Chapter IV. Atomic Structure and The PT 2 2

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Unit IV.

The Electronic Structure of the Atom and the Periodic Table

A. Unit IV: The Electronic Structure of the


Atom and the Periodic Table
Introduction
Our significant means of understanding an atom was brought about in the
20th century, from the proposal of Ernest Rutherford planetary model to Niels
Bohr’s application of quantum theory and waves to the behavior of electrons.
Electron configuration can be described as the arrangement of electrons within the
orbitals shells and subshells of an atom. It is important to understand the behavior
of an electron in atom in order to fully comprehend the electron configuration. An
electron is a subatomic particle that is associated with a negative charge.
Additionally, electrons are associated with energy, more specifically quantum
energy, and show wave-like and particle-like characteristics.
Fully understanding the principles relating to electron configuration will promote
a better comprehension of how to arrange them and give us a better understanding
of each element in the periodic table. The arrangement of the elements in the
periodic table has an especial correlation with electron configuration. After
studying the relationship between electron configuration and the period table, it
was pointed out by Niels Bohr that electron configurations are similar for
elements within the same group or family in the periodic table. Groups occupy the
vertical rows as opposed to a period which is the horizontal rows in the table of
elements. The periodic recurrence of similar properties of elements is one aspect
of periodicity. Another aspect consists of the trends of in the properties of
elements and their compounds.

Learning Outcomes
At the end of this unit you should be able to:

1. Describe and explain the light emitted by the atoms


2. Describe the quantum theory of light
3. Describe the Bohr’s Model of the Hydrogen Atom
4. Compare the Quantum Mechanical Theory of the atom with the Bohr
Model
5. Cite the significance of quantum numbers
6. identify quantum numbers of electrons in an atom
7. Apply the different principles in creating the orbital diagram of the
elements
8. Predict correctly the position of the elements in the Periodic Table using
its electronic configuration
9. Trace the development of the Periodic Table
10. Explain the factors that affect the periodic trends as to atomic size,
ionization energy, electronegativity and electron affinity of atoms

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

11. Determine the valence electrons and charge of the ion being formed
12. Compare and contrast the different properties of the elements in the
Periodic Table

13. To know the relationship between atomic spectra and the electronic
structure of atoms
14. Relate the electron configurations of the elements to the shape of the
periodic table.
15. Determine the expected electron configuration of an element by its place
on the periodic table.

Activating Prior Learning

How would you describe each of the following models of the atom:
- Billiard ball model
- Prout’s hypothesis
- Raisin bread model
- Nuclear model
- Planetary model

A. Atomic Spectra

Learning Objectives:

1. discuss the meaning of the term 'atomic spectrum'


2. distinguish between the two main types of atomic spectra: absorption and
emission spectra and describe how each forms

Let’s Learn

Have you ever wondered watching colorful lights produced from fireworks?
The spectacular colors of fireworks are produced by distinct kind of atom.
When atoms absorbed energy, they become excited they emit light of
certain wavelengths which correspond to certain color. The salts of the
following examples produce distinct color: yellow-orange color of sodium
atom, blue flame of copper, green color of barium, red for rubidium, etc.

The device that measures the spectrum of light, differentiating its


components is called the spectroscope. Although the apparatus Isaac
Newton used in his work on the spectrum of light can be considered a crude
spectroscope, it is generally recognized that the spectroscope was invented
by Gustav Kirchhoff and Robert Bunsen around 1860. We see white light at
daytime from the sun that seems colorless. However, when the light passed
through the slit and the prism of the spectroscope, the light is separates into

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

a very wide spectrum of colors like the rainbow (Figure 1). Light which has
been resolved into its components is called spectrum.

Prism R
O
Y
Star G
light B
I
V

Figure 4-1. Schematic diagram of a spectroscope Resulting spectrum

Light is commonly identified by its color, however a more accurately means


of identifying it is by its wavelength (λ) or its frequency (ν). Wavelength is
the distance between two adjacent crest (highest points) or two adjacent
troughs (lowest points) of the same wave. Figure 2 shows the schematic
diagram of the two waves. Frequency refers to an interval of time, during a
wave performs a full oscillation and returns to its original momentary state.

Figure 4-2. Comparison of Wavelength

Electromagnetic waves always travel at the same speed (3x108 m per second).
This is one of their defining characteristics. In the electromagnetic spectrum there
are many different types of waves with varying frequencies and wavelengths.
They are all related by one important equation:

wavelength x frequency of oscillation = speed of light

λν=c

where c = speed of light

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

We can use this relationship to figure out the wavelength or frequency of any
electromagnetic wave if we have the other measurement. Just divide the speed of
light by whichever measurement you have and then you’ve got the other.

Frequency is measured in units of Hertz, which is also cycles per second (cps) or
simply s-1. Thus 1 Hz = 1cps = s-1. If c is in ms-1 and is used in the above equation,
then the wavelength must be in meters. However, other common units of
wavelength are nanometers, nm and Angstrom, Å. The equivalents are given
below:

1 nanometer, nm = 10-9 meter, m


1 Angstrom, Å = 10-10 meters, m

4-1. Learning Check


Two microwave frequencies are authorized for use in microwave
ovens, 900 and 2560 MHz. Calculate the wavelength of each.

λ of 900 = ___________________________

λ of 2560 = __________________________

You should also take note that wavelength and frequency are inversely related.
The higher the frequency, the shorter the wavelength. Since all light waves move
through a vacuum at the same speed, the number of wave crests passing by a
given point in one second depends on the wavelength.

All electromagnetic radiation is light, but we can only see a small portion of this
radiation, the visible light (Figure 3). Cone-shaped cells in our eyes act as
receivers tuned to the wavelengths in this narrow band of the spectrum. Typically,
our eyes can detect wavelength from 380-700 nanometers.

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

Figure 4-3. The Electromagnetic Spectrum

4-2. Learning Check


Examine very well the wavelength and frequency of blue and
orange light.

a. Which color or light has the shortest wavelength?

b. Which color or light has the lowest frequency?

Light is a form of energy and the relationship between energy, frequency and
wavelength if expressed in the following equation:
E = hν = hc
λ
where: h = Planck’s constant = 6.626 x 10-34 J-s
You should understand that energy is directly proportional to frequency, but
inversely proportional to wavelength. The greater the energy, the larger the
frequency and the shorter (smaller) the wavelength. Given the relationship
between wavelength and frequency — the higher the frequency, the shorter the
wavelength — it follows that short wavelengths are more energetic than long
wavelengths.

