal ion present. In each case, the emitted light produces a
spectrum consisting of only a limited number of discrete
wavelength components. These discontinuous spectra are called
atomic, or line, spectra.
Li Na K

Light emitted when compounds of

the alkali metals are excited in the
gas flames.
36
 Prelude to Quantum Theory
(2) Atomic Emission Spectra
Production of atomic (line) spectrum
of helium

• The light source is a lamp containing

He gas at a low pressure.
• When an electric discharge is passed
through the lamp, He atoms absorb
energy, which they then emit as light.
• The light is passed through a narrow
slit and then dispersed by a prism.
The coloured components of the light
are detected and recorded on a
photographic film.
• Each  component appears as an
image of the slit – a thin line.

Each element has its own distinctive line spectrum

– a kind of atomic fingerprint.
37
 Atomic Emission Spectra
Each element has its own distinctive line spectrum.

Spectra from Raymond Chang, Chemistry 10e, McGraw Hill 38

 Prelude to Quantum Theory
(2) Atomic Emission Spectra
• The hydrogen spectrum – the most well-studied atomic spectrum.
principal  component

n=6 n=5 n=4 n=3

Visible region
Light (reddish purple) Fig. 8-12) The Balmer series for hydrogen atoms – a line spectrum
from a hydrogen lamp The four lines shown are the only ones visible to the unaided eye.
Additional, closely spaced lines lie in the UV region.

• In 1885, Johann Balmer, deduced a formula for the wavelengths of

these spectral lines.
15 −1
1 1
Balmer’s equation: 𝜐 = 3.2881 × 10 s 2
− 2
2 𝑛
where  is the frequency of the spectral line, and n must be an integer > 2.

39
 Prelude to Quantum Theory
(2) Atomic Emission Spectra

What is the SIGNIFICANCE of having

only a limited number of well-defined
wavelength lines for the
hydrogen atomic spectrum?

• Only certain energies are allowed for

the electron in the hydrogen atom.
• Energy of the electron in the
hydrogen atom is ______________.

40
Classical physics Quantum physics
(energy is continuous) (energy is discontinuous, quantized)

Quantum Theory – Max Planck

𝑬 = 𝒉𝝂 h = 6.62607  10-34 J s molecule-1

𝑐 = 𝜆𝜈
𝒉𝒄
𝑬=
𝝀
41
 Prelude to Quantum Theory
An Early Attempt to Understand Atomic
Emission Spectra: The Bohr Model
Nuclear Atom (Rutherford)

How are the

electrons arranged?

According to classical physics,

1. Any orbit should be possible and so is any energy.
2. But orbiting electrons should be constantly accelerating and
should radiate energy.

End result should be destruction!

42
The Bohr Model
• In 1913, Niels Bohr postulated that for a hydrogen
atom:
1. The electron moves about the nucleus with speed u in one (1885-1962)
of a fixed set of circular orbits; as long as the electron
remains in a given orbit, its energy is constant and no energy is emitted.
Thus, each orbit is characterized by a fixed radius, r, and a fixed energy, E.

2. The electron’s angular momentum, ℓ = 𝑚𝑢𝑟, is an integer multiple of

(ℎ/2𝜋), i.e. ℓ = 𝑛 × (ℎ/2𝜋) , with n = 1, 2, 3,…...

3. An electron emits energy as a photon when the

electron falls from an orbit of higher energy and
larger radius to an orbit of lower energy and
smaller radius.

43
 Prelude to Quantum Theory
The Bohr Model Bohr model of the hydrogen atom
• n = 1, 2, 3, and so on.
• Excitation of the atom raises the e- to
higher-numbered orbits.
• Light is emitted when the e- falls to a
lower-numbered orbit.
• Two transitions in the Balmer series of the
hydrogen spectrum are shown.

This theory allows us to calculate:

(1) the radii of the allowed orbits in a hydrogen atom

𝒓𝒏 = 𝒏𝟐 𝒂𝟎 where n = 1, 2, 3… and a0 = 53 pm

(2) the energies of these orbits

−𝑹𝑯 where RH (Rydberg constant) = 2.17868  10−18J
𝑬𝒏 =
𝒏𝟐 -- eqn 1
−𝒁𝟐 𝑹𝑯
𝑬𝒏 =
𝒏𝟐 44
 Prelude to Quantum Theory
The Bohr Model
−𝑹𝑯 where n = 1, 2, 3, …… and
eqn 1: 𝑬𝒏 = RH (Rydberg constant) = 2.17868  10−18J
𝒏𝟐

With equation 1:

➢ The energy of the hydrogen atom is quantized.

