© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 135

5.1 Early Models of the Atom — Dalton to Rutherford

Warm Up
Recall what you learned about atomic structure in Science 10 to answer the following questions.
1. Complete the following table about the three subatomic particles in an atom.

Subatomic Particle Relative Charge Relative Mass Location in Atom

1+
1 amu
outside nucleus

2. The two subatomic particles responsible for almost all of an atom’s mass are the _______________ and the
_______________.

3. Most of an atom’s volume is actually _______________ _______________ (two words).

Think about your favorite detective mystery and why you enjoyed reading it. The most
The Ancient Greeks interesting parts of the story were not only the ultimate answer to the mystery, but also
Had It Right — for how each of the clues were discovered, processed, and then applied to derive that final
Awhile solution.
The story of our eventual understanding of the building blocks of matter is an
equally engaging read because it is like a good mystery novel!
The story begins almost 2500 years ago in ancient Greece with the philosopher
Leucippos and his student Democritus. They reasoned that if a sample of solid matter
such as gold was repeatedly cut into smaller and smaller pieces, the eventual result
would be a particle so small it couldn’t be cut into anything smaller. Democritus used
the term “atomos” (Greek for “uncuttable”) to refer to these smallest particles of matter.
He imagined that particles of different sizes and shapes might be components of all the
different types of matter.
That sounds like a promising start. However, the ancient philosophers relied largely
on intuition rather than experimentation for knowledge, and soon the ideas of another
philosopher replaced the idea that matter was composed of tiny particles. Aristotle
proposed instead that all types of matter were actually made up of different proportions
of four basic elements: earth, air, fire, and water. Unfortunately, this idea and its various
incarnations were embraced for almost 2000 years in the practice of alchemy. During
Figure 5.1.1 Alchemists the next two millennia, alchemy dominated the chemical landscape (Figure 5.1.1). Many
developed a set of symbols for alchemists were searching for a way to change base metals into gold. Although this
the elements and linked them
to the planets. For example,
search was ultimately doomed to failure, some alchemists were actually serious scientists.
gold was associated with the We owe the discoveries of such useful chemical procedures as distillation, the separation
Sun and Mars with iron. of metals from ores, and the preparation of some acids to alchemy.

136 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 Finally, in the last half of the 1600s, the first real scientist emerged. Robert Boyle was
Science Begins and the first person to perform and publish the results of true quantitative experiments. All
the Atom Returns of his observations convinced him that the four-element idea proposed by Aristotle
was incorrect. In 1661, Boyle published the Skeptical Chymist in which he outlined what
we now call the scientific method. He also provided an experimental definition for an
element as being an “unmingled body.” As this definition and Boyle’s insistence on
experimentation gained acceptance, more and more elements were discovered, and
Aristotle’s ideas about matter were eventually discarded.
Further studies over the next 140 years by such scientists as Carl Scheele, Joseph
Priestly, Antoine Lavoisier, and Joseph Proust resulted in mass laws governing compound
composition and chemical reactions. It was these laws that were used by the English
schoolteacher John Dalton to propose a theory about matter first suggested more than
2200 years earlier. In 1808, Dalton published a book called A New System of Chemical
Philosophy in which he presented his atomic theory. The main points of the theory are
shown below.

Dalton’s Atomic Theory

1. All matter is composed of extremely small particles called atoms, which cannot
be broken into smaller particles, created, or destroyed.
2. The atoms of any given element are all identical to each other and different from
the atoms of other elements.
3. Atoms of different elements combine in specific ratios to form compounds.
4. In a chemical reaction, atoms are separated, rearranged, and recombined to form
new compounds.

Dalton’s theory was a major step forward in our understanding of matter.

Experimental evidence had finally led back to an idea that had made sense to some
philosophers thousands of years earlier. But there were exciting revelations about the
atom soon to be discovered.

Quick Check
1. Suggest a reason why Robert Boyle is often called the first true scientist.
________________________________________________________________________

2. Democritus and Dalton both proposed the existence of atoms. How was the development of their ideas
different?
________________________________________________________________________

3. Which part of Dalton’s atomic theory is now known to be incorrect?

________________________________________________________________________

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 137
 The relationship between matter and electric charge fascinated scientists in the 1800s.
Discovering the They wondered, for example, how electricity passed through matter and how it might
Subatomic — behave in the absence of matter. Between 1859 and 1879, work done by Julius Plücker
Thomson’s Atomic in Germany and William Crookes in England using special glass tubes soon led to one of
Model the most important discoveries ever made about matter and the nature of the atom.

One such device Crookes worked with consisted of a negatively charged electrical
Gas Discharge Tubes terminal (a cathode) embedded in one end of a sealed glass tube (Figure 5.1.2). About
and Strange Green two-thirds along the length of the tube, a positive terminal (an anode) in the shape of a
Glows broad flat cross was embedded. The tube was connected to a vacuum pump. When the
electric current was turned on and the air in the tube was pumped out, any air present
began to glow and then change color as the tube emptied. Eventually, when all of the
air was gone, the glow disappeared — almost. Close inspection in a darkened laboratory
revealed a shadow of the anode cross surrounded by faint green glow at the far end of
the tube opposite the cathode and a very faint glow coming from the cathode itself.
Crookes concluded that something must be travelling from the cathode to the anode
inside the tube even though all the air was gone.
cathode ray tube

cathode

anode
mask holder

Figure 5.1.2 Crookes’ glass tube

In Paris, Jean Baptiste Perrin discovered that a magnet placed next to the tube was
able to deflect the mysterious beam, which meant that the beam was actually a stream of
charged particles. Crookes confirmed this and suggested that this “cathode ray” might be
composed of negatively charged particles, but no one paid much attention to that idea.

Many researchers experimented with cathode-ray tubes, as they came to be known.

Cathode Rays and However, it wasn’t until the great English physicist Joseph John Thomson (“J.J.” to his
Subatomic Particles friends) turned his attention to these mysterious rays that a breakthrough came. In 1897,
Thomson set to work to discover the nature of cathode rays. He modified the original
Crookes’ tube by focussing the cathode ray into a thin beam onto a fluorescent target. He
then exposed the beam to an electric field in addition to a magnetic field. He found that
the beam was deflected towards the positive plate in the electric field. This meant that
these mysterious particles must have a negative charge (Figure 5.1.3).

Figure 5.1.3 The deflection of the beam of particles toward the positive magnetic plate indicated that the
particles had a negative charge.

138 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 Thomson knew that the amount of deflection a charged particle experiences in
an electric field depends on the ratio of the particle’s charge to its mass. The larger that
ratio is (the more charge and the less mass), the greater the deflection. By carefully
adjusting the currents in his modified vacuum tube, Thomson was able to calculate the
charge-to-mass ratio (e/m) for cathode rays. He found that value to be –1.76 × 108 C/g (C
stands for coulomb, the SI unit of charge). That was almost 2000 times greater than that
of the hydrogen ion, which was the smallest charged particle known in 1897. Thomson
concluded that these little negative particles were actually about 2000 times lighter than
a hydrogen ion. This astounded him because it meant that he had found a particle far
smaller than the smallest atom!

Thomson repeated the experiments many times with different metals used as the
The Electronic cathode and even different gases inside the tube. Each time the results were the same.
Nature of the Atom This had to mean that these mysterious negative particles were present in atoms of
different elements. In a speech given on April 29, 1897, to the Royal Institution, J.J.
Thomson told his audience that cathode rays were actually tiny negatively charged
“corpuscles” of electricity, each with an identical mass about 2000 times lighter than
an atom of hydrogen. The audience wasn’t yet ready to believe that bits of matter even
smaller than atoms existed.
Soon, however, this revolutionary idea was accepted. This tiny “corpuscle” was
identified as the electron and shown to be a component of every atom. In 1906,
Thomson was awarded the Nobel Prize for his work on the conduction of electricity
through gases in which he discovered the negative charges that became known as
electrons.
In an article in England’s “Philosophical Magazine” in 1897, Thomson suggested
what else might be in an atom. He reasoned that if an intact atom has no charge, then
there must be something positive in an atom to balance the negative charge on the
electron. He discovered that “something” within a few years.
At this point, it’s valuable to consider the significance of what Thomson discovered.
First, he found that atoms were themselves built from even smaller components. Second,
and arguably more important, Thomson discovered that these subatomic particles had
opposite charges. This meant that the building blocks of matter are essentially electrical
entities! Remember that idea, because it will be fundamental to most of the chemistry
you will ever learn.
Thomson soon used hydrogen gas in a further-modified cathode-ray tube
negative to show that positively charged particles (labelled protons in 1920) also existed
electrons in atoms. This led him to propose the first model of the atom since 1808. In 1903,
“plums”
- - Thomson suggested that an atom could be seen as a “spongy ball” or “plum
- pudding” with negative electrons distributed evenly throughout the spongy
- mass of the atom, much like bits of fruit in an English pudding or raisins in a
- - muffin (Figure 5.1.4). The “plum pudding” model as it became known was soon
- replaced, but it was a major advance in the understanding of matter and was
- based on the best data available at the time.
-

positive “pudding”

Figure 5.1.4 Thomson’s atomic model

(1903)

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 139
 Quick Check
1. The electron’s charge was determined in 1909 by the American physicist Robert Milliken to be –1.602 × 10–19
C. Use the e/m ratio for the electron (1.76 × 108 C/g) to calculate the electron’s mass in grams.
Hint: To determine the mass in grams, begin with the provided value of charge in coulombs and use the
e/m ratio as a conversion factor. As the required answer is in grams, the e/m ratio will need to be inverted to
allow the coulombs to cancel, providing an answer in grams.

2. What evidence led Crookes to conclude that the unknown ray in his vacuum tube
(a) originated at the cathode?
________________________________________________________________________

(b) was a beam of charged particles?

________________________________________________________________________

(c) may be a beam of negatively charged particles?

________________________________________________________________________

3. Identify the two most important components of Thomson’s atomic theory.

(a) _____________________________________________________________________

(b) _____________________________________________________________________

In 1895, young Ernest Rutherford, working on his father’s farm in New Zealand, received
Rutherford Changes the news that he’d won a scholarship to study at the University of Cambridge with J.J.
Things Thomson at the prestigious Cavendish Laboratory. Rutherford arrived at Cambridge
in time to work with Thomson during the discovery of negative electric charges. Not
surprisingly, therefore, Rutherford fully believed in the “plum pudding” model of the
atom.
After training with Thomson, Rutherford went to McGill University in Montreal
where he devoted much of his time to studying the nature of the emissions associated
with the newly discovered phenomenon of radioactivity. Rutherford’s work at McGill
would soon give him all the tools he needed to test Thomson’s atomic model. Using
samples of radioactive elements such as radium provided by Marie and Pierre Curie,
Ernest Rutherford and Frederic Soddy discovered three types of emissions associated
with radioactivity. They labeled these emissions as alpha particles, beta particles, and
gamma rays. Their nature and properties are summarized in Table 5.1.1.