4-3. Learning Check


Based from the electromagnetic spectrum, which color in visible
light has the lowest energy? highest energy?
Color with the lowest energy - __________________ 5

Color with the highest energy - __________________


Unit IV. The Electronic Structure of the Atom and the Periodic Table

The electrons in an atom tend to be arranged in such a way that the energy of the
atom is as low as possible. The ground state of an atom is the lowest energy state
of the atom. When those atoms are given energy, the electrons absorb the energy
and move to a higher energy level. These energy levels of the electrons in atoms
are quantized, meaning again that the electron must move from one energy level
to another in discrete steps rather than continuously. An excited state of an atom
is a state where its potential energy is higher than the ground state. An atom in the
excited state is not stable. When it returns back to the ground state, it releases the
energy that it had previously gained in the form of electromagnetic radiation.
Then continuous spectrum, like in a rainbow, comes from white light,
line spectrum is evident in colored compounds. Light spectrum only
has a few wavelengths (not all) or lines. Atoms tend to absorb some
wavelengths when electromagnetic radiation is passed through them
which display only a few narrow absorption lines when recorded.
The major difference between these two is that continuous spectra
has all the wavelengths while line spectrum only contains some of the
wavelengths. Line spectrum can also be generated in emission and
absorption spectrum while continuous spectrum occurs when both
absorption and emission spectra of a single species are put together.
In other words, line spectrum can be in either emission spectrum or
absorption spectrum.

The corresponding spectrum may exhibit a continuum, or may have superposed


on the continuum bright lines (an emission spectrum) or dark lines (an absorption
spectrum), as illustrated in Figure 4-4.

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

Figure 4-4. Comparison of a continuous, emission and absorption spectrum


Thus, emission spectrum are produced by thin gases in which the atoms do not
experience many collisions (because of the low density). The emission lines
correspond to photons of discrete energies that are emitted when excited atomic
states in the gas make transitions back to lower-lying levels.

A continuum spectrum results when the gas pressures are higher, so that lines are
broadened by collisions between the atoms until they are smeared into a
continuum. We may view a continuum spectrum as an emission spectrum in
which the lines overlap with each other and can no longer be distinguished as
individual emission lines.

An absorption spectrum occurs when light passes through a cold, dilute gas and
atoms in the gas absorb at characteristic frequencies; since the re-emitted light is
unlikely to be emitted in the same direction as the absorbed photon, this gives rise
to dark lines (absence of light) in the spectrum.

The emitted light can be observed as a series of colored lines with dark spaces in
between; this series of colored lines is called a line or atomic spectra. Each
element produces a unique set of spectral lines. Since no two elements emit the
same spectral lines, elements can be identified by their line spectrum.

Feedback
Answer the following questions:
1. A light wave is an electromagnetic wave that has both an electric and
magnetic component associated with it. Electromagnetic waves are often
distinguished from mechanical waves. The distinction is based on the fact
that electromagnetic waves ______.
a. can travel through materials and mechanical waves cannot
b. come in a range of frequencies and mechanical waves exist with only
certain frequencies
c. can travel through a region void of matter and mechanical waves
cannot
d. electromagnetic waves cannot transport energy and mechanical waves
can transport energy
2. Consider the electromagnetic spectrum as you answer these questions.
a. Which region of the electromagnetic spectrum has the highest
frequency?
b. Which region of the electromagnetic spectrum has the longest
wavelength?
c. Which region of the electromagnetic spectrum will travel with the
fastest speed?
3. Consider the visible light spectrum as you answer these questions.
a. Which color of the visible light spectrum has the lowest frequency?

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

b. Which color of the visible light spectrum has the shortest wavelength?
c. Which color has a higher energy, yellow or red?

B. Bohr Model of the Hydrogen Atom

Learning Objectives:

1. To understand how the emission spectrum of hydrogen demonstrates


the quantized nature of energy
2. To describe Bohr’s model of the hydrogen atom
3. Illustrate energy state using the energy-level diagram

Let’s Learn

The great Danish physicist Niels Bohr (1885-1962)


introduced the atomic Hydrogen model in 1913. He used the
planetary model of the atom to explain the atomic spectrum
and size of the hydrogen atom. He described it as a
positively charged nucleus, comprised of protons and
neutrons, surrounded by a negatively charged electron
cloud. In the model, electrons revolve around the nucleus in
Niels Bohr atomic shells. The atom is held together by electrostatic
forces between the positive nucleus and negative surroundings.

Bohr, in an attempt to understand the structure of an atom better, combined


classical theory with the early quantum concepts and suggested the following
theories:
1. In an atom, electrons encircle the nucleus in specific allowable paths called
orbits. Each orbit is assigned a quantum number, n, which is restricted to
integer values: 1, 2, 3, 4, 5, 6 . . . . . When the electron is in one of these
orbits, its energy is fixed. The ground state of the hydrogen atom, where its
energy is lowest, is when the electron is in the orbit that is closest to the
nucleus. The orbits that are further from the nucleus are all of successively
greater energy.
2. The electron can remain in an orbit indefinitely.
3. He explained that electrons can be moved into different orbits with the
addition of energy. When the energy is removed, the electrons return back to
their ground state, emitting a corresponding amount of energy - a quantum of
light, or photon. This was the basis for what later became known as quantum
theory.

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

Bohr derived the equations for the energy levels available to the electron in
the hydrogen atom thus,

E = -2π2me4 Z2
h2 n2
where:
m = mass of the electron
e = charge of the electron
h = Planck’s constant
Z = nuclear charge, +1 for hydrogen
n = an integer which may have values starting with 1

upon substitution of the values for m, e, and h, the equation becomes

E = 2.178 x 10-18 Joules


n2

The highest possible value of E in the above equation is zero when the electron is
at an infinite distance from the nucleus (n = ꝏ). The energy of an electron bound
to the nucleus is negative with the lowest value when n = 1.

T
h e
4-4. Learning Check
Using the Bohr model, determine the energy of an electron with
n = 8 in a hydrogen atom.

radius of the orbit corresponding to each level is given by the equation:


r = n2 h2 _
4 π2me4
The first orbit, where n = 1, has a radius of 0.529x10 -11 m. this usually referred to
as the first Bohr radius and given the symbol a0 :
r = n2 a0
The n values, radii and
energies of the six Bohr orbits
are shown in Figure 5.

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

Figure 4-5. The first six electron orbits in the hydrogen atom

Suppose the electron moves from n = 5 orbit to n = 2 orbit with energies

E = - 0.08712x10-18 J

E = - 0.5445x10-18 J

The difference in energy, ∆E is computed as follows:

∆E = Efinal - Einitial = E2 – E5

= (- 0.5445x10-18 J) – (- 0.08712x10-18 J)
= - 0.45738x10-18 J

The negative sign of ∆E means that energy is given off in the process. This
difference in energy is the energy of the quantum of light emitted.