➢ All the allowed energy values are negative. By convention, the

energy of the electron is defined to be zero when it is free of the
nucleus (i.e. n = ). As the electron becomes more tightly bound,
its energy becomes more negative relative to the zero-energy
reference state (free electron).

• Equation 1 can also be used to explain certain features of the

emission spectrum of the hydrogen atom

45
 Prelude to Quantum Theory
The Bohr Model:
The hydrogen atom is quantized
E = h

E = h −𝑹𝑯
𝑬𝒏 =
𝒏𝟐

46
 The Bohr Atom
Class Practice 3

Solution:
eqn 1

eqn 1

eqn 1

47
Energy Levels, Spectrum, and IE of the Hydrogen Atom
Energy-level diagram for the hydrogen atom • The e- in a hydrogen atom
normally stays in the orbit
closest to the nucleus (n=1).
This lowest allowed energy is
called the ground state.

ni = 2
• When the e- gains a quantum
Vis region of energy, it moves to a
higher level (n=2,3,...) and
the atom is in an excited state.

• When the e- drops from a

higher to a lower level, a
unique quantity of energy
ni = 1 is emitted.
UV region

1 1 1 1
∆𝐸 = 𝐸𝑓 − 𝐸𝑖 = 𝑅𝐻 𝑛𝑖 2
−𝑛 2 = 2.179 × 10−18 J 𝑛𝑖 2
−𝑛 2
-- eqn 2
𝑓 𝑓

∆𝐸 = 𝐸𝑓 − 𝐸𝑖 = 𝐸𝑝ℎ𝑜𝑡𝑜𝑛 = ℎ𝜈
48
Quick Summary on Bohr Model of the Hydrogen Atom and
the Emission Spectrum

Assumption:
The electron moves in a circular
orbit of radius r about the
nucleus. The electron has only
a fixed set of allowed orbits.
nucleus
n=1
n = 1, 2, 3, 4, 5, … 
n=2
n=3 −𝑹𝑯
n=4 eqn 1: 𝑬𝒏 =
n=
𝒏𝟐

1 1 1 1
∆𝐸 = 𝐸𝑓 − 𝐸𝑖 = 𝑅𝐻 − = 2.179 × 10−18 J −
𝑛𝑖 2 𝑛𝑓 2 𝑛𝑖 2 𝑛𝑓 2

For absorption, nf > ni ; for emission, ni > nf .

49
Quick Summary on Bohr Model of the Hydrogen Atom and
the Emission Spectrum

Paschen series
(lower energy
(lower energy level = 2) level = 3)

Lyman series
(lower energy level = 1)

The Balmer series for the hydrogen

emission spectrum

50
 Class Practice 4

Solution: 1 1
∆𝐸 = 2.179 × 10−18 J −
∆𝐸 = 𝐸𝑓 − 𝐸𝑖 = 𝐸𝑝ℎ𝑜𝑡𝑜𝑛 = ℎ𝜈 𝑛𝑖 2 𝑛𝑓 2

c = 

51
Class Practice 4 (Con’t)

52
Ionization Energy of Hydrogen and Hydrogen-Like Ions
1 1
• Refer to eqn 2, ΔE = RH ( – ) = h
ni2 nf 2

In ionization of the hydrogen atom, the electron starting in the ground

state (ni =1) is moved to nf =, the ionization energy (Ei) of the H atom
is
Ei = hphoton = RH ( 12 ) = RH
ni
• This also works for hydrogen-like species such as He+ , Li2+ or Be3+.
For these species, the nuclear charge (atomic no, Z) appears in the
energy-level expression.
−Z2)
En = RH ( 2
n
Ei for an atom of the hydrogen-like species (with ni =1) is therefore
Z2 ) = Z2R
Ei = RH ( 2 H
ni
53
 Ionization Energy of Hydrogen &
Class Practice 5 Hydrogen-Like Ions

Solution:

54
 Prelude to Quantum Theory
Inadequacies of the Bohr Model
• Experimentally, the Bohr theory cannot explain the
emission spectra of atoms and ions with more than one
electron.