140 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
Table 5.5.1 Characteristics of Radioactive Emissions

Emission Nature of Emission Penetrating Ability Emission Speed

Alpha (α) helium nuclei penetrates a few cm of air but stopped by a thin ~ 16 000 km/s
particles sheet of aluminum foil
Beta (β) electrons penetrates a few mm of aluminum but stopped by a ~ 200 000 km/s
particles thin sheet of lead
Gamma (γ) high energy waves penetrates at least 30 cm of lead or 300 000 km/s (speed
rays 2 km of air of light)

By 1909, Rutherford had returned to England and joined the University of

Manchester. Working with colleagues Hans Geiger and Ernest Marsden, Rutherford
decided to use alpha particles as a type of “probe” to test the makeup of the atom. The
experiment involved aiming alpha particles emitted from a radioactive source at very thin
(1/2000 mm) sheets of gold foil, and then observing where those alpha particles struck a
fluorescent screen after passing through the atoms in the foil.
Recall that Rutherford had been a student of J.J. Thomson and firmly believed that
the plum pudding model accurately represented the structure of an atom. Based on that
belief, Rutherford fully expected that nothing in Thomson’s “spongy” atom was capable
of significantly altering the path of alpha particles traveling at 16 000 km/s. All the alpha
particles should, therefore, pass through the gold foil without deviating from their
original path. If any deflection did occur, it would be minimal at best.
The vast majority of alpha particles behaved exactly as predicted and passed right
through the gold foil without deviating (Figure 5.1.5). But (and this is a huge “but”) a
few particles deviated through large angles and a very few (about 1 in 20 000) didn’t
go through the foil at all, but rather bounced back! Rutherford wrote in his journal that
“it was quite the most incredible event that has ever happened to me in my life. It was
almost as incredible as if you had fired a 15-inch shell at a piece of tissue-paper and it
came back and hit you.” Rutherford was referring to the fact that nothing in Thomson’s
atomic model was capable of knocking an alpha particle far off its course, let alone
turning it around. Clearly, the model of the atom proposed by Thomson needed a major
revision and Rutherford was able to do just that.

stream of
high-energy
radioactive particles
particle source electrons around
nucleus nucleus

spectral screens
to detect particles
gold foil
lead block

gold foil

flashes of light
from particles
(a) hitting screen (b) � � � � � �

Figure 5.1.5 (a) Rutherford’s gold foil experiment; (b) Rutherford’s atomic model explaining the results of the experiment

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 141
 Rutherford explained the results by suggesting that virtually all the mass of an atom
Rutherford’s Model was concentrated in a very tiny, dense, positive structure at the atom’s centre he called
of the Atom the nucleus. Surrounding this nucleus was a cloud of negatively charged electrons that
accounted for all of atom’s volume but virtually none of its mass. Rutherford calculated
that the nucleus was so small compared to the volume occupied by the surrounding
electrons that the vast majority of an atom was actually empty space! Although
Rutherford’s model for the atom resembled a tiny planetary system with electrons
orbiting a nucleus much like planets orbit the sun, Rutherford himself wrote, “The atom
has often been likened to a solar system where the sun corresponds to the nucleus and
the planets to the electrons….The analogy, however, must not be pressed too far.”
Rutherford was responsible for perhaps the most significant contribution ever made
to our understanding of atomic structure, and he received the Nobel Prize in chemistry in
1908. Shortly after discovering the nucleus, Rutherford realized that his model explained
the charged nature of the atom, but couldn’t account for all of its mass. He believed that a
neutral particle must also exist in the nucleus that added mass but no charge to the atom.
More than 20 years later, James Chadwick discovered that particle, the neutron, just as
Rutherford had predicted.
Several significant changes to Rutherford’s atomic model were still needed to
explain electron behaviour. However, as Rutherford theorized, the atom is an entity
whose tiny positive nucleus accounts for 99.97% of its mass but only about one
trillionth of its volume! The negative electrons move rapidly within the available atomic
volume held by the attraction of the nucleus. Table 5.1.2 is a simplified summary of the
composition of the atom as we view it today.

Table 5.1.2 The Composition of the Atom

Subatomic Particle Relative Charge Relative Mass Absolute Mass Location in Atom
Proton (p+) 1+ 1 amu 1.673 x 10–24 g inside nucleus
Neutron (n0) 0 1 1.675 x 10–24 g inside nucleus
Electron (e–) 1– 0 9.109 x 10–28 g outside nucleus

142 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 Quick Check
1. Why did Rutherford believe the nucleus was so small compared to the size of the atom itself?
________________________________________________________________________

2. Why did Rutherford believe that the nucleus had a positive charge?
________________________________________________________________________

3. To what parts of the gold foil experiment was Rutherford referring when used the following analogies:
(a) a 15-inch shell _______________________________________________
(b) a piece of tissue paper _____________________________________________

4. Experiments show that the diameter of the nucleus of an atom is about 10–14 m and the diameter of an
atom itself is about 10–10 m. If the diameter of the nucleus was actually 2.0 cm (about the width of your
thumb), determine the diameter of the entire atom.

We can use the above table to discuss three important numbers associated with every
Atomic Number, element. The atomic number (Z) of an element equals the number of protons and the
Mass Number, and positive charge on the nucleus of each of its atoms. All of the atoms of a given element
Neutron Number have the same atomic number, and each element’s atomic number is different from that
of any other element. For example, there are six protons in the nucleus of every carbon
atom so Z = 6 for carbon. For nitrogen, Z = 7; for oxygen, Z = 8, and so on. This illustrates
an extremely important point to remember: It is the number of protons that determines
the identity of an atom. While the number of neutrons may vary in atoms of the same
element, the number of protons always remains the same.
The presence of neutrons in the nucleus also contributes mass to an atom. The
mass number (A) for each atom equals the sum of the number of protons and neutrons
in the nucleus. A proton and a neutron each contribute one unit to an atom’s mass
number. For example, an atom of nitrogen with 7 protons and 7 neutrons has a mass
number of 14, and an aluminum atom with 13 protons and 14 neutrons has a mass
number of 27. Any particular atom can be represented using a notation that includes the
element’s symbol, mass number, and atomic number as shown in Figure 5.1.6.

mass number A
atomic number Z
X element symbol

Figure 5.1.6 Notation for showing the mass number and the atomic number of the atom of an element

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 143
 Using this notation, we can see that the neutron number (N) can easily be
calculated by the following: N (neutron number) = A (mass number) – Z (atomic
number). For example,

14 N represents a nitrogen atom with 7 neutrons (read as “nitrogen-14”)

7

19 F represents a fluorine atom with 10 neutrons (read as “fluorine-19”)

9

An atom’s mass is measured relative to an atomic standard. The modern standard is

a carbon-12 atom whose mass is defined as exactly 12 atomic mass units. Therefore, one
atomic mass unit (amu) is defined as exactly 1/12 the mass of a carbon-12 atom.
Chemical changes never involve change to the nucleus but often involve electrons
being added to or removed from neutral atoms that form ions. An ion is an electrically
charged atom or group of atoms. For every electron an atom gains, it also gains that
amount of excess negative charge and becomes a negative ion or anion. Each electron
lost by an atom leaves that amount of excess positive charge on the resulting positive
ion or cation. We can use the notation in Figure 5.1.6 to represent ions as well as neutral
atoms. For example:

24 Mg 2+ shows a magnesium cation 31 P 3– shows a phosphide anion with

12 15
with 12 protons, 12 neutrons, protons, 16 neutrons, and
and 10 electrons 18 electrons

Sample Problem
1. Determine the number of protons, neutrons, and electrons present in a 4+ ion of Pb-207.
2. Write the symbol for this cation using the notation described above.

What to Think about How to Do It

Question 1
1. A 4+ cation has 4 fewer electrons than protons.
The atomic number of Pb is 82. Therefore there are 82
protons present, but only 78 electrons because of the
The number of neutrons is given by:
4+ charge.
207 – 82 = 125 neutrons.

The correct notation is: 207 Pb 4+

2. The number of protons = the atomic number 82
The neutron number is determined by subtracting the
atomic number from the mass number.

144 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 Practice Problems
1. Determine the number of protons, neutrons and electrons present in each of the following:
(a) 40 Ca 2+ (b) 128 Te 2– (c) 52 Cr 3+
20 52 24

2. Write atomic notation for neutral atoms of the following:

(a) bromine-79 (b) gold-197 (c) thorium-232

3. Complete the following table for atoms and ions:

Atomic Mass Number of Number of Number of

Notation Number Number Protons Neutrons Electrons
95 Mo
42

79 34 36

47 109 46

232 Th 4+
90

83 126 83

Although all the nuclei of the atoms of a particular element have the same atomic
Isotopes and Mass number, they may not have the same atomic mass. Isotopes are different forms of the
Spectrometry same element with different numbers of neutrons and therefore different mass values.
For example, 98.89% of naturally occurring carbon atoms have 6 neutrons (carbon-12),
1.11% have 7 neutrons (carbon-13) and fewer than 0.01% have 8 neutrons (carbon-14).
Remember that the chemical behaviour of a particular element is determined
primarily by the number of electrons. The atomic number of any neutral element equals
the number of electrons surrounding the nuclei of that atom, so all of the isotopes of a
particular element have almost identical chemical properties.
The number of naturally occurring isotopes of an element and their relative masses
and abundances may be determined by a mass spectrometer, an instrument based on
the same principles employed by J.J. Thomson to discover the electron (Figure 5.1.7).
Mass spectrometry uses the fact that charged particles moving through a magnetic
field are deflected from their original path based on their charge-to-mass (e/m) ratio. The
greater the ratio, the more deflection occurs. Consider the example of a beam of ionized
neon (Ne1+) containing the isotopes neon-20, neon-21, and neon-22. The beam enters
the magnetic field chamber of a mass spectrometer, and the three isotopes separate
on the basis of their e/m ratios. A detector in the spectrometer records the separations,

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 145
 the percent abundance, and the mass of each isotope. The mass number for neon that
appears on the periodic table is the weighted average of those naturally occurring
isotopes. The sample problem below shows how the calculation is done.

accelerator plate
magnet
most massive ions
deflected least
electrons

accelerator plate

positive ion beam

- from sample
electron trap
gas sample least massive ions detecting screen
+ deflected farthest

Figure 5.1.7 Mass spectrometer

Sample Problem — Calculating Atomic Mass

1. Use mass spectrometry data below to calculate the atomic mass of neon.

Mass of Atom in amu Percent Abundance in

Isotope (relative to 12C = 12.0000) Nature
neon-20 19.9924 90.48
neon-21 20.9938 0.27
neon-22 21.9914 9.25

What to Think about

1. The calculated atomic mass is the weighted average of the masses of each isotope.
The sum of the three (mass) ´ (% abundance) products will therefore represent the atomic mass of neon.

How to Do It
(mass Ne-20)(% abundance) + (mass Ne-21)(% abundance) + (mass Ne-22)(% abundance)
(19.9924 amu)(90.48/100) + (20.9938 amu)(0.27/100) + (21.9914 amu)(9.25/100) = 20.18 amu

146 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 Sample Problem
Sample Problem — Calculating Isotope Percent Abundance
1. Boron has two naturally occurring isotopes. Calculate the percent abundances of boron-10 and boron-11 using
the following data:

Atomic mass of boron 10.81 amu

Isotopic mass of boron-10 10.0129 amu
Isotopic mass of boron-11 11.0093 amu

What to Think about How to Do It

1. The weighted averages of the isotopes
yield the atomic mass of 10.81 amu.
The sum of the fractional abundances ( )(10.0129 amu) + (1 – x) (11.0093 amu) =
(x
must be 1. So if x = abundance of boron- 10.81 amu
10, then the abundance of boron-11 must
be 1 – x.
Use the method shown in the previous
sample problem.