The wavelength of the light corresponding to this transition may be computed as


follows:
∆E = hc
λ

Solving for wavelength,


λ = hc
∆E
= (6.626 x 10-34 J.sec) (3 x 108 m s-1)
0.45738 x 10-18 J

= 4.346 x 10-7 m x 1nm


10-9m
= 434.6 nm

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

The correspondence between transitions of the electron and the major lines in the
visible region of the hydrogen spectrum is shown in Figure 6.

An empirical formula to describe the positions (wavelengths) λ of the hydrogen


emission lines in the series was discovered in 1885 by Johann Balmer. It is known
as the Balmer formula:

1 = RH ( 1 – 1 )
λ 22 n2

The constant RH = 1.09737×107m−1 is called the Rydberg constant for hydrogen.


In equation, the positive integer n takes on values n=3, 4, 5, 6 for the four visible
lines in this series. The series of emission lines given by the Balmer formula is
called the Balmer series for hydrogen. Other emission lines of hydrogen that were
discovered in the twentieth century are described by the Rydberg formula, which
summarizes all of the experimental data:

1 = RH ( 1 – 1 ) , where ni = nf + 1, nf + 3, . . . .
λ n2f n2i

When nf = 1, the series of spectral lines is called the Lyman series. When nf = 2,
the series is called the Balmer series, and in this case, the Rydberg formula
coincides with the Balmer formula. When nf = 3, the series is called the Paschen
series. When nf = 4, the series is called the Brackett series. When nf = 5 , the series
is called the Pfund series. When nf = 6 , we have the Humphreys series. As you
may guess, there are infinitely many such spectral bands in the spectrum of
hydrogen because nfnf can be any positive integer number.

Figure 4-6. The Balmer series—the spectral lines in the visible region
of hydrogen's emission spectrum

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

4-5. Learning Check


Refer to Figure 3 and determine the color of the light that
corresponds to the n = 5 n = 2 and n = 3 n = 2
transitions in the hydrogen atom.

n=5 n=2 : _____________________


n=3 n=2 : _____________________

The movement of electrons between these energy levels produces a spectrum.


The Balmer equation is used to describe the four different wavelengths of
Hydrogen which are present in the visible light spectrum. These wavelengths
are at 656, 486, 434, and 410nm. These correspond to the emission of
photons as an electron in an excited state transitions down to energy level
n=2. The Rydberg formula, below, generalizes the Balmer series for all
energy level transitions. To get the Balmer lines, the Rydberg formula is used
with an nf of 2.

4-6. Learning Check


What does it mean to say that the energy of the electrons in an atom is
quantized?
Using the Bohr model, determine the energy, in joules, necessary to
ionize a ground-state hydrogen atom. Show your calculations.

Feedback

1. An emission spectrum gives one of the lines in the Balmer series of the
hydrogen atom at 410 nm. This wavelength results from a transition from an
upper energy level to n=2. What is the principal quantum number of the
upper level?

2. The Bohr model of the atom was able to explain the Balmer series because:
a. larger orbits required electrons to have more negative energy in order to
match the angular momentum.
b. differences between the energy levels of the orbits matched the difference
between energy levels of the line spectra.
c. electrons were allowed to exist only in allowed orbits and nowhere else.
d. none of the above

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

3. One reason the Bohr model of the atom failed was it did not explain why
a. accelerating electrons do not emit electromagnetic radiation.
b. moving electrons have a greater mass.
c. electrons in the orbits of an atom have negative energies.
d. electrons in greater orbits of an atom have greater velocities

C. Quantum Theory: Quantum Mechanical Model of the Atom

Learning Objectives:

1. Describe the quantum theory of light;


2. Describe the quantum mechanical model of the atom and how it compares with
the Bohr model;
3. Give significance of quantum numbers;
4. Identify quantum numbers of an electron in a given atom.
5. To understand how the electron’s position is represented in the wave
mechanical model

Let’s Learn

The Quantum Theory

Quantum theory is the theoretical basis of modern physics that explains the nature
and behavior of matter and energy on the atomic and subatomic level.

In 1900, physicist Max Planck presented his quantum theory to the German
Physical Society. Planck had sought to discover the reason that radiation from a
glowing body changes in color from red, to orange, and, finally, to blue as its
temperature rises. He found that by making the assumption that energy existed in
individual units in the same way that matter does, rather than just as a
constant electromagnetic wave - as had been formerly assumed - and was
therefore quantifiable. The existence of these units became the first assumption of
quantum theory.

Light consists of packets or bundles of energy with each bundle containing a


definite amount of energy. Planck called the bundles of energy quanta. The size
of the packet or bundle is smaller for light of lower frequency.

If light is of a single frequency, then the bundles or quanta are of the same energy
content (monochromatic). However, if light is of different frequencies, then the
bundles or quanta have different energy content (polychromatic).

The Development of Quantum Theory


 In 1900, Planck made the assumption that energy was made of individual
units, or quanta.

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

 In 1905, Albert Einstein theorized that not just the energy, but the
radiation itself was quantized in the same manner.
 In 1924, Louis de Broglie proposed that there is no fundamental difference
in the makeup and behavior of energy and matter; on the atomic and
subatomic level either may behave as if made of either particles or waves.
This theory became known as the principle of wave-particle duality:
elementary particles of both energy and matter behave, depending on the
conditions, like either particles or waves.
 In 1927, Werner Heisenberg proposed that precise, simultaneous
measurement of two complementary values - such as the position and
momentum of a subatomic particle - is impossible. Contrary to the
principles of classical physics, their simultaneous measurement is
inescapably flawed; the more precisely one value is measured, the more
flawed will be the measurement of the other value. This theory became
known as the uncertainty principle, which prompted Albert Einstein's
famous comment, "God does not play dice."

Light can be viewed as stream of particles called photons. Each photon carries the
quantum or packet of energy given by the equation E = hν. Since the constant h is
very small, the bundles of energy are very small. Thus, the particulate nature of
light is not obvious to us.

The Quantum Mechanical Model of an Atom

The theory of light has a dual nature: wavelike or continuous and particulate
(consisting of photons). This was also applied to matter by Louis de Broglie
(1892). He suggested that particles properties such as mass, velocity and
momentum also have wavelike properties such as wavelength.

The dual behavior of particles is not obvious in our day-to-day experience


because the wavelength associated with a particle is detectable or measurable only
for particles with very small masses, like the electron or ant atom or molecule.

German Physicist, Erwin Schrodinger (1887-1961), applied the idea of an electron


having wavelike properties. He derived the equation for the energy of an atom
and found that by assuming wavelike behavior for the electron, the quantized
nature of the energy of the electron becomes an inevitable consequence.