• Fundamentally, the postulate of quantized angular

momentum forcing an electron into a circular orbit has
no basis.
Classical
Physics

Bohr theory

New Quantum
Physics (1926)
55
Two Ideas Leading to Quantum Mechanics
• Wave-Particle Duality
➢ Einstein suggested particle-like properties of
light could explain the photoelectric effect.
➢ Diffraction patterns suggest photons are
wave-like. Louis de Broglie
(Nobel Prize 1929)

• de Broglie, 1924

➢ Small particles of matter may at times

display wave-like properties.

56
 Quantum Mechanics
de Broglie Relation
– Electrons can be wave-like
Einstein: E = mc2 (where m is the mass of the
photon and c is the speed
Planck: h = mc2 of light)

h/c = mc = p (where p is the momentum

of the photon)
p = h/λ

The momentum, p, can be replaced by its equivalent – the product

of the mass of the particle, m, and its velocity, u.

ℎ ℎ ( is called de
de Broglie Relation: 𝜆= = Broglie wavelength)
𝑝 𝑚𝑢
57
 Quantum Mechanics
de Broglie Relation
ℎ ℎ ( for particles is called de Broglie
𝜆= =
𝑝 𝑚𝑢 wavelength)

 de Broglie called the waves associated with material particles

“matter waves”.
 In one equation de Broglie summarized the concepts of waves
and particles (the momentum, mv, is a particle property, whereas 
is a wave property), with noticeable effects if the objects are small.

How to show small particles do

have wave properties?

58
 Quantum Mechanics

Wave properties of electrons demonstrated

(a) Diffraction of X-rays by the (b) Diffraction of electrons by metal

regular array of atoms in a thin aluminium, confirming the wave-
metal aluminium (atoms are ~2 Å). like properties of electrons.

59
 Quantum Mechanics
Class Practice 6

Solution:

60
 Quantum Mechanics
Class Practice 7

What is the de Broglie wavelength associated with a 2.5 g

Ping-Pong ball traveling at 15.6 m/s? (h = 6.626 10−34 Js)

Solution:

 = 6.626 x 10-34 Js / (2.5 x 10-3 kg x 15.6 m/s)

 = 1.7 x 10-32 m

c.f.  = 24.2 pm (2.4 x 10-11 m) in Class Practice 6

61
 Quantum Mechanics
The Uncertainty Principle
• In order to know the behaviour of subatomic particles,
the two variables that must be measured are
(i) the position of the particle (x), and
(ii) its momentum (p = mu).

• Niels Bohr and Werner Heisenberg found that there

must always be uncertainties in measurement such Heisenberg
and Bohr
that h
ΔxΔp ≥
4π
• Heisenberg Uncertainty Principle:
The position and momentum of a particle cannot be measured
with great precision simultaneously. Knowing one quantity with
high precision means that the other must necessarily be imprecise.

62
The Uncertainty Principle
h
ΔxΔp ≥
4π

Heisenberg Uncertainty Principle implies that

• for a very precise measurement of position, x, many values of
momentum, p, are possible;
• for a very precise measurement of momentum, p, many values
of position, x, are possible.

63
 Quantum Mechanics
Class Practice 8

Solution:

64
 Quantum Mechanics
Class Practice 9

The hydrogen atom has a radius on the order of 0.05 nm.

(i) Assuming that we know the position of an electron to an accuracy of 1% of the
hydrogen radius, calculate the uncertainty in the velocity of the electron using
the Heisenberg uncertainty principle.
(ii) Then compare this value with the uncertainty in the velocity of a ball of
mass 0.2 kg and radius 0.05 m whose position is known to an accuracy of 1% of
its radius.
Given the following information:
Mass of the electron (m) = 9.11  10−31 kg
Planck’s constant (h) = 6.626  10−34 Js = 6.626  10−34 kgm2s-1
 = 3.14

65
 Quantum Mechanics
Class Practice 9 (Con’t)
Solution:
(i) From Heisenberg Uncertainty Principle, the smallest possible uncertainty
in the product xp is h/4.