2. Solve for ((xxx)) and (1 – xx) and then express 11.0093 x + 10.0129 x = 11.0093 – 10.81
those fractions as percentages to answer 0.9964 x = 0.1993
the question.
x = 0.2000 and 1 – x = 0.8000
Therefore % abundance boron-10 = 20.00 %
and % abundance boron-11 = 80.00 %

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 147
 Practice Problems — Using Mass Spectrometry Data
1. Use the mass spectrometry data below to calculate the atomic mass of gallium.

Mass of Atom in amu Percent Abundance in

Isotope (relative to 12C = 12.0000) Nature
gallium-69 68.9256 60.11
gallium-71 70.9247 39.89

2. The following neon ions enter the magnetic field chamber of a mass spectrometer. Arrange them in order
from the isotope that will be deflected most to the isotope deflected least.

22 Ne 1+ 21 Ne 1+ 20 Ne 1+
10 10 10

Most Deflection Least Deflection

3. Chlorine has two naturally occurring isotopes. Calculate the percent abundances of chlorine-35 and
chlorine-37 using the following data:

Atomic mass of chlorine 35.453 amu

Isotopic mass of chlorine-35 34.9689 amu
Isotopic mass of chlorine-37 36.9659 amu

148 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 5.1 Activity: Linking the Giant
Question

Procedure
1. Consider the following researchers mentioned in this section:

Robert Boyle Julius Plücker James Chadwick Frederic Soddy

Carl Scheele Jean Baptiste Perrin Ernest Marsden
Joseph Priestly William Crookes Hans Geiger
Joseph Proust J.J. Thomson Robert Milliken
Antoine Lavoisier Marie and Pierre Curie James Chadwick
John Dalton Ernest Rutherford

Construct an “Atomic Theory Timeline” diagram and include all of the names given above including dates and
which discovery each individual made that contributed (directly or indirectly) to our understanding of the atom.

2. Write a point-form biography of any one scientist listed above focusing on all of his or her major scientific
achievements.

3. Exchange you biography with a classmate or present your biography to the class.
Record and Discussion
1. In looking at your timeline and the discoveries of the different scientists, what can you conclude about the
development of scientific knowledge?

2. Why did you choose the scientist whose biography you wrote?

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 149
5.1 Review Questions
1. Briefly describe the structure of the atom as proposed by each of the following:
(a) John Dalton

(b) J.J. Thomson

(c) Ernest Rutherford

2. What evidence led J.J. Thomson to propose that the mysterious negative particles he was studying were smaller
than atoms?

3. How did the discovery of radioactivity contribute to Ernest Rutherford’s atomic model?

4. Why was Rutherford so surprised by the results of his gold foil experiment?

5. Complete the following table for neutral atoms.

Atomic Mass Number of Number of Number of

Notation Name Number Number Protons Neutrons Electrons
77 54

210 84

neptunium-237

97 150

257 100

6. Write the notation for the following neutral atoms.

(a) An atom with 78 protons and 117 neutrons

(b) An atom with a mass of 237 having 90 electrons
(c) An atom with 69 electrons and 100 neutrons

150 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
7. Write the notation for the following ions.

(a) A 3+ cation with 80 electrons and 117 neutrons

(b) A 1– anion with 54 electrons and 78 neutrons
(c) An ion with 66 electrons, 69 protons and 100 neutrons

8. Use the following mass spectrometry data to calculate the atomic mass of magnesium.

Mass of Atom in amu Percent Abundance in Nature

Isotope (relative to 12C = 12.0000)
magnesium-24 23.9850 78.99
magnesium-25 24.9858 10.00
magnesium-26 25.9826 11.01

9. An atom’s volume is mostly empty space containing a cloud of negative electrons surrounding a very tiny positive
nucleus. Therefore “solid matter” as we know it is really an illusion. Suggest a reason why all matter doesn’t simply
collapse.

10. Silver has two naturally occurring isotopes. Calculate the percent abundances of silver-107 and silver-109 using the
following data:

Atomic mass of silver 107.87 amu

Isotopic mass of silver-107 106.9051 amu
Isotopic mass of silver-109 108.9045 amu

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 151
5.2 Quantum Theory and the Bohr Model of the Atom

Warm Up
1. (a) List three properties of waves such as water waves or visible light.
_______________________________________________________________________

(b) What would you expect to happen when two water waves moving in opposite directions met each other?
_______________________________________________________________________

2. (a) List three properties of solid objects or particles such as the marbles in a bag.
_______________________________________________________________________

(b) What you would expect to happen when two marbles moving in opposite directions met each other?
_______________________________________________________________________

3. Are any of your answers to question 1 identical to question 2? (Stay tuned…)

_______________________________________________________________________

A serious challenge to Rutherford’s atomic model arose almost immediately. A very secure
Waves Behaving like prediction of the physics available at the end of the 1800s was that accelerating charges
Particles? Well Hit should radiate energy. Because orbiting electrons are accelerating charges, electrons in
Me with a Planck! atoms should lose energy. That prediction was catastrophic for Rutherford’s model. It
meant that all atoms, and so also all matter, should collapse in a fraction of a second as
their electrons lost energy and spiraled into the nucleus! Obviously, a significant piece
of the atomic puzzle was missing and even Rutherford himself was ready to abandon
his view of the atom. Yet, his conclusions and his nuclear model were correct. The real
problem was that the physics of the day needed to be re-written to explain the behaviour
of electrons in atoms.
To begin to understand how the solution came about, we must consider the work
of German physicist Max Planck. In 1900, this conservative professor began nothing short
of a revolution in physics. He proposed that energy, long considered to be strictly a wave
phenomenon, could be shown to behave like particles in the form of very tiny, discreet
energy packets or bundles he called quanta (plural for quantum). Planck called this the
quantum theory and arrived at his conclusions (reluctantly) by studying the energy
radiated from heated solids. Planck developed the following equation for the energy
associated with each packet or quantum:
E = hν
where E = energy, ν = frequency, h = a very tiny proportionality constant (h = 6.626 ×
10–34J.s) called Planck’s constant. According to Planck, energy could only be absorbed or
emitted in whole numbers of quanta, that is, one quantum of energy (EE = hν), two quanta
(EE = 2hν), three quanta (EE = 3hν) and so on, but nowhere in between. Think of each energy
quantum as a glass marble in a bag of identical marbles (Figure 5.2.1). In the same way
that you could only ever add or remove a specific amount of glass from the bag in the
form of a whole number of marbles, so too could amounts of energy only be absorbed or
emitted in the form of whole numbers of quanta.

152 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 Figure 5.2.1 Quanta of energy are like marbles in bag. The marbles can only be removed as whole units.

At the end of the 1800s, the behaviour of waves and the behaviour of particles
were seen as very different and mutually exclusive. Waves were disturbances that moved
through space, could pass through and interfere with each other, and could have any
value within a range. Particles were objects with definite boundaries that bounced off
each other when they collided and could only exist in certain whole-number quantities.
A firm experimental and mathematical foundation supported the idea that waves were
fundamentally different from particles. To now suggest that waves could behave like
particles was almost sacrilegious! Planck himself wrote about his work: “By nature, I
am peacefully inclined and reject all doubtful adventures. …However, a theoretical
interpretation had to be found at any cost….I was ready to sacrifice every one of my
previous convictions about physical laws.”
Planck’s theory wasn’t taken very seriously at first. But in 1905, a 26-year-old
clerk in a Swiss patent office named Albert Einstein wrote five papers that changed
the scientific world forever. One of those papers used the quantum theory to explain a
phenomenon involving light called the “photoelectric effect” that had baffled physicists
until then. According to Einstein, the only way to make sense of the photoelectric effect
was to consider light as being composed of tiny discreet packets of energy. (These were
later called “photons” by American chemist Gilbert Lewis.) Einstein’s paper was the first
practical application of the quantum theory and as a result, the theory soon began to
gain widespread acceptance. In 1921, Einstein was awarded the Nobel Prize in physics for
his explanation of the photoelectric effect.

Quick Check
1. Briefly state what it means for something to be a “quantized.”
_______________________________________________________________________

2. Give three common examples of things considered to be “quantized.”

_______________________________________________________________________

3. According to Planck, could an amount of energy equal to 2.5hν

hν be absorbed or emitted by an object?
Explain.
_______________________________________________________________________

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 153
 One of the scientists who paid particular attention to the work of Planck and Einstein
The Bohr Model was a young Danish physicist named Niels Bohr. As a young grad student, Bohr had met
Ernest Rutherford at the Cavendish Laboratory in Cambridge and then worked with
Rutherford at the University of Manchester. Bohr believed in the nuclear atomic model
and started to see a way to “save” it using the quantum theory. If energy was indeed
quantized and so could be seen to have only certain values and not others, perhaps the
energies associated with electrons orbiting the nucleus had similar restrictions.
Bohr was working on this idea at Rutherford’s laboratory in Manchester in 1912.
In the middle of his experiments and calculations, he returned to Copenhagen to get
married. He was so excited about his work that he managed to convince his new bride
to cancel their honeymoon and return to England with him. Soon thereafter, Niels Bohr
completed one of the most brilliant papers on atomic structure ever written. In doing so,
he managed to rescue Rutherford’s nuclear model of the atom.
Scientific theories are carefully constructed on a firm foundation of data gathered
from a multitude of meticulously documented, rigorously controlled, and perpetually
repeatable experiments. Bohr’s theory was no exception. In section 5.1, we discussed
the conduction of charges through gases in glass discharge tubes. Those experiments
in the later years of the 1800s not only led to Thomson’s discovery of the electron, but
also provided Bohr with valuable data for his ideas about the nature of those electrons in
atoms.

Bohr knew that when high voltage was applied across the electrodes of a sealed glass
Quantum Theory tube containing a gas such as hydrogen, the gas was heated and emitted light. As part
Rescues the Nuclear of his investigations, Bohr looked at this light through a spectroscope. A spectroscope
Model is a device similar to a prism, which separates the light into its component wavelengths.
When Bohr viewed the light from the heated hydrogen through the spectroscope, he
saw only a series of coloured lines against a black background, rather than a continuous
rainbow of colour. For hydrogen, the same pattern of four coloured lines was always
seen: a red, blue-green, blue, and violet line (Figure 5.2.3). For each gaseous element
used, a bright-line pattern unique to that element called a bright-line spectrum always
appeared (much like a bar code on a modern grocery item).
The phenomenon had mystified scientists. None could explain why only certain
colours of light, each corresponding to specific wavelength, frequency, and energy,
were emitted by the heated gases — until Bohr. Bohr realized that by applying quantum
principles to the behaviour of hydrogen’s lone electron, he could not only account for
the existence of the bright-line spectrum, but also save Rutherford’s nuclear model of the
atom.

410.1 433.9 486.0 656.1

Wavelength (nm)

Figure 5.2.2 Hydrogen’s bright-line spectrum

154 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 Bohr’s Postulates
Bohr’s postulates for hydrogen are summarized below:

1. The hydrogen atom had only certain allowed energy levels or stationary
states. Each of these states corresponded to a circular electron orbit of a fixed
size. The larger the allowed orbit, the greater the energy associated with it.
No other orbits existed in the atom. Each allowed energy state was given an
integer number “n” that Bohr called a quantum number with allowed values
that ranged from 1 to ∞ (i.e., n could equal 1, 2, 3…etc). The lowest energy
(smallest) orbit corresponded to the lowest allowed energy state called the
ground state and was designated as n = 1. The larger orbits of greater energy
were designated as n = 2, n = 3, n = 4, etc. and were said to be excited states.