A major problem with Bohr's model was that it treated electrons as particles that
existed in precisely-defined orbits. Based on de Broglie's idea that particles could
exhibit wavelike behavior, Austrian physicist Erwin Schrödinger theorized that
the behavior of electrons within atoms could be explained by treating them
mathematically as matter waves. This model, which is the basis of the modern
understanding of the atom, is known as the Quantum Mechanical or Wave
Mechanical Model.

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

The Quantum Mechanical or Wave Model came from the following history:

1. Louis de Broglie: Electrons behave with wave and particle properties


at the same time.
λ= h
m⋅ν

2. Werner Heisenberg: It is impossible to know both the position and velocity of


an electron simultaneously - Heisenberg's Uncertainty Principle.
3. Erwin Schrodinger: refined the wave-particle theory proposed by de Broglie.
He developed an equation that treated an electron like a wave and predicted
the probable location of an electron around the nucleus called the atomic
orbital.

The quantum mechanical model of the atom treats an electron like a wave.

Quantum Number

The quantum mechanical model describes the probable location of electrons in


atoms by the quantum numbers. The first three quantum numbers describe fully
an orbital. Since an orbital is an energy state, n, l, and (ml) therefore the define an
energy state of the atom.

1. Principal quantum number (n) describes the shell or energy level or better the
average relative distance of an electron from the nucleus. It also indicates the
relative size and energy of atomic orbitals. n=integers: n= 1, 2, 3, etc.

As n increases:
- orbital becomes larger
- electron spends more time farther away from nucleus
- atom's energy level increases

2. Angular or azimuthal quantum number (l) describes the shape of the orbital or
the region of space occupied by the electron. The allowed values l of depend
on the value of n and can range from 0 to n − 1:
ɭ = 0, 1, 2,…, n−1
For example, if n = 1, l can be only 0; if n = 2, l can be 0 or 1; etc.. For a given
atom, all wave functions that have the same values of both n and l form a

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

subshell. The regions of space occupied by electrons in the same subshell usually
have the same shape, but they are oriented differently in space.
To simply so as not to be confused, the l values have been given letter symbols as
follows:
l (numerical value) 0 1 2 3 ...
l (equivalent subshells) s p d f ...
Principal quantum numbers consist of sublevels or subshells. Sublevels define the
orbital shapes (s, p, d, f)

Figure 4-7. The Orbitals in Subshells within the Shells of atoms

Figure 4-8. The Shapes of the Orbitals

The main factor affecting an electron's probability distribution for s orbitals,


which are spherical, is the distance from the nucleus (the radius). But, for other
types of orbitals such as p, d, and f orbitals, the electron's angular position relative

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

to the nucleus becomes a factor in the probability density. This will make you
appreciate more interesting orbital shapes, such as the ones in image below.
Let us consider the number of orbitals in each sublevel:
s : 1 orbital
p : 3 orbitals
d : 5 orbitals
f : 7 orbitals

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

Figure 4-9. Schematics showing the general shapes of s, p, d, and f orbitals.


Image credit: UCDavis Chemwiki, CC BY-NC-SA 3.0 US

3. Magnetic quantum number (ml) describes the orientation in space of a


particular orbital. It is called the magnetic quantum number because the effect
of different orientations of orbitals was first observed in the presence of a
magnetic field. Consequently, its value depends on the orbital angular
quantum number l. Given a certain l, ml is an interval ranging from –l to +l,
so it can be zero, a negative integer, or a positive integer.

ml = −l, (−l+1),(−l+2),…,−2,−1, 0, +1, +2, …( l –1), ( l –2), + l

Here is an example: If n=3, and l =2, then what are the possible values of ml?

Since ml must range from –l to +l, then ml can be: -2, -1, 0, +1, or +2. This
means that there are 5 possible orientations of the orbitals or we can say that
there are 5 different d orbitals.

4-6. Learning Check


Describe the allowed combinations of the n, l, and m quantum
numbers when n = 3.

Orbitals n l ml
3s _______ _______ _______
3p _______ _______ _______
_______ _______ _______
_______ _______ _______
3d _______ _______ _______
_______ _______ _______
_______ _______ _______
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_______ _______ _______
_______ _______ _______
Unit IV. The Electronic Structure of the Atom and the Periodic Table

4. Spin quantum number (ms) designates the direction of the electron spin and
may have a spin of +1/2, represented by↑, or –1/2, represented by ↓. This
means that when ms is positive the electron has an upward spin, which can be
referred to as "spin up." When it is negative, the electron has a downward
spin, so it is "spin down." The significance of the electron spin quantum
number is its determination of an atom's ability to generate a magnetic field
or not.

4-7. Learning Check


Identify the quantum numbers of the last electron of the
following atoms:
Quantum No. Li (2s1) Cl (3p5) Zn (3d10)
n _______ _______ _______
l _______ _______ _______
ml _______ _______ _______
ms _______ _______ _______

Feedback

A. For each set of quantum numbers below, determine and identify whether the
combination of the quantum numbers is possible or not. If not, state the
reason.
1. n=2 l=1 ml = -2
2. n=3 l=0 ml = +3

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

3. n=6 l=0 ml = 0
4. n=5 l=3 ml = -1
5. n=3 l=4 ml = +3

B. How many possible orbitals are there for


1. n = 4 - ___________
2. n = 6 - ___________

C. Identify the subshell in which electrons with the following quantum numbers
are found:
a. n = 3 l=1 ____________
b. n = 5 l=3 ____________
c. n = 2 l=0 ____________

D. Choose from the given choices the most appropriate answer for
each question
1. The magnetic quantum number describes the:
a. Number of electrons
b. Average distance of the most electron dense regions from the
nucleus
c. Spatial orientation of the orbital
d. Shape of the orbital
2. How many electrons can inhabit all of the n=4 orbitals?
a. 14
b. 24
c. 32
d. 36
3. The principle quantum number is related to:
a. the shape of the orbital
b. the spatial orientation of the orbital
c. the average distance of the most electron-dense regions from the
nucleus
d. the number of electrons
4. Which of the following sets is not an acceptable set of quantum numbers?
a. n = 2 l=1 ml = -1
b. n = 7 l=3 ml = +3
c. n = 2 l=1 ml = +1
d. n = 3 l=1 ml = -3
5. How many orbitals are in the 5s subshell?
a. 2
b. 5
c. 1
d. 3
6. How many orbitals are in the 4d subshell?
a. 3

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

b. 6
c. 4
d. 5
7. How many total electrons can the ‘p’ orbitals hold?
a. 1
b. 6
c. 7
d. 3
8. What are the quantum numbers that describe a 3p orbital?
a. n = 3 l=1 ml = +1
b. n = 3 l=1 ml = 0
c. n = 3 l=1 ml = -1
d. All of the above
9. Probabilities are used because of Heisenberg's Uncertainty Principle. This
principle states that the _________ and ________ of an electron can be
measured but not simultaneously.
a. charge, velocity
b. charge, position
c. position, velocity
d. charge, spin
10. Why are electrons assigned quantum numbers?
a. Quantum numbers are designed to find the possible location of
electrons
b. Quantum numbers are designed to find the possible velocity of
electrons
c. Quantum numbers are designed to find the possible spin of electrons
11. The quantum mechanical model describes electrons as:
a. Particles
b. Waves
c. Particles with wave-like properties
d. Small, hard spheres

D. Electronic Configuration of the Element

Learning Objectives:

After going through this module, you are expected to:

1. write the predicted ground-state electron configurations of atoms

21
Unit IV. The Electronic Structure of the Atom and the Periodic Table

2. specify the shell and subshell symbols and their positions.