The uncertainty in position of the electron (x) is 1% of 0.05 nm, i.e.

x = (0.01)(0.05 nm) = 5  10−13 m

 The uncertainty in momentum of the electron is

ℎ 6.626  10 34 𝑘𝑔 𝑚2 𝑠 −1
∆p = = = 1.05  10−22 kgms−1
4𝜋∙∆𝑥 4(3.14)(5  10 𝑚)
13

Recall that p = (mv) = mv (because the mass of the electron should be constant)
Hence, the uncertainty in velocity of the electron is
∆𝑝 1.05  10−22 𝑘𝑔𝑚𝑠−1
∆𝑣 = = = 1.15  108 ms-1 = 1  108 ms-1
𝑚 9.11  10 𝑘𝑔
−31
(a very large number!)

66
 Quantum Mechanics
Class Practice 9 (Con’t)

(ii) The uncertainty in position of the ball (x) is 1% of 0.05 m (i.e. 5  10−4 m).
Thus the uncertainty in velocity is

∆𝑝 ℎ 6.626  10−34 𝑘𝑔𝑚2𝑠−1

∆v = = =
𝑚 4𝜋 ∙ ∆𝑥 ∙ 𝑚 (4)(3.14)(5 × 10−4 𝑚)(0.2 𝑘𝑔)

= 5  10−31 ms-1
(a very small number!)

67
 Quantum Mechanics
The Uncertainty Principle

Wave-particle
duality
(de Broglie) Conclusion:
Bohr model must be incorrect because
an electron cannot be constrained to a
1-D orbit (1-D in the sense that the e-
cannot move off a circular path of a fixed
Uncertainty radius).
principle
(Heisenberg)

68
Wave-particle duality …..
Uncertainty Principle…..
Then how are we to view electrons
in atoms?

69
Wave Mechanics
• Two types of waves: traveling waves and
standing waves
• In a traveling wave, every portion of a long rope goes
through an identical up-and-down motion. The wave
transmits energy along the entire length.

Traveling waves
• In a standing wave, the crests and in a string
troughs of the wave occur at fixed
positions and the amplitude of the wave at the fixed
ends is zero. Points that undergo no displacement at
all are called nodes.

The string can be set into motion by plucking it. The blue
boundaries outline the range of displacements at each point.
Standing waves
The nodes are marked by bold dots.
in a string
70
Standing Waves
one half-wavelength

• It can be said that the permitted wavelengths

of standing waves are quantized.
two half-wavelengths
• The wavelengths are equal to twice the path
length (L) divided by a whole number (n).
three half-wavelengths

where n = 1, 2, 3, … and the

2𝐿
𝜆= total no. of nodes = n + 1
𝑛 -- eqn 3
Standing waves
in a string

71
Standing Waves

• de Broglie argued that if an electron does

behave like a standing wave in the hydrogen
atom, the length of the wave must fit the
circumference of the orbit exactly.

• Otherwise, the wave would partially cancel

itself on each successive orbit → the
amplitude of the wave would be reduced to
zero, and the wave would not exist.

The electron as a matter wave

72
Particle in a Box: Standing Waves, Quantum
Particles, and Wave Functions
• In 1927, Erwin Schrödinger suggested that an electron (or
any other particle) exhibiting wavelike properties should
be describable by an equation, called a wave function
(). Erwin Schrödinger
(Nobel Prize 1933)
• Consider a particle is confined to move in a 1-d box (a
line), the wave function for this so called “particle in a box”
corresponds to a standing wave within the boundary of
the system being described.

• If the length of the box is L and the particle moves in the

x direction, the equation for the standing wave is

2 𝑛𝜋𝑥
𝜓𝑛 𝑥 = sin where n = 1, 2, 3, …
𝐿 𝐿
The standing waves of
a particle in a 1-d box
73
 Particle in a Box
Wave Functions

2 𝑛𝜋𝑥
𝜓𝑛 𝑥 = sin where n = 1, 2, 3, …
𝐿 𝐿

• This wave function is a sine function.