2. As long as an electron moved in an allowed orbit or stationary state, the electron

(and therefore the atom) did not radiate or absorb energy.

3. The electron could only move from one allowed orbit to another if it absorbed or
emitted an amount of energy exactly equal to the energy difference between
the two orbits, ∆E. This meant that the hydrogen atom could only change from
one stationary energy state to another.

Postulate 1 employed Planck’s theory by quantizing the energies allowed for the
Bohr’s Postulates hydrogen atom (and thus the electron). Because only certain-sized orbits were allowed,
— Another Look the atom was restricted to existing in only certain energy states and not others. Think
of the electron as a ball on a staircase. Just as the ball can only rest on any particular
stair and so have only certain amounts of potential energy and not others, so too is the
electron restricted to only specific energies.
Postulate 2 meant that the nuclear model of the atom proposed by Rutherford
would not collapse as predicted. Although the postulate violated the laws of classical
physics, Bohr insisted that it must be true, even though he didn’t know why.
Postulates 1 and 3 explained the origin and nature of hydrogen’s bright-line
spectrum. An atomic spectrum could not be continuous (i.e., a complete rainbow of
colours) because an atom’s energy states could only be certain values and not others.
When a sample of hydrogen gas is heated in a discharge tube, the electrons in the
hydrogen atoms absorb sufficient amounts of energy to “jump” to larger orbits.
n=3 (In any one hydrogen atom, only one electron is involved, but in a sample
of the gas, the electrons of many hydrogen atoms are undergoing many
�E=hv transitions). Once in a higher energy orbit, any electron could then return to
n=2
a lower energy orbit by emitting a specific amount of energy corresponding
n=1 exactly to the difference between the higher and lower energy orbits (Figure
5.2.3). If the frequency of that emitted energy corresponds to any part of the
visible spectrum, then a bright line of that specific colour would be seen. Four
of hydrogen’s electron transitions emitted energy in the visible spectrum.
If an excited electron emits energy and drops to n = 2 from a higher
energy orbit, the wavelength of the emitted energy corresponds to a
Figure 5.2.3 When the electron moves to
particular colour of visible light. If an electron drops from n = 3 to n = 2, the
an inner energy level, it emits energy. energy difference between the two orbits (and therefore the energy emitted)

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 155
 corresponds to that of red light. Hence the red line appears in the emission spectrum. The
blue-green line results from an electron transition from n = 4 to n = 2, the blue line from
an electron transition from n = 5 to n = 2, and the violet line from an electron transition
from n = 6 to n = 2. This series of four bright lines in the visible spectrum is called the
Balmer series, named after the Swiss schoolteacher who first derived a mathematical
relationship between the lines in hydrogen’s visible emission spectrum (Figure 5.2.4).
Bohr’s model of the hydrogen atom was successful in explaining the mystery of
bright line spectra. His calculations and predictions worked for hydrogen and he even
calculated the radius of the orbit for hydrogen’s electron in its ground state. In 1922, Niels
Bohr was awarded the Nobel Prize in physics.

��������� ��� ��� ���

Hg

Ne

���

��������� ��� ��� ���

���

Figure 5.2.4 (a) The emission spectra of hydrogen, mercury, and neon; (b) The absorption spectrum of
hydrogen

The diagram on the left in Figure 5.2.5 shows the circular orbits Bohr envisioned for the
The Emission hydrogen electron and the transitions associated with the Lyman, Balmer, and Paschen
Spectrum of emission spectra. The diagram on the right shows that the energy differences between
Hydrogen — Two various stationary states (n) decrease as the energies of those states increase. The arrows
Views pointing down represent electrons falling to lower energy states and thus emitting
energy. Electrons absorbing energy could be indicated by arrows pointing up and would
represent absorption spectra.
Any electron transitions from an excited state down to n = 1 result in the emission
of energy in the ultraviolet region of the electromagnetic spectrum (the Lyman series).
Any transitions from excited states down to the third and fourth orbits result in energies
in the infrared region being emitted (the Paschen and Brackett series respectively).

156 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 Lyman series
nm (ultraviolet) Hydrogen atom electron transitions
94
m
95n

nm
n=7
n=6

97
m
n=5

3n
nm
10
122 n=4
m
656 n 486 nm
Brackett series
E(n) to E(n=4)
434 nm
n=1 n=3
410 nm Paschen series
187 Balmer series E(n) to E(n=3)
5 nm (visible)
n=2 n=2
12 Balmer series
82 E(n) to E(n=2)
nm
n=3
10
94
nm
n=4 Paschen series n=1
(infrared) Lyman series
E(n) to E(n=1)
n=5 n=6
Figure 5.2.5 The Lyman, Balmer, and Paschen emission series for hydrogen

Quick Check
1. Describe the appearance of hydrogen’s “bright-line” spectrum.
_______________________________________________________________________

2. Briefly indicate how electrons generate each visible line in hydrogen’s emission spectrum.
_______________________________________________________________________

_______________________________________________________________________

3. Which electron transitions in the emission spectrum generate lines in the UV region of the electromagnetic
spectrum?
_______________________________________________________________________

In 1885, a Swiss schoolteacher named Johann Balmer found an equation that was able
Using Some to determine the wavelengths of the lines in the visible portion of hydrogen’s emission
Simple Equations spectrum. Three years later, the Swedish physicist Johannes Rydberg derived an equation
(Extension) that could be used to calculate the wavelengths of all of hydrogen’s spectral lines.
This is worth mentioning because if a mathematical relationship exists for a natural
phenomenon, it usually means there’s a theoretical foundation waiting to be discovered.
Both Balmer’s and Rydberg’s equations were based on data, rather than theory. Neither
equation had any physical meaning in terms of atomic structure, but both worked.
The physical meaning was supplied by Niels Bohr. Bohr derived an equation for
the energy associated with the electron in each allowed orbit. He correctly predicted
the visible, ultraviolet, and infrared spectral lines in hydrogen’s emission spectrum by
calculating the energy differences between those stationary states.
Although a rigorous mathematical treatment of this material is not intended here,
we will present two equations that are quite straightforward. The first equation gives the

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 157
 change in energy ∆EE (energy of photon released) when an electron initially in a higher
energy orbit (with a higher quantum number nh) drops to a lower energy orbit (and so
with a lower quantum number n l).
∆EE = b (1/nl2 – 1/nh2)
where b is a constant with value of 2.18 × 10–18 J.
The second equation arises from the fact that, according to Planck’s equation,
the energy of this photon, ∆EE = hν. Because ν = c/
c/λ
/λ, we can replace ∆EE with hc/
hc/λ
/λ . Now
dividing both sides of the equation by hc yields:
1/ = b/hc (1/nl2 – 1/nh2)
1/λ
This equation allows us to solve for the wavelength λ of the spectral line we would
observe when the electron lost energy as it made the above transition.
The combination of the constants, b/hc, is itself a constant. Remembering that
Planck’s constant, h = 6.626 × 10–34J.s and that the speed of light, c = 3.00 × 108m/s, we
can combine these three constants to give b/hc hc = 1.097 30 × 107 m–1. Let’s use this to
calculate the wavelength of the spectral line we would see when hydrogen’s electron
made the transition from n = 4 down to n = 2.

Sample Problem — Calculating the Wavelength of Emission Spectral Lines

Calculate the wavelength λ (in nm) of the spectral line seen in hydrogen’s emission spectrum when hydrogen’s
electron falls from the fourth allowed orbit (n = 4) to the second allowed orbit (n = 2).

What to Think about How to Do It

1. Consider the equation: 1/λ = (1.097 30 × 107 m–1) (1/nl2 – 1/nh2)
1/ = (1.097 30 x 107 m–1)
1/λ
= (1.097 30 × 107 m–1) (½2 – ¼2)
(1/nl2 – 1/nh2)
The values of nl and nh are = (1.097 30 × 107 m–1) (0.1875)
given in the question: n = = 2.0574 × 106 m–1
4 and n = 2.
λ= 1 = 4.8604 × 10–7 m
2.0574 × 106 m–1
2. Convert this to
nanometers. 9
This value corresponds 4.860 × 10–7 m × 1.0 × 10 nm = 486.04 nm
m
exactly to the green
line seen in hydrogen’s
emission spectrum.

Practice Problem
1. Use equation ∆EE = b (1/nl2 – 1/nh2) and the value for b given above to calculate the energy released when an
excited hydrogen electron drops from the fourth allowed orbit (n = 4) to the second allowed orbit (n = 2).

158 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 5.2 Activity: Coloured Flames
CAUTION! This activity should only be done under a fume hood with the supervision of a qualified chemistry
instructor.
Question
1. How do the colours of flames produced when various metal chloride salts are heated in a Bunsen flame differ?
2. How does the light from each of those flames appear when viewed through a spectroscope?

Materials (per pair of students)

• samples of the various salts such as: KCl, LiCl, SrCl2, CuCl2, and CaCl2
• several clean inoculating loops
• bunsen burner
• spectroscope
Procedure
1. Moisten the end of an inoculating loop in clean water and dip the end into one of the solid chloride salts.
2. Darken the room and hold the end of the loop in the flame of a Bunsen burner and observe the flame colour
with your naked eye, and then through the spectroscope. Record what you see.
3. Repeat the procedure for each salt.
Results and Discussion
1. Record your results in the table below.

Tested Colour and Appearance in Spectroscope

2. When the flames are viewed through the spectroscope, did the light from those flames yield continuous spectra
or spectra displaying bright lines?

3. Some of the flame colours may have appeared similar. If so, did they appear as similar when viewed through the
spectroscope or were there obvious differences?

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 159
5.2 Review Questions
1. Explain the serious problem initially associated with 7. Briefly explain why hydrogen’s visible emission
Rutherford’s atomic model. spectrum does not resemble a continuous spectrum
or rainbow.

2. State Planck’s quantum theory in your own words.

8. Describe what you would expect to see if hydrogen’s

visible emission and absorption spectra were
superimposed upon each other.

3. Why was this theory not accepted by most physicists

at first?

9. Explain why, when hydrogen’s electron transitions

occur from excited states down to n = 1 or to n = 3,
no visible spectral lines are observed.
4. What finally convinced the scientific community
that Planck’s theory was credible?

10. Calculate the energy released when an excited

hydrogen electron returns from n = 5 to n = 2.
5. Explain how the work of Planck and Einstein
contributed to Bohr’s theory about electron
behaviour.

11. Calculate the wavelength of the spectral line seen

when the electron transition described in 10 above
6. State how Bohr’s theory “saved” Rutherford’s nuclear occurs, and use the wavelength to identify the
atomic model. colour of this line.

160 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
5.3 Beyond Bohr — The Quantum Mechanical Model of the
Atom (Extension)

Warm Up
1. How did Max Planck and Albert Einstein contribute to the development of Niels Bohr’s atomic theory?