3. define the position of electrons in different shells of an atom.
4. use orbital filling diagrams to describe the locations of electrons in an
atom.

Let’s Learn

The electron configuration, also called electronic structure of an atom describes


the arrangement of electrons distributed among the orbital shells and subshells.
Usually, the electron configuration is used to describe the orbitals of an atom in
its ground state (lowest energy state), but it can also be used to describe electron
at higher energies called excited state. It can also be used to represent an atom that
has ionized into a cation or anion by compensating with the loss of or gain of
electrons in their subsequent orbitals.

The various physical and chemical properties of elements can be correlated to


their unique electron configurations. The valence electrons, electrons in the
outermost shell, are the determining factor for the unique properties of the
element.

We will be learning how to write the arrangement of electrons in an atom in its


ground state. When assigning electrons to orbitals, we must follow a set of three
rules or principles:
 the Aufbau Principle
 the Pauli-Exclusion Principle
 Hund's Rule

Aufbau Principle

The 'Aufbau' is a German word for 'building up'. The Aufbau principle, also
called the building-up principle, states that electron's occupy orbitals in order of
increasing energy. The order of is as follows:
1s<2s<2p<3s<3p<4s<3d<4p<5s<4d<5p<6s<4f<5d<6p<7s<5f<6d<7p . . .
Another way to view this order of increasing energy is by using the Mnemonic
Device shown in Figure 7, thus the proper writing of the location of electrons in
an atom.

22
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Figure 4-10. Mnemonic Devise for the filling of orbitals

Pauli Exclusion Principle

 According to this principle, an orbital can have maximum two electrons


and these must have opposite spins.
 In other words, no two electrons in an atom can have all the four
quantum numbers exactly the same.

The Pauli Exclusion Principle states that, no two electrons in an atom can have
the same four electronic quantum numbers. As an orbital can contain a maximum
of only two electrons, the two electrons must have opposing spins. This means if
one is assigned an up-spin (+1/2), the other must be down-spin (-1/2).

Let us illustrate this with beryllium which has four electrons. One electron is
placed in the 1s orbital. This electron has the quantum numbers:

n=1 l=0 ml = 0 ms = +1/2

If the next electron also occupy the 1s orbital, the quantum numbers of the second
electron would be:

n=1 l=0 ml = 0 ms = -1/2

Pauli Exclusion Principle is satisfied with the helium electrons for the quantum
numbers are not at all identical. The two electrons occupying the same orbital are
identical in their three quantum numbers: n, l, ml, but differ in ms. Since there are
only two possible values of ms, then a maximum of two electrons can occupy an
orbital.

23
Unit IV. The Electronic Structure of the Atom and the Periodic Table

The next two more electrons will occupy the next 2s orbital and will have the
following quantum numbers:
n=2 l=0 ml = 0 ms = +1/2

n=2 l=0 ml = 0 ms = -1/2

The electronic configuration of beryllium is one where there are two electrons in
the 1s orbital and another two electrons in the 2s orbital. This can be written as 1s 2
2s2.

The superscripts indicate the number of electrons in the orbital.

Electronic configuration or structure can also be shown in an orbital diagram


using arrows to represent electrons and boxes to represent orbitals. Beryllium will
have this diagram:
1s 2s

↑↓ ↑↓

The direction of arrows represents the spin of the electrons. When it is positive
the electron has an upward spin, which can be referred to as "spin up." When it is
negative, the electron has a downward spin, so it is "spin down."

4-8. Learning Check


Complete the table by indicating the maximum number of
electrons which can be accommodated in each main energy level.

Main Energy Number of Subshells Maximum No.


Level Orbitals Involved of Electrons
1 1 s ________
2 4 s, p ________
3 9 s, p, d ________
4 16 s, p, d, f ________

Hund’s Rule

24
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Let us take a look on the electronic configuration of nitrogen having seven


electrons. Applying the two principles we had just discussed, there are three
possible arrangements for the electrons of nitrogen as shown in Figure 7. They
differ on the arrangement of electrons in the 2p orbitals and take note that the
orbitals in this set are degenerate – same energy.

1s 2s 2px 2py 2pz

A ↑↓ ↑↓ ↑↓ ↓

B ↑↓ ↑↓ ↑ ↑ ↓

C ↑↓ ↑↓ ↑ ↑ ↑

Figure 4-11. Orbital diagrams showing the possible arrangements


of the nitrogen electrons

Which of the above presentation is the arrangement of electrons of nitrogen at its


ground state?

The arrangement in A has high energy since the two electrons are in the same
orbital repel. Hence, this is not its ground state. Let us take note that the motion of
electrons is said to be correlated. They avoid each other because of their charge
(same charge repel) and prefer to stay in separate orbitals if there are available
orbitals of the same energy.

Another property of electrons which correlates their motion is their spin.


Electrons of the same spin will tend to avoid each other in space and will lead to
lower energy. Therefore, the ground state of nitrogen is C where three electrons
are in separate orbitals of the same spin.

According to Hund’s rule, the electrons are filled in the degenerate orbitals of the
same subshell. Electron pairing in p, d and f orbitals cannot be done until each
sub-shell is occupied singly. This is because electrons are the same in charge and
they repel each other. This repulsion is minimized if two electrons move away
from each other by acquiring different degenerate orbitals. All the orbitals which
are singly occupied have parallel spins which can be either clockwise or
counterclockwise. If the electrons have parallel spin then there will be less inter-
electronic repulsions and high spin multiplicity. So in order to maximize spin
multiplicity, the pairing of electrons in a sub-shell does not take place until each
sub-shell is singly occupied.

25
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Figure 4-12. The 2p sublevel, for the elements boron (Z = 5), carbon (Z = 6), nitrogen
(Z = 7), and oxygen (Z = 8). According to Hund’s rule, as electrons are added
to a set of orbitals of equal energy, one electron enters each orbital
before any orbital receives a second electron.