Consider the case where n = 2,

When

74
 Particle in a Box
What can we understand from  and n?
Consider n,
The standing waves of
a particle in a 1-d box • The particle that we are considering is freely moving
with a KE given by the expression:
1 2
𝑚2 𝑢 2 𝑝2
𝐸𝑘 = 𝑚𝑢 = =
2 2𝑚 2𝑚

• To associate this KE with a wave, use de Broglie’s

relation ( = h/p) to get
𝑝2 ℎ2
𝐸𝑘 = =
2𝑚 2𝑚𝜆2
2𝐿
𝜆=
• ∵ the s of the matter wave must fit eqn 3, 𝑛
ℎ2 ℎ2 𝑛 2 ℎ2
 𝐸𝑘 = = =
2𝑚𝜆2 2𝑚 2𝐿/𝑛 2 8𝑚𝐿2

Conclusion:
The ___________________________gives rise to
quantization of the wave’s energy, with allowable
values determined by the value of n.
75
What can we understand from  and n?
Particle in a Box

Consider ,
• According to Max Born, wave mechanics does not
answer the question “what is the precise position of a
particle?” but rather, “what is the probability of finding
a particle within a specified volume of space?”

➢ That is,  has no physical significance.

➢ But the square of the wave function (2) gives the

probability of finding an electron near a particular
point in space (i.e. it gives the electron charge
density).

➢ Electron probability  Electron charge density

➢ 2 is called the electron probability density

Fig. 8-20) The probabilities of a particle in a one-dimensional box

The squares of the first three wave functions and their energies are shown in
relation to the position of the particle in the box. At 2 = 0, there is no chance of
finding the particle at that point. Notice that even when  is –ve, 2 is +ve.
76
 Particle in a Box
Class Practice 10

Solution:

77
 Particle in a Box
Class Practice 11

Hint:

78
 Particle in a Box

Class Practice 11 (Con’t)

Solution:

79
Particle in a Box: Standing Waves, Quantum
Particles, and Wave Functions
• Extending the particle-in-a-box model to a 3-d box, the particle can
move in all directions (x, y, and z) and the quantization of energy is
described by the following equation.

2
ℎ 2 𝑛𝑥 2 𝑛𝑦 𝑛𝑧 2
𝐸𝑛𝑥 𝑛𝑦 𝑛𝑧 = + 2 + 2
8𝑚 𝐿𝑥 2 𝐿𝑦 𝐿𝑧

• There is one quantum number for each direction. Thus, three

quantum numbers are needed in a 3-d system.

Now, apply this idea to a hydrogen atom.

80
Quantum Theory of the Hydrogen Atom
• With the ideas from Wave Mechanics, a conceptual model for
understanding the hydrogen atom is developed. This provides the
basis for understanding multielectron atoms, the organization of
elements in the periodic table, and, ultimately, the physical and
chemical properties of the elements and their compounds.

• In 1927, Erwin Schrödinger proposed an equation for the hydrogen

atom that incorporated both the particle and the wave nature of the
electron. The Schrödinger equation is a wave equation that must be
solved to obtain the energy levels and wave functions needed to
describe a quantum mechanical system.

81
 Quantum Theory
The Schrödinger Equation
• Solutions to the Schrödinger equation for the hydrogen atom give not
only energy levels but also wave functions. These wave functions are
called orbitals.
• Wave functions are most easily analyzed in terms of the three
variables required to define a point w.r.t. the nucleus.

Schrödinger equations for the hydrogen atom:

(when the usual Cartesian coordinates are used)

(when the spherical polar coordinates are used)

82
 Quantum Theory
The Schrödinger Equation
• In spherical polar coordinate system, r is the
distance of the point from the nucleus, and the
angles  and  describe the orientation of the
distance line, r, with respect to the x, y, and z axes.

• When this coordinate system is used, the orbitals

can be expressed in terms of one function R that
depends only on r, and a second function  that
depends on  and .
𝜓 𝑟, 𝜃, 𝜙 = 𝑅 𝑟 Υ(𝜃, 𝜙)

• R(r) is called the radial wave function and Υ(𝜃, 𝜙)

is the angular wave function.

• Each orbital has three quantum numbers to

define it (∵ 3-d system).

83
 Quantum Theory
The Schrödinger Equation

Schrödinger equation can only be solved

exactly for the hydrogen atom.
For multi-electron systems, approximation
must be made for solution.