2. State the main points of Bohr’s atomic theory in your own words.

Niels Bohr’s theory firmly established the concept of fixed atomic energy levels. Although
Particles Behaving there were a few fine details of hydrogen’s line spectrum that the theory couldn’t account
Like Waves for, his model of the hydrogen atom appeared very promising. Unfortunately, when
Bohr’s theory was applied to the line spectra of atoms having more than one electron, it
didn’t work at all. All attempts to modify the theory to make it work were unsuccessful. It
soon became clear that the atomic puzzle hadn’t yet been solved.
Bohr assumed that an atom had only certain allowable energy levels in order to
account for hydrogen’s observed line spectrum. However, that assumption was not
rooted in any physical theory. In other words, Bohr knew the energy levels had to be
there, but not why they had to be there. It appeared that a new theory containing some
bold ideas about the atom might be needed.
That new theory was eventually called quantum mechanics, and it had its
beginnings in 1923 with the ideas of a young French aristocrat. Louis de Broglie had
originally earned a degree in history and was trying to decide on a subject for his doctoral
thesis in physics. He had just learned that a professor in Missouri named Arthur Compton
had proven the existence of the light quanta (later called photons) proposed by Albert
Einstein. A fascinating idea occurred to de Broglie: If waves behaved like particles, could
it also be possible for particles to have wave properties? By proposing that matter was
wavelike, de Broglie was also suggesting a reason, or theoretical foundation, for an
electron’s fixed energy levels. To understand this reason, we must briefly discuss some
aspects of wave behaviour.

Consider a string of length L under tension fixed at both ends, such as a guitar string
Wave Behaviour (Figure 5.3.1). When the string is plucked, it begins to oscillate as a wave. As it oscillates,
only certain frequencies (and therefore wavelengths) are possible if the wave is to be
maintained. This stable or “standing” wave must have a wavelength ((λ) such that a whole
number (n)) of half-wavelengths ((λ/2) fit within the length L of the string. Any fractional
amount of half-wavelengths will cause the wave to break down by a process known as
destructive interference. Thus a stable wave can only exist if integral numbers of half-
wavelengths exist within the length L of the string. That is:
L = 1(
1(λ/2), L = 2(
2(λ/2), L = 3(
3(λ/2), L = 4(
4(λ/2), L = 5(
5(λ/2),…etc, or if:
L = n(λ
( /2), where n is a whole number: 1, 2, 3, 4,…etc.
(λ

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 161
 Any situation where n is not a whole number, such as 3.3, will result in the
wave breaking down. This means that there is a quantum restriction equal to λ/2 on
the maintenance of the wave. Unless 1, 2, 3, 4 or any whole number of quanta (half-
wavelengths) exists in the length of the string, no wave can be maintained.

Vibrating string Vibrating electron

n=3 wavelengths

n=1 L=1( �)
2
1 half-wavelength

n=2 L=2( �) n=5 wavelengths

2
2 half-wavelengths

n=3 L=3( �)
2
3 half-wavelengths

L=n( �) n=3.3 wavelengths

2 (not allowed)

Figure 5.3.1 Both for a guitar string and an electron, only certain wavelengths allow a standing wave to be
maintained.

Now imagine bending this string around and closing it into a circle representing an
electron orbit. De Broglie considered what the requirements would be for a stable orbit if
electrons did exhibit wave motion. He proposed that the only stable electron orbits were
those whose size, and corresponding energy, allowed for standing electron waves to be
maintained. Orbits of any other size would cause the electron wave to break down. Look
again at Figure 5.3.1:

A condition for maintenance of a A condition for maintenance of

standing wave within a string of a stable electron orbit: a circular
length L is a whole number n of standing electron wave.
half-wavelengths.

An important consequence of prescribing a wave nature to the electron is that it tells

De Broglie’s us why the energies of electrons in atoms are quantized. In his Ph.D. thesis, De Broglie
Equation derived an equation to calculate the wavelength of a particle. He did so by combining
two now-famous equations, one proposed by Albert Einstein and the other by Max
Planck.

According to Einstein: E = mc2 where E is energy, m is mass, and c is the speed of light
According to Planck: E = hν where E is energy, ν is frequency, and h is Planck’s constant
Note also that because c = λν, then ν = c/λ
Therefore: mc2 = hc/λ

162 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 De Broglie knew that any particle having a mass could never reach the speed of
light, so he replaced the value c with v to represent the velocity of a particle. This gave:
mv2 = hv/λ
Cancelling common terms yielded mv = h/λ and so h = mvλ
Re-written as: λ = h/mv

This is de Broglie’s equation and it is significant for several reasons:

• First, it tells us that any moving particle, whether it’s an electron or a baseball, has a
wavelength that we can calculate.
• Second, it shows us that a particle’s wavelength is inversely proportional to its mass: as
the mass of a particle decreases, its wavelength increases and vice versa.
• Third (and perhaps most important), because the value of Planck’s constant is so very
small (6.626 × 10–34J.s), virtually any particle big enough for us to see has a wavelength
so incredibly small that it can’t even be measured. However, particles with a mass as
small as an electron have wavelengths that are very significant.

We can demonstrate this by calculating the de Broglie wavelength for two particles, one
Calculating we are familiar with and another we are not. A 100-kmph major league fastball and a
Wavelengths hydrogen electron each have a wavelength (Figure 5.3.2). Using SI units, the baseball has
a mass of 0.120 kg and a velocity of 44.4 m/s. It thus has a wavelength λ given by:
6.626 × 10–34 J • s
λ= = 1.24 × 10–34 m
(0.120 kg)(44.4 m/s)

Figure 5.3.2 All moving particles, large (a baseball) or tiny (an electron), have a wavelength that can be
calculated.

To put this wavelength into perspective, consider that a hydrogen atom has a
diameter of approximately 2.4 × 10–10 m. That means the baseball’s wavelength is not
only far smaller than the baseball, it’s also about 1024 times smaller than the smallest
atom! Of course, no instrument can measure anything that small, and this result tells us
that a baseball’s particle nature is virtually all there is. That makes sense to us because
“large” objects that we can see and that our frame of reference, personal experience, and
common sense tell us are particles behave precisely the way we expect them to — like
particles. Such objects don’t pass through each other or create diffraction or interference
patterns, and they certainly don’t cancel themselves out. So obviously, to concern
ourselves with a wave nature that is so insignificant would be ridiculous.
Now let’s calculate the de Broglie wavelength for a much more elusive particle
such as hydrogen’s electron. The electron has a mass of 9.11 × 10–31 kg and an estimated

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 163
 velocity of approximately 0.7% the speed of light, which works out to 2.2 × 106 m/s. De
Broglie’s equation therefore yields:
6.626 × 10–34 J • s
λ = (9.11 × 10–31 kg)(2.2 × 106 m/s = 3.3 × 10–10 m

Although this is certainly a small wavelength, it is 1.5 times larger than the
hydrogen atom itself and therefore represents a significant aspect of the electron’s nature.
Imagine yourself shrinking down and entering hydrogen’s nucleus. Looking out from that
nucleus at the electron, you might see a wave rather than a particle!

If the wave nature of electrons is so prominent, should we expect them to behave as

Particle-Wave other waves do? Should they produce diffraction patterns, be able to pass through each
Duality other, interfere with each other, and even cancel themselves out? As bizarre as it sounds,
the answer is yes!
The answer sounds bizarre because we have no experience with particles or waves
on the scale of the atomic or subatomic. In that world, where masses and distances are
so small, neither particles nor waves behave the way we expect them to. In fact, the
distinction between particles and waves doesn’t even exist in that tiny realm. In the
macroscopic world of large objects, we have either particles or waves, but in the quantum
world, they are the same thing!
Many in the scientific community, including Niels Bohr, were initially skeptical about
particles also being waves. Then, in 1927, Clinton Davisson and Lester Germer working
at Bell Labs in the United States confirmed that electrons did indeed behave like waves.
A beam of electrons directed at a nickel crystal generated a diffraction pattern similar
to that produced by electromagnetic waves such as X-rays. This proved de Broglie’s
hypothesis and brought the theory of dual-nature full circle. Not only did waves behave
like particles, but particles behaved like waves. Particle-wave duality set the stage for a
very strange proposal soon to come about the nature of electrons.
In 1929, Louis de Broglie won the Nobel Prize in physics. The Swedish physicist
who introduced him at the ceremony in Stockholm said, “When quite young, you threw
yourself into the controversy raging around the most profound problem in physics. You
had the boldness to assert, without the support of any known fact, that matter had not
only a corpuscular nature, but also a wave nature. Experiment came later and established
the correctness of your view.”

Quick Check
1. What important concept concerning atomic structure was Bohr’s theory responsible for?
_____________________________________________________________________

2. Why did Bohr’s atomic model need to be replaced?

_____________________________________________________________________

3. If particles have a wave nature, why can’t we detect that behaviour in the “big” macroscopic world?
_____________________________________________________________________

_____________________________________________________________________

164 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 Sample Problem — Using de Broglie’s Equation
Use de Broglie’s equation to calculate the wavelength of an M4 carbine rifle bullet having a mass of 4.1 g traveling
at 884 m/s.

What to Think about How to Do It

1. Remember that you should expect this
wavelength to be very small given the relatively
large mass of the α-particle.

2. Use de Broglie’s equation: h/mv λ = h

Make sure to convert km/s into m/s to do the
mv
calculation, and write the units for joules as
kgm2/s2.
6.626 × 10–34 J • s = 1.8 × 10–34 m
= (0.0041 kg)(884 m/s)
3. Express all quantities in scientific notation and
pay attention to significant figures in your final
answer.

Practice Problems — Using de Broglie’s Equation

1. Calculate the de Broglie wavelength of an α-particle having a mass of 6.64 × 10–27 kg travelling at 16 000 km/s.

2. Calculate how fast the carbine rifle bullet in the sample problem above would have to travel to have a de
Broglie wavelength equal to that of green light — approximately 486 × 10–9m .

3. Andy Roddick holds the record for the fastest tennis serve at 240 km/h. Calculate the de Broglie wavelength of
a tennis ball with mass of 56 g travelling at 240 km/h.

As mentioned earlier, not everyone was comfortable with the idea that electrons could
Heisenberg, be both a particle and a wave. Around 1925, two competing mathematical theories
Schrödinger, and existed that attempted to explain and predict electron behaviour. Werner Heisenberg, a
Orbitals young German physicist, developed “matrix mechanics,” which involved complicated and
difficult equations. It treated the electron as a pure particle with quantum behaviour.