If you assign electrons to orbitals, an electron will be filled first to all the orbitals
with similar energy (also referred to as degenerate orbitals) before pairing with
another electron in a half-filled orbital. Atoms at ground states tend to have as
many unpaired electrons as possible.

4-9. Learing Check


Write the electronic configuration of the following atoms. Show an
orbital diagram for each arrangement.
1. 12Mg ____________________________________________
2. 15P ____________________________________________
3. 26Fe ____________________________________________
4. 53I ____________________________________________
5. 61Pm ____________________________________________

4-10. Learning Check

For each electronic configuration of atoms below, indicate whether


it describes a ground state or excited state. If it is written in its
excited state, write its ground state configuration
a. O : 1s2 2s2 2p2 2p2
8

_____________________________________________
b. 20Ca : 1s2 2s2 2p6 3s2 3p6 3d1 3d1
_____________________________________________
c. 25Mn : 1s2 2s2 2p6 3s2 3p6 4s2 3d1 3d1 3d1 3d1 3d1
____________________________________________________________________

d. Kr : 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p2 4p2 4p2
36

_____________________________________________

26
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Feedback
Answer the following questions:
1. What atom matches this electron configuration? 1s22s22p63s1
a. Sodium
b. Magnesium
c. Aluminum
d. Potassium
2. What atom matches this electron configuration?
1s22s22p63s23p64s23d10
a. Zinc
b. Copper
c. Nickel
d. Germanium
3. What is the electron configuration for a Sulfur atom?
a. 1s22s22p63p6
b. 1s22s22p63s23p6
c. 1s22s22p63s23p4
d. 3p4
4. What atom matches this electron configuration?
1s22s22p63s33p64s23d104p65s24d105p66s24f145d8
a. Mercury
b. Gold
c. Platinum
d. Thallium
5. An orbital can at most hold how many electrons?
a. 1 electron
b. 2 electrons
c. 3 electrons
d. 4 electrons
6. The electron configuration of an atom is 1s22s22p6. The number of
electrons in the atom is
a. 3
b. 6
c. 8
d. 10
7. How many orbitals are in the 3s sublevel?
a. 1
b. 2
c. 3
d. 4
8. How many orbitals are in the 4p sublevel?
a. 2
b. 3
c. 4
d. 6

27
Unit IV. The Electronic Structure of the Atom and the Periodic Table

9. How many orbitals are in the 6f sublevel?


a. 2
b. 4
c. 7
d. 14
10. After filling 5s, electrons would fill...
a. 5p
b. 4d
c. 5d
d. 3f

E. The Periodic Table


Learning Objectives:

After going through this lesson, you are expected to:


1. explain the discovery of the elements was influence by the development
of the concept of an element;
2. state the periodic law and describe how the present form of the periodic
law evolved starting from the work of Mendeleev to that of Moseley;
3. explain the factors that affect the atomic size, ionization energy,
electronegativity and electron affinity of atoms;
4. determine the valence electron configuration of an element from its
position in the periodic table;
5. relate the similarities in the properties of the elements with their position
in the periodic table and their electronic configuration;
6. correctly predict the position of the elements in the Periodic Table using
its electronic configuration
7. explain the trends of the following properties of element in the periodic
table:
- metallic luster
- number of valence electrons
- atomic size
- ionic size
- ionization energy
- electron affinity
- electronegativity
8. discuss the factors that affect atomic size, ionization energy and
electronegativity
9. relate ionization energy and electron affinity to ion formation

28
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Let’s Learn

The Periodic Law

The discovery of the Elements

We should understand that the discovery of elements is a necessary prerequisite in


the development of the periodic table. The concept of an element as we presently
know has not always been the way it was known to man.

From the Ancient times to the 16 th century, ten of the substances that we classify
as elements nowadays were already recognized such as gold, silver, tin, copper,
lead, antimony, carbon, sulfur, iron and mercury have been known since antiquity.
In 1669, phosphorus was the first element to be chemically discovered by Hennig
Brandt (German), refer to Table 4-1. They were recognized as elements yet during
those times, because their common idea about elements, Empedocles (c. 495–
435 B.C.) proposed that there only four basic roots of all materials: air, water,
earth and fire.

Table 4-1. The Discovery of the Elements

Early The elements Carbon, Sulfur, Iron, Tin, Lead, Copper, Mercury,
history Silver, and Gold are known to humans.
Pre-a.d. 1600: The elements Arsenic, Antimony, Bismuth, and Zinc are
known to humans.
1669 German physician Hennig Brand discovers Phosphorus.
1735 Swedish chemist Georg Brandt discovers Cobalt.
c. 1748 Spanish military Leader Don Antonio de Ulloa discovers Platinum .
1751 Swedish mineralogist Axel Fredrik Cronstedt discovers Nickel .
1766 English chemist and physicist Henry Cavendish discovers Hydrogen .
1772 Scottish physician and chemist Daniel Rutherford discovers Nitrogen .
1774 Swedish chemist Carl Wilhelm Scheele discovers Chlorine .
1774 Swedish mineralogist Johann Gottlieb Gahn discovers Manganese .
1774 English chemist Joseph Priestley and Swedish chemist Carl Wilhelm
Scheele discover Oxygen .
1781 Swedish chemist Peter Jacob Hjelm discovers Molybdenum .
c. 1782 Austrian mineralogist Baron Franz Joseph Müller von Reichenstein
discovers Tellurium .
1783 Spanish scientists Don Fausto D'Elhuyard and Don Juan José D'Elhuyard,
and Swedish chemist Carl Wilhelm Scheele discover Tungsten .
1789 German chemist Martin Klaproth discovers Uranium.
1789 German chemist Martin Klaproth discovers Zirconium.