84
 Quantum Theory
Assigning Quantum Numbers
• By specifying three quantum numbers in a wave function 𝜓, we obtain an
orbital.
• From the solutions of the Schrödinger equation for the hydrogen atom, the
following relationships involving the three quantum numbers have been
obtained.
1. Principal Quantum Number, n
n = 1, 2, 3, 4, …. -- eqn 4
(positive, nonzero integer)
2. Angular Momentum Quantum Number, ℓ
ℓ = 0, 1, 2, 3,…, n – 1 -- eqn 5
(may be zero or a positive integer, but not > n – 1)

3. Magnetic Quantum Number, mℓ

mℓ = −ℓ, (−ℓ + 1) , … −2, −1, 0, 1, 2, …, (ℓ − 1), +ℓ -- eqn 6
(may be a negative or positive integer, including zero)
Total no. of mℓ = 2ℓ+ 1
85
 Quantum Theory

E.g.) Applying Relationships Among Quantum Numbers

4, 5 and 6.

86
 Quantum Theory
Assigning Quantum Numbers
• Principal quantum number (n) – size and energy of the orbital.
(The higher the value of n, the greater the electron energy and
the farther, on average, the electron is from the nucleus.)

• Angular momentum quantum number (ℓ) – shape of atomic

orbitals (sometimes called a subshell).
(The number of subshells in a principal shell is the same as
the number of allowed values of the ℓ.)

• Magnetic quantum number (mℓ) – orientation of the orbital

in space relative to the other orbitals in the atom.
(The number of orbitals in a subshell is the same as the number of
allowed values of mℓ for the particular value of ℓ.)

87
 Quantum Theory

Quantum Numbers for the First Four Levels of

Orbitals in the Hydrogen Atom
size
and shape orientation
energy
/ subshell

88
 Quantum Theory
Principal Shells and Subshells
Shells and subshells of a hydrogen atom

1
𝐸𝑛 = −2.179 × 10−18 J J (same as eqn 1)
𝑛2

(Orbital energies for a hydrogen atom depend only on n.)

89
 Quantum Theory
Class Practice 12

Solution:

90
Orbitals of the Hydrogen Atom
• Recall that solutions to the Schrödinger equation for the hydrogen
atom give wave functions. These wave functions are called
orbitals. (That means orbitals are wave functions, mathematical
solutions of the Schrödinger wave equation. And 2 is a quantity
related to probability density distributions.)

• An orbital is derived using the mathematical tools of quantum

mechanics. It is a representation of the 3-d volume (i.e. the region
in space) in which an electron is most likely to be found.

91
 Orbitals of the Hydrogen Atom
s Orbitals

(a) (b) (c)

Three representation of the electron probability density for the 1s orbital.

(a) The probability density is represented by the height above the xy plane.
(b) A contour map of the 1s orbital probability density in the xy plane, pointing
out the 95 % contour.
(c) A reduced scale 3D representation of the 95 % contour of a 1s orbital.

92
 Orbitals of the Hydrogen Atom

s Orbitals
Three-dimensional representations of the 95% electron
probability density for the 1s, 2s and 3s orbitals

The size is increasing

93
 Orbitals of the Hydrogen Atom

p Orbitals

Representations of the three 2p orbitals

95% probability surfaces

94
 Orbitals of the Hydrogen Atom

d Orbitals

Representations of the five d orbitals

95% probability surfaces

95
Electron Spin: A Fourth Quantum Number
• The three quantum numbers (n, ℓ, mℓ) provide a description of electron
orbitals.
• There are two possibilities for electron spin and this requires
a 4th quantum number, the electron spin quantum number,
ms.

The value of ms may

be + ½ or -½;
not dependent of other
quantum numbers.

 

Electron spin visualized

Two possibilities for electron spin are shown with their associated
magnetic fields. Two electrons with opposing magnetic fields that cancel,
leaving no net magnetic field for the pair.
96
E.g.) Choosing an Appropriate Combination of the
Four Quantum Numbers: n, ℓ, mℓ, m𝒔 Petrucci Example 8-12

97
Multielectron Atoms
• In multielectron atoms, there is mutual repulsion between electrons.
This factor has to be considered to solve (approximate) the
Schrödinger equation for this many-particle problem. The results
obtained are that the orbitals obtained are of the same types as
those for the hydrogen atom. The angular parts of the orbitals of a
multielectron atom are unchanged, but the radial parts are different.

