OPEN UNIVERSITY AUSTRALIA

CHEM1030

CHEMISTRY OF MATERIALS 1

ATOMIC AND MOLECULAR THEORY

PARTS 1 & 2
A./Prof. Kay Latham, School of Applied Sciences, RMIT UNIVERSITY, Melbourne, Australia.
Room: 3.2.26. Tel:9925 2635. E-mail: kay.latham@rmit.edu.au
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Made by RMIT University for Open University Australia

under Part VB of the Copyright Act 1968
in reliance on (circle one of the following)

s.135ZJ = periodicals s.135ZK = anthologies s.135ZL = books

on 29/11/2012 (date)
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FOREWORD

Before commencing this section it is expected that the student will have a basic understanding of
the nature of : atoms, ions and molecules; of the key components of an atom; and a familiarisation
with the Periodic Table. It is therefore recommended that all students complete all reading and
exercises in Chapter 1 ‘Introduction: Matter, Measurement and Molecules’ of the recommended
text: Brown, LeMay, Bursten, Murphy, Langford and Sagatys (2010) Chemistry The Central Science:
A Broad Perspective 2e, Pearson, before attempting this course.
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PART 1 ATOMIC STRUCTURE

What happens when we turn on a neon light ? The electrons in the neon atoms, excited to a
higher energy by electricity, emit light when they return to lower energy. The ‘glow’ that
results is explained by one of the most revolutionary discoveries of the twentieth century,
the quantum theory. The quantum theory is a sophisticated model which scientists have
developed to rationalise experimental data, and represents our current understanding of the
behaviour of electrons in atoms.
In this section we explore the quantum theory and its importance in chemistry. We begin by
looking more closely at the nature of light and how our description of light was changed by
the quantum theory. We explore some tools used in quantum mechanics, the ‘new’ model for
the description of atoms. We then use the quantum theory to describe the arrangements of
electrons in atoms – the electronic structure of atoms.

The electronic structure of an atom refers not only to the number of electrons in an atom
but also to their distribution around the nucleus and to their energies. The quantum
description of the electronic structure of atoms helps us to understand the arrangement of
elements in the periodic table – why, some elements are unreactive gases, whereas some are
soft, reactive metals. Later we will see how the concepts of quantum theory are used to
explain trends in the periodic table and the formation of bonds between atoms.

Essential Reading and Exercises: Chapter 5 ‘Electronic Structure of Atoms’, and

Chapter 6 ‘Periodic Properties of the Elements’ of the recommended text: Brown, LeMay,
Bursten, Murphy, Langford and Sagatys (2010) Chemistry The Central Science: A Broad
Perspective 2e, Pearson (abbreviated to Brown et al.).
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1.0 WAVE PROPERTIES OF LIGHT

Much of our present understanding of the electronic structure of atoms has come from analysis of
the light emitted or absorbed by substances. Visible light is an example of electromagnetic radiation, or
radiant energy. Radiation carries energy through space. There are many types of electromagnetic
radiation including: radiowaves which carry music, infrared (heat), and x-rays used to image bones and
teeth (Fig. 1.0). However, all share certain fundamental characteristics.

Figure 1.0: The electromagnetic spectrum is a display of various types of electromagnetic radiation arranged in order of
increasing wavelength. For example, visible radiation has wavelengths between 400 nm (violet) and 750 nm
(red). [Source: Brown, LeMay, Bursten, Murphy, Langford and Sagatys (2010) Chemistry The Central Science: A Broad
Perspective 2e, Pearson]

All types of electromagnetic radiation travel at the same speed - the speed of light, c, and they all have
wave-like character like the waves that move through water. Water waves are the result of energy
being imparted to water eg. dropping of a stone. This energy is expressed as the up-and-down
movements of the water. If we were to take a cross-section through a water wave (Fig. 1.1a) we
would see that it exists as a series of peaks and troughs which repeat in a regular manner. The
distance between two adjacent peaks is termed the wavelength, the height of each individual peak and
trough is termed the amplitude, and the number of waves passing a particular point per second is
termed the frequency of the wave. Figs 1.1b and c illustrate the impact of varying wavelength,
amplitude and frequency. All types of waves can be classified according to these terms.

a) b) c)

Figure 1.1 Characteristics of electromagnetic waves. The shorter the wavelength, λ, the higher the frequency, ν. The
wavelength in b) is half as long as that in a), and the frequency of the wave in b) is therefore twice as great
as the frequency in a). [Source: Brown, LeMay, Bursten, Murphy, Langford and Sagatys (2010) Chemistry The Central
Science: A Broad Perspective 2e, Pearson]
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1.1 QUANTUM ENERGY AND PHOTONS