29
Unit IV. The Electronic Structure of the Atom and the Periodic Table

1791 English clergyman William Gregor discovers Titanium.


1794 Finnish chemist Johan Gadolin discovers Yttrium.
1797 French chemist Louis-Nicolas Vauquelin discovers Chromium.
1798 French chemist Louis-Nicolas Vauquelin discovers Beryllium.
1801 English chemist Charles Hatchett discovers Niobium.
1801 Spanish-Mexican metallurgist Andrés Manuel del Río discovers
Vanadium.
1802 Swedish chemist and mineralogist Anders Gustaf Ekeberg discovers
Tantalum.
1803 English chemist and physicist William Hyde Wollaston discovers
Palladium.
1803 Swedish chemists Jöns Jakob Berzelius and Wilhelm Hisinger, and German
chemist Martin Klaproth discover black rock of Bastnas, Sweden, which led
to the discovery of several elements.
1804 English chemist and physicist William Hyde Wollaston
discovers Rhodium .
1804 English chemist Smithson Tennant discovers Osmium .
1804 English chemist Smithson Tennant discovers Iridium .
1807 English chemist Sir Humphry Davy discovers Potassium .
1807 English chemist Sir Humphry Davy discovers Sodium .
1808 English chemist Sir Humphry Davy discovers Barium .
1808 English chemist Sir Humphry Davy discovers Strontium .
1808 English chemist Sir Humphry Davy discovers Calcium .
1808 English chemist Sir Humphry Davy discovers Magnesium .
1808 French chemists Louis Jacques Thênard and Joseph Louis Gay-Lussac
discover Boron.
1811 French chemist Bernard Courtois discovers Iodine.
1817 Swedish chemist Johan August Arfwedson discovers Lithium.
1817 German chemist Friedrich Stromeyer discovers Cadmium.
1818 Swedish chemists Jöns Jakob Berzelius and J. G. Gahn discover Selenium.
1823 Swedish chemist Jöns Jakob Berzelius discovers Silicon.
1825 Danish chemist and physicist Hans Christian Oersted discovers Aluminum.
1826 French chemist Antoine-Jérôme Balard discovers Bromine.
1828 Swedish chemist Jöns Jakob Berzelius discovers Thorium.
1830 Swedish chemist Nils Gabriel Sefström rediscovers Vanadium.
1839 Swedish chemist Carl Gustav Mosander discovers Cerium.
1839 Swedish chemist Carl Gustav Mosander discovers Lanthanum .
1843 Swedish chemist Carl Gustav Mosander discovers Terbium .
1843 Swedish chemist Carl Gustav Mosander discovers Erbium .
1844 Russian chemist Carl Ernst Claus discovers Ruthenium .
c. 1861 German chemists Robert Bunsen and Gustav Kirchhoff discovers Cesium .
c. 1861 German chemists Robert Bunsen and Gustav Kirchhoff

30
Unit IV. The Electronic Structure of the Atom and the Periodic Table

discovers Rubidium .
1861 British physicist Sir William Crookes discovers Thallium .
1863 German chemists Ferdinand Reich and Hieronymus Theodor Richter
discovers Indium .
1875 Paul-émile Lecoq de Boisbaudran discovers Gallium .
1878 Jean-Charles-Galissard de Marignac receives partial credit for the discovery
of Ytterbium .
1879 Swedish chemist Per Teodor Cleve discovers Holmium .
1879 Swedish chemist Per Teodor Cleve discovers Thulium.
1879 Swedish chemist Lars Nilson discovers Scandium.
1879 Swedish chemist Lars Nilson receives partial credit for the discovery
of Ytterbium.
1880 French chemist Paul-Émile Lecoq de Boisbaudran discovers Samarium.
1880 French chemist Jean-Charles-Galissard de Marignac discovers Gadolinium.
1885 Austrian chemist Carl Auer (Baron von Welsbach)
discovers Praseodymium.
1885 Austrian chemist Carl Auer (Baron von Welsbach) discovers Neodymium.
1885 German chemist Clemens Alexander Winkler discovers Germanium.
1886 French chemist Henri Moissan discovers Fluorine.
1886 French chemist Paul-Émile Lecoq de Boisbaudran discovers Dysprosium.
1894 English chemists Lord Rayleigh and William Ramsav discover Argon.
1895 English chemist Sir William Ramsay and Swedish chemists Per Teodor
Cleve and Nils Abraham Langlet discover Helium.
1898 English chemists William Ramsay and Morris Travers discover Krypton.
1898 English chemists William Ramsay and Morris Travers discover Neon.
1898 English chemists William Ramsay and Morris Travers discover Xenon.
1898 French physicists Marie and Pierre Curie discover Polonium.
1898 French physicists Marie and Pierre Curie discover Radium.
1899 French chemist André Debierne discovers Actinium.
1900 German physicist Friedrich Ernst Dorn discovers Radon.
1901 French chemist Eugène-Anatole Demarçay discovers Europium.
1907 French chemist Georges Urbain discovers lutetium.
1907 French chemist Georges Urbain receives partial credit for the discovery
of Ytterbium.
1917 German physicists Use Meitner and Otto Hahn discover Protactinium.
1923 Dutch physicist Dirk Coster and Hungarian chemist George Charles de
Hevesy discover Hafnium.
1925 German chemists Walter Noddack, Ida Tacke, and Otto Berg
discover Rhenium.
1933 French chemist Marguerite Perey discovers Francium.
1939 Italian physicist Emilio Segré and his colleague Carlo Perrier
discover Technetium.
1940 Edwin M. McMillan (1907-91) and Philip H. Abelson prepare Neptunium.

31
Unit IV. The Electronic Structure of the Atom and the Periodic Table

1940 Dale R. Corson, Kenneth R. Mackenzie, and Emilio Segré


discover Astatine.
1940 University of California at Berkeley researcher Glenn Seaborg and others
prepare Plutonium.
1944 University of California at Berkeley researchers Glenn Seaborg, Albert
Ghiorso, Ralph A. James, and Leon O. Morgan prepare Americium .
1944 University of California at Berkeley researchers Glenn Seaborg, Albert
Ghiorso, and Ralph A. James prepare Curium .
1945 Scientists at the Oak Ridge Laboratory in Oak Ridge, Tennessee,
discover promethium .
1949 University of California at Berkeley researchers prepare Berkelium .
1950 University of California at Berkeley researchers Glenn Seaborg, Albert
Ghiorso, Kenneth Street, Jr., and Stanley G. Thompson
prepare Californium .
1954 University of California at Berkeley researchers prepare Einsteinium .
1954 University of California at Berkeley researcher Albert Ghiorso and others
prepare Fermium .
1960s & Researchers at the Joint Institute of Nuclear Research, in Dubna, Russia; the
1970s Lawrence Berkeley Laboratory at the University of California at Berkeley;
and the Institute for Heavy Ion Research in Darmstadt, Germany, continue
to prepare new Transfermium elements.

Plato (c. 427–347 B.C.) referred to these four "roots" as stoicheia elements.
Because of the questionable notion about elements, very little development was
made on the discovery of elements till 16th century. Arsenic (discovered in 1250)
and platinum (discovered in 1557) were discovered by the Arab alchemist named
Jabir ibn Hayyan.

By 1700, about 12 elements were known, but they were not yet recognized as they
are today.

Aristotle (384–322 B.C.), a student of Plato's, proposed that an element is "one of


those simple bodies into which other bodies can be decomposed and which itself
is not capable of being divided into others." Except for nuclear fission and other
nuclear reactions discovered more than 2,000 years later, by which the atoms of
an element can be decomposed into smaller parts, this definition remains accurate.