98
Energy of orbitals in a single electron atom
Energy only depends on principal quantum number n

n=3

n=2

In a hydrogen atom, all orbitals with the same principal

quantum number n are degenerate.

1s1 (the electron in the ground-state

n=1 hydrogen atom)

99
Energy of orbitals in a multi-electron atom
Energy depends on n and l

n=3 l=2

n=3 l=1
n=3 l=0

n=2 l=1
n=2 l=0
In a multi-electron atom, different subshells in the
same principal shell are no longer degenerate.

n=1 l=0
100
Penetration and Shielding
Figure 8-34)
Orbital energy-level diagrams
for the hydrogen atom and a
multielectron atom (showing
n = 1, 2, and 3 only)

• For the hydrogen atom, orbitals within a principal shell, for example, 3s, 3p, and 3d,
have the same energy and are said to be energetically degenerate.

• In a multielectron atom, orbitals within a principal shell have different energies. In

general, for a multielectron atom, orbital energies increase with the value of n and
for a fixed value of n, with the value of ℓ.

• Note that the energy of a given orbital (e.g., 1s) decreases as the atomic number, Z,
increases.
101
Penetration and Shielding
• Electrons in orbitals closer to the nucleus screen or shield the nucleus
from electrons farther away.

• The screening electrons reduce the effectiveness of the nucleus in

attracting the particular more-distant electron, reducing the nuclear
charge the outer electron feels.

• The electrons in s orbitals are more effective at screening the nucleus

from outer electrons than are electrons in p or d orbitals.

• The ability of electrons in s orbitals that allows them to get close to the
nucleus is called penetration.

Screening ability: s>p>d An electron in an orbital with good

penetration is better at screening
Penetrating ability: s>p>d than one with low penetration.

102
 Penetration and Shielding
Shielding / Screening

Inner electrons shield outer electrons from experiencing the

full strength of nuclear charge. This reduces the actual
nuclear charge felt by more-distant electron.

Na 1s22s22p63s1
Z = 11

Zeff, effective nuclear charge, is the

actual nuclear charge felt by an electron.

103
 Penetration and Shielding

The probability of finding the e anywhere in a spherical

shell of radius r and an infinitesimal thickness.
Figure 8-36) Radial distribution functions
Graphs of the value of r2R2(r) as a function of r for the orbitals in the first three
principal shells. Note that the smaller the orbital angular momentum quantum
number, the more closely an electron approaches the nucleus. Thus, s orbital
electrons penetrate more, and are less shielded from the nucleus, than electrons
in other orbitals with the same value of n.

104
Electron Configurations
Rules for Assigning Electrons to Orbitals
• Electrons occupy orbitals in a way that
minimizes the energy of the atom.
Aufbau Principle

The order of filling of electronic subshells

Beginning with the top line, follow the arrows

• Pauli Exclusion Principle

No two electrons in an atom can have the same four quantum numbers
(i.e. The two electrons occupying the same atomic orbital must have
opposite spins) The two electrons in the same orbital
must be anti-parallel.

• Hund’s Rule
Electrons will fill in orbitals of equivalent energy in such a way that as
many spins remain unpaired and in parallel way as possible .
105
Electron Configurations
• For example, the electron configuration of a carbon atom can be
given as follows:

spdf notation (condensed): C 1s22s22p2

spdf notation (expanded): C 1s22s22px12py1

Paired electrons must
have opposing spins

orbital diagram: C

Electrons in different, singly occupied orbitals of the same subshell have the
parallel spins (arrows pointing in the same direction). Such electron
configuration is found to be the lowest energy state (ground-state) of an
atom. For atoms with electron configurations that are not the most stable,
they are said to be in an excited state.

106
 Electron Configurations
The Aufbau process
• Z = 7 – 10, N through Ne
In this series of four elements, the filling of the subshell is
completed. The number of unpaired electrons reaches a maximum
(three) with nitrogen and then decreases to zero with neon.