Although the wave model of light explains many aspects of its behaviour, there are several
phenomena this model cannot explain. The three phenomena most pertinent to our understanding
of the behaviour of light towards atoms include:

i. Blackbody radiation - the emission of light from hot objects,

ii. The photoelectric effect - the emission of electrons from metal surfaces on which light shines, &
iii. Emission spectra - the emissions of light from electronically excited gas atoms.

i). Hot Objects – when solids are heated, they emit radiation, as seen in the bright white light from
a tungsten light bulb and the intense orange of molten steel. The wavelength distribution
depends on the temperature i.e. “red hot” objects are cooler than “white hot” objects. The wave
nature of light does not explain how an object can glow when its temperature increases. In 1900,
the German scientist, Max Planck, explained it by assuming that energy comes in packets called
quanta, and can only be absorbed or released by atoms in these discrete amounts.
To understand quantisation, consider the notes produced by a violin (continuous) and a piano
(quantised). A violin can produce any note when the fingers are placed at an appropriate spot on
the bridge, whereas a piano can only produce notes corresponding to the keys on the keyboard.

ii). Photoelectric Effect and Photons – experiments have shown that light shining on a clean
metal surface can cause electrons to be ejected from the metal. The electrons will only be
ejected if the photons have sufficient energy (work function): below the threshold frequency no
electrons are ejected, and above the threshold frequency, the excess energy appears as the
kinetic energy of the ejected electrons.

To explain this effect, Einstein used Planck’s assumption, and stated that the radiant energy
striking the metal surface behaved not as a wave but rather as if it were a stream of tiny energy
‘packets’. The energy packet, called a photon, behaving like a tiny particle.

Thus, extending Planck’s theory, Einstein concluded that each photon must have an energy
equal to Planck’s constant (h = 6.63 × 10 -34 Js) times the frequency of the light:

Energy of photon, E = h ν

Therefore, if one knows the wavelength of light, one can calculate the energy in one photon, or
packet, of that light:

c = λν
E = hν

iii). Emission (Line) Spectra and the Bohr Model

Radiation composed of only one wavelength is called monochromatic.

Radiation that spans a whole array of different wavelengths is called continuous.

When radiation from a light source, such as a light bulb, is separated into its different
wavelength components, a spectrum is produced. White light can be separated into a continuous
spectrum from red to green to purple. Note that on the continuous spectrum there are no dark
spots, which would correspond to different lines (Fig. 1.2).
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Figure 1.2

A continuous spectrum is produced when white light is

passed through a prism. [Source: Brown, LeMay, Bursten,
Murphy, Langford and Sagatys (2010) Chemistry The Central
Science: A Broad Perspective 2e, Pearson]

However, not all radiation is continuous. A gas placed in a partially evacuated tube and
subjected to a high voltage produces single colours of light. For example, the light emitted from
neon is red-orange, whilst the light emitted from hydrogen is lilac. The spectrum that we see
here contains radiation of only specific wavelengths; this is called a line spectrum (Fig. 1.3).

Figure 1.3 Atomic emission – different gases emit light of different characteristic wavelength upon excitation by an
electrical discharge – hydrogen (left), neon (middle). The spectrum produced from the electrical discharge
from sodium (right top), and hydrogen (right bottom). [Source: Brown, LeMay, Bursten, Murphy, Langford and
Sagatys (2010) Chemistry The Central Science: A Broad Perspective 2e, Pearson]

In 1913, Niels Bohr offered an explanation for these line spectra based on the work of Planck
and Einstein. Together, these three scientists have paved the way for understanding how
electrons are arranged in atoms.

Bohr’s ‘planetary’ model of an atom (Figure 1.4), stated that : electrons in an atom can only
occupy certain orbits of specific radii (corresponding to certain definite energies); that electrons
in permitted orbits have specific, ‘allowed’ energies; energy is only emitted or absorbed by an
electron as it moves from one allowed energy state to another; and energy is gained or lost as a
photon :

E = hν

Figure 1.4 Bohr’s ‘planetary’ model of an atom

Colours from excited gases therefore arise because electrons move between energy states in the
atom. Since the energy states are quantised, the light emitted from excited atoms must be
quantised and appear as line spectra.
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1.2 THE WAVE BEHAVIOUR OF MATTER

Knowing that light has a particle nature (as well as a wave nature), it seems reasonable to ask
whether matter has a wave nature ? This question was answered by Louis deBroglie. Using Einstein’s
and Planck’s equations, deBroglie derived:

λ=h/mv Eq. 1.3

The momentum, m v, is a particle property, whereas λ is a wave property.

Matter waves is the term used to describe wave characteristics of material particles. Therefore, in
one equation deBroglie summarised the concepts of waves and particles as they apply to low-mass,
high-speed objects.