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 165
 An Austrian physicist named Erwin Schrödinger rejected the idea of an electron as
a particle. He decided to view the electron mathematically as a pure wave to eliminate
some of the strange quantum aspects of electron behaviour. In his “wave mechanical”
description of the electron, Schrödinger used an equation to describe the electron as a
“wave function.” The math was easier than the matrix approach, and the wave equation
was popular with many physicists.
Each of the two scientists believed that his interpretation was correct, yet neither
seemed able to sufficiently predict the mysterious comings and goings of electrons.
Within a year, it became clear that matrix and wave mechanics were actually different
ways of getting to the same answers. Soon Heisenberg and Schrödinger became crucial
contributors as quantum mechanics was eventually united into one theory.
Figure 5.3.3 Erwin
Schrodinger

In June of 1925, while teaching at the University of Gottingen, Heisenberg suffered a

Heisenberg’s severe hay fever attack and took a leave of absence to an isolated island in the North
Principle Sea. During his stay, he focussed on the problem of electron measurement. After much
thought, he came up with one of the most important principles of modern physics.
Heisenberg identified a fundamental uncertainty associated with measuring any particles.
He called it the uncertainty principle. In the form of a simple equation, the principle
stated that it was impossible to know exactly both where any particle was located and
where it was going at the same time. Furthermore, the more certain you became of one
measurement, the less certain you were of the other.
Much like de Broglie’s hypothesis, the equation for the Heisenberg uncertainty
principle appeared quite straightforward, but the ramifications were enormous! The
principle can be written this way:
(m∆v)(∆x
)(∆xx)) ≥ h/2π
)(∆x
where m = mass of a particle, ∆v = uncertainty in velocity of a particle, ∆ ∆xx = uncertainty
in the position or location of a particle, and h = Planck’s constant. Think of the symbol
∆ as representing the “plus or minus value” or the “spread of results” in the velocity and
location.
The equation shows that the uncertainty in where a particle of constant mass is
Figure 5.3.4 Werner going (∆v)
vv)) multiplied by the uncertainty in where a particle is located (∆
(∆xxx)) is greater
Heisenberg than or equal to a very tiny constant (h/2π). This means that the two values are inversely
related.
The equation tells us that as we become more certain about an object’s position ∆ ∆x
decreases. As ∆ ∆xx decreases, the uncertainty in where the object is going, ∆v, vv, increases and
vice versa. This certainly isn’t our experience in the world of large objects. For objects big
enough to see, such as cars and baseballs, it’s easy at any point in time to say both where
they are and where they’re going. If it wasn’t, then the world of large moving objects
would be a very dangerous place to live! But the world at the atomic scale is much less
cooperative.
Once again, a similarity to de Broglie becomes evident as we see an inverse
relationship involving Planck’s constant. And once again, the fact that the constant is so
incredibly small means that the uncertainty principle only matters on an atomic scale.

166 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 The key to understanding this principle at the atomic level is to ask ourselves how we
Seeing and “see” anything. To locate any particle of matter, whether it’s a baseball or an electron,
Measuring we must somehow illuminate it. We see things, whether they are big or small, because
light energy in the form of photons bounces of those objects, is collected and eventually
interpreted by our brain or by instruments.
For example, suppose we were given a flashlight and told to locate a baseball
thrown into a dark room. No problem; we simply turn on the flashlight and immediately
know where the ball is and where it’s going. Of course the countless photons striking the
baseball have no measurable effect on it because of the ball’s large mass. But what if we
used an atomic bomb to supply the energy to illuminate the baseball? Obviously that
amount of energy would blow the ball (and the room and building) away so that nothing
meaningful concerning its position or motion could be known.
“Seeing” an electron also requires that some form of illuminating radiation bounce
off of the electron, and there lies the problem. Because the mass of an electron is so
unimaginably small, even the energy of one photon striking the electron is more than
enough to blow it away in much the same way that the bomb would blow away the
baseball. Stated another way, for quantum systems, the very act of measuring something
causes a significant change in what we’re measuring. This applies to any measuring
method we know. So if Heisenberg was right, then finding electrons and predicting their
behaviour with certainty isn’t only difficult, it’s impossible!

The obvious question is how can we then describe electrons in atoms at all? The answer
Schrödinger’s comes in the form of a compromise from Schrödinger’s wave equation. The equation
Equation is complicated and we needn’t worry about solving it here, but what it tells us about
electrons is important. Schrödinger represented the electron as a wave function he called
ψ (Greek letter psi).
The wave function is obtained by solving the equation using the allowed energy
states associated with electrons in atoms. Its square, ψ2, gives the probability of finding
those electrons within a region of space around the nucleus. The regions in which there
is the highest probability of finding electrons are called atomic orbitals. So atomic
orbitals represent those regions in three-dimensional space around a nucleus where
electrons with a particular energy are most likely to be found. We can view an orbital
as a probability volume or a “charge cloud” representing a 3D picture of where we will
probably encounter electrons around the atom’s nucleus. For different allowed energy
states, different numbers and types of orbitals exist. We will discuss these in the next
section.
So it seems that probability is woven into the fabric of matter at its most basic level
and many scientists, including Albert Einstein, resisted this idea. One of Einstein’s most
famous statements regarding his objection to the uncertainty principle was, “God does
not throw dice.”
Note the difference between Bohr’s electron orbit and an electron orbital. No
evidence exists that electrons follow a particular path around the nucleus, and Bohr’s
atomic model of a negative particle in a specific orbit has been abandoned. Rather,
quantum mechanics describes electron behaviour using the mathematics of waves to
determine the probability of finding an electron around the nucleus. This is an orbital.
Werner Heisenberg was awarded the Nobel Prize in 1932 and Erwin Schrödinger
received the honor the following year for their contributions to quantum mechanics.

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 167
 At this point, it’s valuable to summarize the three important aspects of the quantum
mechanical view of the atom.

1. The energies of electrons in atoms are quantized because of their wave nature.
This relates to the idea that only certain allowed energy states associated with
standing electron waves can exist.

2. The Heisenberg uncertainty principle states that it is impossible to

simultaneously state both where an electron is and where it’s going.

3. Atomic orbitals are those regions in 3D space around a nucleus where electrons
with a particular energy are most likely to be found.

Quick Check
1. How did Heisenberg and Schrödinger see the electron differently?
_____________________________________________________________________

2. According to quantum mechanics, how can “throwing dice” apply to describing electron behaviour?
_____________________________________________________________________

_____________________________________________________________________

3. Contrast Bohr’s electron orbit with the quantum mechanical electron orbital.
_____________________________________________________________________

_____________________________________________________________________

168 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 5.3 Activity: Uncle Werner says, “Consider This”
Question
Why must the Heisenberg uncertainty principle be considered when discussing quantum systems?
Procedure
Consider the following two scenarios and answer the questions below each one.
Scenario 1
Student A and student B are each given identical laboratory thermometers. They are asked to measure the
temperature of the water in a large heated swimming pool as accurately as possible. The water temperature is
approximately 35°C. Each thermometer reads 25°C before the measurement.

Student A lowers the thermometer bulb into the water in the pool. She waits for the reading to stabilize and then
records the temperature.

Student B places 5 mL of pool water into an insulated test tube and then places the thermometer in the test tube.
He waits for the reading to stabilize and then records the temperature.

Which reading will more accurately reflect the water temperature in the pool and why?
Scenario 2
Student A and student B are each blindfolded, given a hockey stick, and placed in identical airplane hangars.
Somewhere in the hangar where student A is standing is a school bus. Somewhere in the hangar where student B is
standing is a small balloon floating at eye level. The students are told to find the object in their hangar by swinging
their hockey stick as fast as they can until they hit that object. As soon as they find it, they must stop at the place
where they encounter the object.

Which student’s final position will more accurately reflect the final location of the object they are looking for and
why?
Record and Discussion
1. Use the above scenarios and your answers to the questions to make a general statement about why the
Heisenberg uncertainty principle cannot be ignored when discussing quantum systems.

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 169
5.3 Review Questions
1. How were the Bohr and de Broglie pictures of the (b) Explain what Einstein’s reference to throwing
electron different? dice represents.

2. How did de Broglie’s hypothesis suggest a reason for 9. Suggest a reason why we can ignore Heisenberg’s
the allowed energy states of electrons in atoms? uncertainty principle when locating macroscopic
objects such as cars and baseballs.

3. Why can wave-nature be ignored when describing

the behaviour of macroscopic particles?

10. Consider the de Broglie wavelengths for a 100 kmph

4. Why must wave nature be considered when fastball and a hydrogen electron calculated earlier
describing the behaviour of particles as small as in this chapter. How fast would the baseball have to
electrons? travel to have a wavelength equal to the hydrogen
electron? (Hint: replace the baseball’s wavelength
with that of the electron and solve for velocity, v.)
5. Complete the following statements:
As a particle’s mass increases, its wave nature
_________________ (increases or deceases).

As a particle’s mass decreases, its wave nature

_________________ (increases or decreases).
11. State a major contribution that the following
6. How can de Broglie’s theory be seen as the opposite scientists made to our understanding of the atom by
of Planck’s quantum theory? writing one sentence for each:

(a) Niels Bohr

7. What do the two theories of Max Planck and

Louis de Broglie, taken together, mean about the
existence of pure particles or pure waves? (b) Louis de Broglie

8. Consider the following quote from Albert Einstein: (c) Erwin Schrödinger
“Quantum mechanics is very worthy of regard, but
an inner voice tells me that it is not the ‘true Jacob’…
In any case, I am convinced that He does not throw
dice.” (d) Werner Heisenberg
(a) To whom was Einstein referring by “He”?

170 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
5.4 Applying Quantum Mechanics to Electrons in Atoms

Warm Up
1. What part of Bohr’s theory remains as part of the quantum mechanical view of the atom?
________________________________________________________________________________________
2. Quantum mechanics replaces the concept of an electron orbit with an orbital. What is an electron orbital?
________________________________________________________________________________________
3. The laws of probability are a necessary part of describing electron behaviour. Why?
________________________________________________________________________________________

In this section, we will apply the quantum mechanical model of the atomto describing
Starting with electrons in the atoms of the elements. We will begin with hydrogen and then use that
Hydrogen — information to expand our discussion to include multi-electron atoms.
One on One In section 5.3, the analogy of a guitar string helped to explain the requirement
of standing waves for the allowed energy states of electrons in atoms. If we solve
Schrödinger’s wave equation for the allowed energy states for hydrogen, we see that each
energy state results in different numbers and types of orbitals. The equation shows us
that the higher the energy, the greater the number and types of orbitals present.

In an atom, these three-dimensional electron waves or orbitals are more complicated

Quantum Numbers than a standing wave on a guitar string. To describe them, quantum mechanics employs
the use of special numbers called quantum numbers Each quantum number specifies
something different about the orbitals and electrons. We will discuss these numbers as
we investigate the orbitals associated with each of allowed energy states for hydrogen.

The Principal Quantum Number (n)

The first quantum number is called the principal quantum number (n). It indicates
the relative size of the atomic orbital.

We have already been introduced to this number because it also represents the
allowed energy states for the electron. We know that the value of n can be a positive
integer (1, 2, 3, and so on).
When hydrogen’s electron is in the lowest allowed energy state or ground state,
then n = 1. Schrödinger’s equation shows us where an electron possessing that amount
of energy will most likely be found. When we represent this pictorially, we see an electron
“probability density diagram” resembling a spherical cloud. The cloud is what you might
see if you could take many snapshots of the hydrogen electron around the nucleus and
then superimpose all of them onto one picture. At the centre of this cloud is the hydrogen
nucleus. The cloud’s density is not uniform throughout, but is greater near the nucleus

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 171
 and decreases as we move away. This tells us that the probability of locating the electron
is higher closer to the nucleus and lower further away from the nucleus.
As we move out from the nucleus, we find that hydrogen’s electron in its ground
state is likely to spend most of its time a slight distance from the nucleus, rather than
at the nucleus itself. This is called the “radial probability.” It’s interesting to note that the
electron’s distance from the nucleus to the region of highest probability corresponds
exactly to the orbit for this electron that Bohr calculated. Remember, however, that Bohr
assumed the electron followed a circular path and would always be found at that distance
from the nucleus. Quantum mechanics describes this as the most probable distance from
the nucleus for the electron.
When we enclose the cloud in a volume representing about a 90% probability of
finding the electron, we call this the 1s orbital. The number “1” represents the principal
quantum number, telling us the size of the orbital, and the letter “s” refers to the type or
“shape” of the orbital. Figure 5.4.1(a) shows an artistic representation of what a spherical
1s orbital might look like if viewed from the outside. Figure 5.4.1(b) is a cross-sectional
view showing radial probability (indicated by greater dot density a slight distance from
nucleus).