107
 Electron Configurations

The Aufbau Process – Sc through Zn

• In this series, electrons fill the d orbitals of the third shell. The d
subshell has a total capacity of ten electrons.

Two exceptions:
Cr and Cu
Special stability for
configurations in which a
3d subshell is half filled
with electrons (as with Cr)
or completely filled (as
with Cu).

108
 Electron Configurations
Class Practice 13

109
 Class Practice 13 (Con’t)

Solution:

110
 Electron Configurations

Four blocks (s,p,d,f)of elements according to the subshells being filled

111
 Electron Configurations
Class Practice 14

Solution:

112
 Electron Configurations
Class Practice 15

Solution:

113
 Part Three:
Periodic Trends

114
Periodic Trends
(1) Atomic Radii
• The size of an atom is determined by considering its radius (R).

E.g.

(a) Metal atoms (b) Non-metal atoms

Metallic radius Covalent radius

a H2 molecule

115
 Atomic Radius
Fig. 9-11) A comparison of some atomic and ionic radii
The values given, in picometers (pm), are
metallic radii for metals, single covalent radii for
nonmetals, and ionic radii for the ions indicated.
Gold spheres represent neutral atoms; blue
spheres represent cations; and green spheres
represent anions.

• Cations are smaller than the atoms

from which they are formed.
• Anions are larger than the atoms
from which they are formed.

116
 Atomic Radius

Going down a group...

• Down a group, atomic radii increase with the addition of
successive electron shells (i.e. n )

Moving across a period...

• Across a period, atomic radii decrease.

• From left to right of a period, each element has one more

proton (nuclear charge increases) and one more electron
which is added to the same shell. As electrons in the same
shell shield each other ineffectively, the effective nuclear
charge .
 Atoms become more compact.

117
 Class Practice 16

Solution:

118
(2) Ionization Energy
• Ionization energy is the quantity of energy a gaseous atom must absorb to be
able to expel an electron.

• Ionization energies decrease as First ionization energies as a function of atomic number

atomic radii increase. Generally

increase from lower left corner of
periodic table to the upper right
corner.

(1) More energy is required to ionize noble

gas atoms than to ionize atoms of the
elements immediately preceding or following
them. The maxima on the graph come at
the atomic numbers of the noble gases.

(2) The alkali metals are the most easily

ionized of all groups. The minima in the
graph come at their atomic numbers.
119
 Ionization Energy

Successive Ionization Energies of Sodium

Log I.E.

5 Sharp Observation:
rise • A general increase in
I.E.
• Can be divided into
4 three parts
• 2nd & 10th e−s are much
closer to the nucleus
Sharp than the preceding ones
3 rise

1 2 3 4 5 6 7 8 9 10 11
No. of successive I.E.
120
 Ionization Energy

• Li → Ne: [2.3.3] pattern

• Be > B N
Be O
• N >O B

• Ne has the largest IE

Be: 1s22s2 (full-filled subshell)

Extra
N: 1s22s22p3 (half-filled subshell)
stability
Ne: 1s22s22p6 (full-filled quantum shell)

Conclusion:
Other than the principal quantum shells, there are also
subshells comprising the electronic structure.

121
 Ionization Energy
Class Practice 17

Refer to the periodic table, arrange the following in the expected order of
increasing first ionization energy, I1: As, Sn, Br, Sr.
Solution:

122
(3) Electron Affinity
• Defined as the enthalpy change that occurs when an atom in the
gas phase gains an electron.

e.g.1) F(g) + e− → F−(g) EA = Hea= −328 kJmol−1

F(1s22s22p5) + e− → F−(1s22s22p6)
Note that a more negative value of EA indicates a
higher affinity for the atom to gain an electron.

• When a nonmetal atom gains a second electron, EA values are

positive because the electron is to be added to a negative ion.
There is strong repulsion.

O(g) + e− → O−(g) EA = −141.0 kJmol−1

O−(g) + e− → O2−(g) EA = +744 kJmol−1
123
 Electron Affinity
Electron affinities of main-group elements
[Values are in kJ/mol mole for the process X(g) + e– → X–(g)]
General trend: The smaller atoms to the right of the periodic table
tend to have more negative E.A.

End of Topic 124