As a consequence of deBroglie’s discovery, we now have techniques such as X-ray diffraction and
electron microscopy to study small objects.

SUB-ATOMIC MATTER HAS BOTH SIGNIFICANT WAVE (λ) AND PARTICLE (m)
PROPERTIES, i.e. WAVE-PARTICLE DUALITY.

The particle of matter most important to chemists is the ELECTRON.

The particle properties of electrons were well established experimentally early in the 20th century.
Experimental evidence for the wave nature of electrons was obtained in 1927 when Davison and
Germer diffracted (a wave property) electrons through a metal crystal.

Equation 1.3 suggests every particle of mass (from electrons to planets) has wave properties.
However since

λ.m.v=h (remember h is a constant)

If m is very large, then λ must be very small. Hence wave properties associated with a large mass
cannot be detected.

Example

What is the wavelength associated with an electron travelling at half the speed of light?

Data: m = 9.11 x 10-31 kg

c = 3.00 x 108 m s-1

λ = (6.63 x 10-34) / (9.11 x 10-31) (0.5) (3 x 108) = 4.85 x 10-12 m

What is the wavelength associated with a one tonne (1000 kg) elephant travelling at about 10 m.s-1?

λ = (6.63 x 10-34) / (1.00 x 103) (10) = 6.63 x 10-38 m

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1.3 THE HEISENBERG UNCERTAINTY PRINCIPLE

‘It is not possible to determine simultaneously the position and momentum of a small particle with
complete exactness.’

This means for example if we want to ‘see’ an electron (regarding this as a particle), we must use light
photons to indicate its position. But in ‘locating’ the electron these photons change its position and/or
momentum, so we can never locate the electron exactly.

Mathematically, Δ (m . v) . Δx ~ h Eq. 1.4

m = mass of particle
Δv = uncertainty in speed of particle
Δx = uncertainty in position of particle

So, Δ (m . v) . Δx ~ h

Δ v . Δx ~ h / m
(m is constant)

From this relationship Δv and Δx are large if m is very small, e.g. as with sub-atomic particles.

Conversely if m is very large then Δv and Δx are very small, e.g. the uncertainty in the position of a one
tonne elephant is very small.

Exercise:
An electron is accelerated to one tenth the speed of light. Its velocity can be measured with an
uncertainty of ± 1%. What is the uncertainty in its position?

Δ v . Δx ~ h / m

v = 0.1 (3 10 8) = 3 10 7, Δv = 1% v = 0.01 (3 10 7) = 3 10 5 m s-1

Δx = h / Δv. m = (6.63 10 -34) / (9.11 10 -31) (3 10 5) = 2.4 10 -9 m

Exercise:
A cricket ball weighing about 0.5 kg is travelling at about 100 km/hour. Its velocity can be measured
with an uncertainty of ± 1%. What is the uncertainty in its position?

Δ v . Δx ~ h / m

v = 100 km.hr -1 = 28 m s-1, Δv = 1% v = 0.01 (28) = 0.28 m s -1

Δx = h / Δv. m = (6.63 10 -34) / (0.5) (0.28) = 4.7 10 -33 m

Much more certain of ball’s position than of electron’s position.

If the electron is regarded as a wave, then the uncertainty in position and momentum is allowed for,
since the position of a wave is uncertain to the extent of its wavelength.
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SUMMARY - THE CHARACTERISTICS OF LIGHT

WAVES wavelength, λ, nm (λ lamda)

frequency, ν, Hz (ν nu)
speed of emr in a vacuum (c ~ 3 x 108 m/s)

Relationship between wavelength and frequency

λ= c /ν Eq. 1.1

Example: red light λ ~ 700 nm, ν ~ 4 x 1014 Hz

QUANTA (energy ‘packets’) - A quantum of light energy is referred to as a photon, and the energy
(E) of a single photon is given by,

E =h.ν Eq. 1.2

Where Planck’s constant, h, = 6.63 x 10-34 J/Hz (Note: 1J = 1kg.m2.s-2)

Example: red light E = (6.63 x 10-34 ) (4 x 1014) = 2.7 x 10-19 J

DUALITY - Light has WAVE-like AND PARTICLE-like properties.

Energy is transferred through space as electromagnetic radiation (emr) that can be described as
either waves or particles (quanta).

MATTER AS A WAVE

In 1924 de Broglie suggested electrons had both wave and particle properties - light energy may be
treated as a wave or a particle.
λ=h/m.v Eq. 1.3

Where (m = mass of particle, v = speed, m.v = momentum)

This equation indicates the relationship between wave property λ, and mass or momentum of a particle.

Heisenberg Uncertainty Principle

The Electron has both significant wave and particle properties

Position and momentum (velocity) of an electron cannot both be known with certainty