(a) (b)

Figure 5.4.1 (a) A view of a spherical 1s orbital from the outside; (b) A cross-sectional view of a spherical
1s orbital

The Second Quantum Number (l)

The second quantum number is called the angular momentum quantum number
(l). It is related to the shape of an atomic orbital.

The different values of l at each energy level represent the number of orbital shapes or
sublevels that exist in that energy level. That number equals the energy level itself. So for
n = 1, there is only one orbital type or shape, namely the s orbital.
Each new energy level has one new orbital shape in addition to those existing in the
previous level. So if hydrogen’s electron is “excited” and absorbs enough energy to reach
the second allowed energy state, then n = 2 and two orbital shapes or sublevels exist.
There is an s orbital with a shape identical to the 1s, except larger, called the 2s orbital.
This means that the electron with this greater amount of energy will spend more of its
time farther from the nucleus. There is also a new shape: a p orbital. As n = 2, we call it a
2p orbital and it resembles a dumbbell or long balloon pinched in the middle (where the
nucleus is located).

172 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 The Third Quantum Number (ml)

The third quantum number, called the magnetic quantum number (ml) tells us the
orientation in space of a given atomic orbital.

The number of possible different orientations in space for any orbital shape also
represents the number of individual orbitals of that particular shape or sublevel.
Only a single s orbital exists in any given energy level because a spherical cloud
can only have one orientation in 3D space. However, this new p sublevel includes three
separate orbitals, each with a different spatial orientation. If we consider a 3D set of
Cartesian coordinates, one is oriented along an imaginary xx-axis (with the nucleus at the
origin) called a 2px orbital. The other two are oriented along the y- and z-axes and are
called the 2py and 2pz orbitals respectively. Each of these 2p orbitals is identical in energy
to the others. For hydrogen, they are also identical in energy to the 2s orbital. Chemists
call orbitals of equal energy “degenerate” orbitals.
In Figure 5.4.2, note that the lobes of each p orbital in the first three diagrams
disappear at the origin where the nucleus is located. This means that the amplitude of
the electron wave at the nucleus is zero. A wave amplitude of zero is called a node, and it
tells us that there is a zero probability of locating the electron here. In the far left diagram
in Figure 5.4.2, all three 2p orbitals are shown together. Once again, the nucleus is at the
centre or origin.

y y y Py

z z z
Pz
x x x
Px

2px orbital 2py orbital 2pz orbital

Figure 5.4.2 The p orbitals are each shown individually in the first three diagrams. The last diagram shows
them all together.

We noted earlier that the number of different sublevels in any energy level equals
the value of n. We also see here that a total of four orbitals exists in the second energy
level. So the value n2 tells us the number of orbitals existing in the nth energy level. In this
case, there are 22 = 4 orbitals: one 2s and three 2p orbitals.
The three quantum numbers, taken together, will always specify a particular atomic
orbital because they tell us all we need to know about that orbital: its size, shape, and
orientation in space.
If hydrogen’s electron absorbs enough energy to reach the third allowed energy
state, then n = 3 and three different orbital shapes or sublevels exist. As expected, we
see one spherical 3s orbital and three dumbbell-shaped 3p orbitals. But we also discover
a third sublevel whose orbitals have a more complicated shape. This is called the 3d
sublevel and it contains five different orbitals, each with a different spatial orientation.
Orbitals in a given sublevel are equal in energy to each other, and in hydrogen’s case, are
also equal in energy to all of the other orbitals in the energy level. This means that in a
given energy level, hydrogen’s electron has an equal likelihood of occupying any of them.
Although the d orbitals are shown in Figure 5.4.3, you may not be required to
remember either their shapes or their names. You should, however, know that there are
five of them.

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 173
 z z z

y y y
x x x
dyz dxz dxy

z z

y y
x x
dx2-y2 d z2

Figure 5.4.3 The d orbitals

Notice that as n = 3, there are three sublevels: 3s, 3p, and 3d. Also, there are a total
of nine orbitals: one 3s orbital, three 3p orbitals, and five 3d orbitals corresponding to 32.
Finally, let’s elevate hydrogen’s electron to the fourth energy level, where n = 4. A
higher energy level means that the electron will spend more of its time farther from the
nucleus than when it possesses energy equal to n = 1, 2, or 3. Therefore, the orbitals or
“charge clouds” are larger.
In the fourth energy level, we see the expected 4s, three 4p, and five 4d orbitals. As
well, because n = 4, we also see a fourth shape called the 4f sublevel. Each higher energy
level introduces another sublevel with a greater number (by two) of more complicated
orbitals than the previous ones, and so there are seven 4f orbitals, each with a more
complicated shape than the d orbitals. You should remember the number of f orbitals as
well. The fourth energy level results in 42 = 16 orbitals: one 4s, three 4p, five 4d, and seven
4f orbitals, all of which are equal in energy in the case of hydrogen.
Let’s summarize what we have learned about energy levels and orbitals using a
table and a diagram. Table 5.4.1 shows the sublevels and orbitals for the first four energy
levels. Figure 5.4.4 is the energy diagram for hydrogen showing the sublevels and orbitals
present from n = 1 through n = 4. Each circle represents an orbital. Note that all the
sublevels are of equal energy in each allowed energy state.

Table 5.4.1 Sublevels and orbitals for the first four energy levels

Principal Quantum Number of Orbital Total Number

Number or Shapes or Sublevels of Orbitals per
Energy Level (n) per Energy Level (n) Energy Level (n2)
1 1 – 1s sublevel 1 – the 1s orbital
2 2 – 2s sublevel 4 – one 2s orbital
2p sublevel three 2p orbitals
3 3 – 3s sublevel 9 – one 3s orbital
3p sublevel three 3p orbitals
3d sublevel five 3d orbitals
4 4 – 4s sublevel 16 – one 4s orbital
4p sublevel three 4p orbitals
4d sublevel five 4d orbitals
4f sublevel seven 4f orbitals

174 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 4s 4p 4d 4f

3s 3p 3d

energy
2s 2p

1s

Figure 5.4.4 Energy diagram for hydrogen. Each circle represents an orbital

Quick Check
1. State what each of the three quantum numbers described above tells us about atomic orbitals.
_______________________________________________________________________
_______________________________________________________________________

2. (a) What is the difference between a 1s and a 2s orbital?

_______________________________________________________________________

(b) What is the difference between a 2px orbital and a 2py orbital?
_______________________________________________________________________

3. How many different orbitals are available to an excited hydrogen electron in the fourth energy level?
_______________________________________________________________________

Hydrogen is the simplest atom with one proton in the nucleus surrounded by one
The Orbitals of Multi- electron in a 1s orbital in its ground state. There are no electron-electron interactions, and
Electron Atoms in any excited state, all of the atomic orbitals available to that single electron are of equal
energy.
We might expect a different situation, however, for multi-electron atoms. Electrons
are charged particle-waves. It seems reasonable to conclude that they will affect each
other when two or more of them occupy the same region of space around an atom’s
N e- S
nucleus — and they do.
To describe those electrons in multi-electron atoms, we must introduce several
1
ms = + additional considerations.
2
Experiments have shown that the single electron in hydrogen generates a tiny
magnetic field as if the electron were a spinning charge. Also, in any sample of hydrogen,
e- N analyzing the many atoms present shows two opposing magnetic fields. This tells us that
S
in half of the atoms, the electrons seem to spin in one direction and, in the remainder of
the atoms, in the other direction. An electron’s spin is as fundamental a part of its nature
1
ms = – as its charge.
2

Figure 5.4.5 The spin

quantum number (ms) The fourth quantum number is called the spin quantum number (ms). It tells us the
identifies which possible spin two possible electron spins, either +½ or –½.
and electron has.

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 175
 We already know that we can identify any orbital in an atom by the use of the first three
The Pauli Exclusion quantum numbers, but we must use all four quantum numbers mentioned to specify any
Principle electron in an atom.
This is based on the fact that any atomic orbital can hold a maximum of two
electrons. When two electrons are in the same orbital, their spins must be opposite.
Originally proposed in 1925 by the Austrian physicist Wolfgang Pauli, this can be viewed
as the first rule governing electrons in multi-electron atoms.

1. The Pauli exclusion principle: No two electrons in the same atom can be
described by the same set of four quantum numbers.

If two electrons are in the same atomic orbital, they therefore have the same first
three quantum numbers. Because they then must have opposite spins, their fourth
quantum numbers are different.

We noted earlier that the total number of orbitals existing in any level n equals n2.

If two electrons can occupy each orbital, the maximum number of electrons that can
exist in any energy level n is given by 2n2 .

A further consideration for multi-electron atoms is the effect of electron-electron

repulsions on the relative energies of the sublevels in a given energy level. For hydrogen,
where no repulsive forces exist, all of the sublevels in any energy level have identical
energies. This is not the case for atoms of other elements. Although the same types of
orbitals exist in multi-electron atoms, their relative energies are different. Repulsive forces
cause a sublevel with a greater number of orbitals to have a greater energy. Therefore the
order of sublevel energies is:
s < p < d < f.
Consider Figure 5.4.6. Compare this energy diagram for a multi-electron atom with
Figure 5.4.4 for hydrogen. Note that in several cases energies get closer together as n
increases. In these cases, repulsive forces are such that some sublevels containing smaller
orbitals actually have higher energies than some larger orbitals. For example, observe the
relative energy of the 3d compared to the 4s sublevel.

4f 4f
6s 6s
5p 5p
4d 4d
5s 5s
increasing energy

4p 4p
3d 3d
4s 4s

3p 3p

3s 3s

2p 2p

2s 2s

1s 1s

Figure 5.4.6 Energy diagram for multi-electron atoms

176 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 Quick Check
1. What does the fourth quantum number tell us about electrons?
_______________________________________________________________________

2. Why can’t two electrons in the same atom have the same four quantum numbers?
_______________________________________________________________________

3. What is the maximum number of electrons that can exist in the energy levels n = 1 through n = 4?
_______________________________________________________________________

We are now in a position to organize electrons into orbitals for the atoms of the elements.
Electron Understanding this organization will prove to be a powerful tool as we discuss the
Configurations and periodic table and bonding in the next chapter. In beginnning this process, we introduce
Orbital Diagrams the second rule associated with describing electrons in multi-electron atoms.

2. The Aufbau principle: When filling orbitals, the lowest energy orbitals available
are always filled first. (“Aufbau” means a building or a construction in German.)

The order for filling orbitals is given above in Table 5.4.1, showing sublevel energies.
We start at the lowest energy orbitals and move up.
Let’s begin with hydrogen. In its lowest energy or ground state, hydrogen’s electron
exists in the 1s orbital. We can represent this in two ways:
1. We can use a shorthand notation called an electron configuration, which is written
in the format nl# showing the energy level, sublevel, and number of electrons
respectively. Hydrogen’s electron configuration is therefore written as: 1s1. Read as
“one s one,” this tells us that hydrogen’s one electron resides in the 1s orbital in its
ground state.
2. We can construct an orbital diagram, which depicts electrons and their spin
using arrows facing up and down. The arrows are placed inside boxes or over lines
representing individual orbitals in sublevels. Hydrogen’s orbital diagram is shown as:

↑
1s
The configuration for the next element, helium, is 1s2. This is read “one s two” rather
than “one s squared.” Following the Pauli exclusion principle, the orbital diagram shows
the two electrons with opposite spins in the now full 1s orbital:

↑↓
1s
To indicate increasing sublevel energy, the boxes can be written vertically or also
left to right to save space on a page. Let’s continue below by moving past helium to the
elements in period 2 of the periodic table using horizontally written orbital diagrams.

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 177
 Note that period 2 corresponds to the second energy level, n = 2. Following the Aufbau
principle:

Electron Orbital Diagram

Configuration INCREASING ENERGY

1s 2s 2p

lithium 1s2 2s1 ↑↓ ↑

beryllium 1s2 2s2 ↑↓ ↑↓

For the 2p sublevel:

↑↓ ↑↓ ↑
boron 1s2 2s2 2p1

Note that the sum of the superscript numbers equals the total number of electrons
present.
We must now use the third rule governing orbitals in multi-electron atoms:

3. Hund’s rule: When orbitals of equal energy are being filled, the most stable
configuration is the one with the maximum number of unpaired electrons with
the same spin.

So carbon and nitrogen’s orbital diagrams are:

↑↓ ↑↓ ↑ ↑
carbon 1s2 2s2 2p2

↑↓ ↑↓ ↑ ↑ ↑
nitrogen 1s2 2s2 2p3

After nitrogen, we must again begin to pair electrons:

↑↓ ↑↓ ↑↓ ↑ ↑
oxygen 1s2 2s2 2p4

↑↓ ↑↓ ↑↓ ↑↓ ↑
fluorine 1s2 2s2 2p5

↑↓ ↑↓ ↑↓ ↑↓ ↑↓
neon 1s2 2s2 2p6

After a noble gas, a new period begins in the periodic table and so too, a new
energy level. As we begin period 3, let’s represent the elements up to scandium in Table
5.4.2 using electron configurations only. We can condense electron configurations using
core notation, in which the configuration of the previous noble gas is represented by
that noble gas symbol in square brackets as shown in the table. Outer electrons are
indicated in bold type.

178 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 Table 5.4.2 Electron Configurations of Period 3 Elements up to Scandium

Element Full Electron Configuration Core Notation

sodium 1s2 2s2 2p6 3s1 [Ne] 3s1
magnesium 1s2 2s2 2p6 3s2 [Ne] 3s2
aluminum 1s2 2s2 2p6 3s2 3p1 [Ne] 3s2 3p1
silicon 1s2 2s2 2p6 3s2 3p2 [Ne] 3s2 3p2
phosphorus 1s2 2s2 2p6 3s2 3p3 [Ne] 3s2 3p3
sulphur 1s2 2s2 2p6 3s2 3p4 [Ne] 3s2 3p4
chlorine 1s2 2s2 2p6 3s2 3p5 [Ne] 3s2 3p5
argon 1s2 2s2 2p6 3s2 3p6 [Ne] 3s2 3p6
potassium 1s2 2s2 2p6 3s2 3p6 4s1 [Ar] 4s1
calcium 1s2 2s2 2p6 3s2 3p6 4s2 [Ar] 4s2
scandium 1s2 2s2 2p6 3s2 3p6 4s2 3d1 [Ar] 4s2 3d1

Notice in the table that, as we move from argon to potassium, the 4s sublevel starts
to fill before the 3d sublevel. After the 4s sublevel, the 3d sublevel starts to fill, reaching
the first transition metal, scandium. Although the 3d sublevel fills after the 4s sublevel,
the 3d sublevel still contains electrons that spend most of their time nearer the nucleus
and so is inside the 4s sublevel. Some periodic tables indicate the electron configurations
in order of sublevel size and so will show scandium’s configuration as [Ar] 3d1 4s2.
Figure 5.4.7 is a simple way of remembering the order for filling sublevels. We begin
at the top with the 1s and fill that sublevel. After reaching the end of each arrow, we then
start at the top of the next arrow below it. When using this diagram, you must remember
how many electrons each sublevel can hold.

1s
increasing energy

2s 2p
3s 3p 3d
4s 4p 4d 4f
5s 5p 5d 5f
6s 6p 6d
7s 7p

Figure 5.4.7 This diagram indicates the order for filling sublevels.

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 179
 Sample Problem — Drawing an Orbital Diagram
Draw the orbital diagram and write the full electron configuration and the core notation for an atom of cobalt in
its ground state.

What to Think about

1. Cobalt’s atomic number is 47 and so the orbital diagram must account for 47 electrons. Cobalt is a transition
metal in period 4 in the periodic table. We should expect the highest energy electrons to be in the 3d subshell.
2. Remember how many electrons are placed in each subshell as you fill the orbitals and employ Hund’s rule as
necessary.
3. Sketch the diagonal diagram to help you remember the order that subshells fill.
4. Represent each electron in an orbital using an arrow as in the notation described above.

How to Do It
Orbital diagram for cobalt: increasing energy

↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑ ↑ ↑

1s 2s 2p 3s 3p 4s 3d

Electron configuration: 1s2 2s2 2p6 3s2 3p6 4s2 3d7

Core notation: [Ar] 4s2 3d7 or [Ar] 3d7 4s2

Practice Problem
1. Write the full electron configuration and draw the orbital diagram for an atom of titanium in its ground state.

180 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
 Recall that a cation has fewer electrons than the original neutral atom and an anion has
Ions and Other more. This means that the electron configurations for ions will be different than those for
Charged Topics neutral atoms.
The process is easily shown using examples. To write the electron configuration
for the S2– anion, we simply need to add two more electrons to the last unfilled sublevel.
Thus the configuration: 1s2 2s2 2p6 3s2 3p4 for the S atom becomes: 1s2 2s2 2p6 3s2 3p6 for
the S2– anion. Notice that the sulphide anion now has the same electron configuration as
the nearest noble gas argon. The sulphide ion is therefore considered to be isoelectronic
with argon because the two species have the same number and configuration of
electrons.
To write cation configurations, electrons are always removed from the outermost
orbitals with the highest energy first. Therefore, it is sometimes worthwhile to first write the
neutral atom’s configuration in core notation with the final orbitals listed from smallest
to largest, rather than in the order the orbitals fill. Then remove the appropriate electrons
from the outer orbitals first.
For example, if asked to write the configuration for the Sn4+ ion, first write the
configuration for a neutral Sn atom as [Kr] 4d10 5s2 5p2 rather than writing [Kr] 5s2 4d10
5p2.
Now remove the four outermost electrons to give the configuration for Sn4+: [Kr]
4d . This avoids the error of removing two 4d electrons to give [Kr] 5s2 4d8. Note that an
10

Sn2+ ion would form by losing the two 5p electrons, as they are at higher energy than the
5s.
As a final note, there are several exceptions to the orbital filling order discussed
here. The elements Cr, Cu, Mo, Ag, and Au are examples of such exceptions. Your teacher
may choose to discuss these and others and the possible reasons.
We shouldn’t be surprised that irregularities exist. We have already seen ample
evidence that the quantum world is full of surprises!

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 181
 5.4 Activity: A Post-it® Periodic Table
Question
Can we organize a series of Post-it® notes on a standard periodic table to represent the order that orbitals are filled
according the Aufbau principle?
Materials
• a small pad of each of four different colors of Post-it® or other sticky notes
• transparent tape
Procedure
Refer to the diagonal diagram in Figure 5.4.7 showing the order for filling sublevels.

1. Obtain a pad of small Post-it® or other sticky notes. Choose a separate color for each of the four shapes, s, p, d,
and f, and write the symbol for each of the 19 sublevels (1s, 2s, 2p, etc....) on a separate note.

2. Place the notes from left to right on a flat surface in the correct order that each sublevel fills.

3. Obtain a blank copy of the periodic table from your teacher. Number each horizontal period of the table,
beginning with 1 for the top period containing H and He, down to 7 for Fr.

4. Now “read” the periods left-to-right like words on a page, moving down at the end of each.
Trim the bottom portion of each Post-it® note to fit, and stick the appropriate sublevel symbol onto each section
of each period as you read it.
Record and Discussion
1. Once you’re finished, confirm the correct location of each Post-it® note sublevel symbol with your teacher. Then
place transparent tape over each to permanently attach it to the periodic table. Save this completed table for
the discussion coming up in the next chapter.

182 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9
5.4 Review Questions
1. If hydrogen’s electron exists in a spherical orbital, why doesn’t this mean that the electron moves around the
nucleus in a circle?

2. What is the difference between a 1s orbital and a 2s orbital? What does that difference indicate about an electron
possessing energy equal to n = 2 as compared to n = 1?

3. Describe the two differences between a 2px orbital and a 3py orbital.

4. The lobes of a p orbital disappear at the nucleus. What does this tell us about electrons in p orbitals?

5. You may have heard in previous science classes that the maximum numbers of electrons that can exist in the first
four energy levels are 2, 8, 8, and 18 respectively. Do you agree with those numbers and if not, what should they
be?

6. The electron configuration for phosphorus, written in core notation, is [Ne] 3s2 3p3.
What two things does Hund’s rule tell us about the three electrons in the 3p sublevel?

7. Use the periodic table to complete the following table:

Atom or Ion Full Electron Configuration Core Notation

Ge
Zn2+
Sr
Br -
Sn
In3+

© Edvantage Interactive 2011 ISBN 978-0-9864778-2-9 Chapter 5 A Closer Look at Matter 183
8. (a) Use the periodic table to identify the neutral atoms having the following electron configurations:

Electron Configuration Element Name

[Ne] 3s2
[Ar] 4s2 3d5
[Kr] 5s2 4d10 5p3
[Xe] 6s2 4f 7

(b) Notice where each of these elements is located on the periodic table. Look at the highest energy sublevel being
filled (bold type) in each of the atoms in the table, and identify the four different sections of the periodic table
associated with each of these four sublevels.

9. Consider the following six stable ions: N 3–, O 2–, F–, Na+, Mg 2+, and Al 3+.
(a) How many electrons are present in each ion?

(b) Write a single electron configuration representing all of the ions.

(c) Which neutral atom possesses this electron configuration? What does this suggest about a possible reason for
some ion formation?

10. (a) Complete the following table for some elements in two families of the periodic table.

Alkali Metals Core Notation # Outer Electrons Halogens Core Notation # Outer Electrons
lithium fluorine
sodium chlorine
potassium bromine
rubidium iodine

(b) Consider the numbers of outer electrons present and suggest a reason why elements belonging to the same
chemical family demonstrate similar chemical behaviour.

(c) What change occurs in the atoms as we move down each chemical family?

11. (a) On a separate sheet of paper, draw an orbital diagram for an atom of iron with sublevel energy increasing
vertically. Arrange equal energy orbitals in each sublevel horizontally.

(b) Use a highlighter to label the electrons that would be lost when the Fe3+ cation forms.

184 Chapter 5 A Closer Look at Matter © Edvantage Interactive 2011 ISBN 978-0-9864778-2-9