Eventually, English chemist Robert Boyle (1627–1691) revived Aristotle's


definition and refined the definition of an element as a substance which cannot be
decomposed into any number of distinct substances. For this definition, number
of known elements doubled for it provided a tool for testing whether a substance
is an element or not.

In 1789, French physicist-chemist Antoine Lavoisier (1743–94)


reaffirmed Boyle’s description of an element and further boost the

32

Antoine Lavoisier
Unit IV. The Electronic Structure of the Atom and the Periodic Table

discovery of more elements. He said that an element is the last point which
analysis is capable of reaching and into which we are able to reduce bodies by
decomposition. Lavoisier was able to publish the first textbook of chemistry that
contained the list of chemical elements based on their similar properties.
The Dalton’s atomic theory in the first decade of the 19th century provided an
explanation of the operational definition of Boyle and Lavoisier definition of
element. His definition of an element, a substance that consist of a single kind of
atom that cannot be further decomposed into simpler substances led to the
discovery of more elements. By 1869, a total of 63 elements had been discovered.
Other factors that led to the discovery of more elements aside from Dalton’s
theory were:

 improved analytical techniques so that elements with very similar


properties were separated and identified. For example, cadmium was
isolated from zinc ores
 development of the electrolytic method of decomposing compounds.
Substances which could not be decomposed by heating could often be
broken down by electrolysis, many of the more active metals such as
potassium, sodium, barium, strontium, calcium and magnesium were
discovered when their compounds were electrolyzed.
 development of the spectroscope for studying the light emitted by atoms.
All elements, if heated, would produce characteristic patterns of color. No
two elements exhibit the same spectral pattern. This helped in establishing
the identity of some elements such as cesium (from caesius, Latin word
for sky blue) and rubidium (from rubidius, Latin word for deepest red)

In 1914, Henry Moseley (187-1915), an English physicist, identified the atomic


number (equal to the number of protons or nuclear charge) as a fundamental
quantity which is unique to each element. The discovery of this property which
distinguishes the atoms of one element from the atoms of any other element
played a vital role in the synthesis of new elements.

Most of the elements listed under the column of the 1900s in Table 4-1 are man-
made. As the number of known elements grew, scientists began to recognize
patterns in properties and began to develop classification schemes.

Classification of Elements and the Periodic Law

When we deal on material things, it is a natural tendency to classify them


according to our choice. Just like the fruit vendor classifying kinds of fruits into
small, medium, and large. Teachers would also classify their students into male
and female or may arrange them alphabetically depending on our purpose of
putting them in order.

In the pursuit of knowledge, we use classification in understanding the subject of


our study.

33
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Chemists were investigating patterns in the properties of the elements that were
known at the time. Several attempts were made to group elements together over
the coming decades. Some of the elements were very similar in their properties
and there were several of these groups of elements.

Some of these groups and similarities of their properties are described below:

 Lithium (Li), Sodium (Na) and Potassium (K)


- They are very reactive and as a consequence they are not found to
occur in nature as free metals
- All are soft metals which can be cut with a sharp knife
- All react with water resulting in analogous compounds. The
compounds formed are all basic:
2 Li(s) + 2 H2O(l) → 2LiOH(aq) + H2(g)
2 Na(s) + 2 H2O(l) → 2NaOH(aq) + H2(g)
2 K(s) + 2 H2O(l) → 2KOH(aq) + H2(g)

- All form compounds with the halogens (F, Cl, Br, I) resulting in
compounds with analogous formulas, e.g., LiCl, NaCl, KCl, or LiX,
NaX, KX where X is any of the halogens.

 Chlorine (Cl), Bromine (Br), and Iodine (I)


- Chorine is a pale green gas, bromine is a reddish brown liquid and
iodine is a purple solid. Although they differ in states at room
temperature, liquid bromine and solid iodine are very volatile. They
evaporate to give a vapor very easily.
- All are very reactive, forming compounds with nearly all of the other
elements, especially with the metals.
- They form compounds with analogous formulas and similar
properties.

2 Na(s) + Cl2 → 2 NaCl(s)


2 Na(s) + Br2 → 2 NaBr(s)
2 Na(s) + I2 → 2 NaI(s)

- The three compounds NaCl, NaBr and NaI are white and crystalline,
soluble in water and have salty taste. Halogen, the name of this group
of elements, is derived from the Greek word halogenliterally means
salt former in keeping with the property of these elements to combine
with metals to form ionic compounds which are also called salts.

 Sulfur (S), Selenium (Se) and Tellurium (Te)

- They are moderately reactive.


- They form analogous compounds with hydrogen:
H2S, H2Se, H2Te.

34
Unit IV. The Electronic Structure of the Atom and the Periodic Table

- They form analogous compounds with sodium:


Na2S, Na2Se, Na2Te.

In 1817, German chemist Johann Wolfgang Döbereiner


recognized triads of elements with chemically similar
properties, such as lithium, sodium and potassium, and showed
that the properties of the middle element could be predicted
from the properties of the other two. He noticed that the atomic
weight of middle element, sodium fell midway between the
J.W. Dobereiner weights of lithium and potassium, elements possessing similar
chemical properties. He concluded that the atomic mass and the
density of the middle element in each triad is the approximate average of the
masses and densities of the first and the third elements.

Figure 4-13. Triads Element Classification of Döbereiner

In 1863, A. E. Beguyer de Chancourtois had the idea to plot the


elements in a spiral around the surface of the cylinder divided
into 16 vertical sections according to the elements’ atomic
masses. In every vertical strip, the elements with the same
physical and chemical properties were grouped together. He
called his device telluric helix. He stated from the result of his
experiments that the properties of elements were the same that of
A.E. Beguyer de
Chancourtois the properties of elements were the same as the properties of
numbers.

35
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Figure 4-14. Telluric Helix of A. E. Beguyer de Chancourtois


After several decades, John Newlands (1838-1898), an English
chemist, wrote a paper in 1863 which classified the 56 established
elements into 11 groups based on similar physical properties,
noting that many pairs of similar elements existed which differed
by some multiple of eight in the order of increasing atomic
weight. Below is an example of his grouping:
John Newlands
1 2 3 4 5 86 7
1 2 3 4 5 6 7 8
Li Be B C N O F Na Mg Al Si P S Cl K
do re mi fa sol la si do re mi fa sol la si do

the eight element sodium has properties similar to the that of the first element
lithium. The same property exhibited by potassium with sodium. Since Newlands
was also a musician, he likened his grouping trend with his musical notes. In 1864
Newlands published his version of the periodic table and proposed the Law of
Octaves (by analogy with the seven intervals of the musical scale). This law stated
that any given element will exhibit analogous behavior to the eighth element as
arranged in the table.

Who Is The Father of the Periodic Table?

There has been some disagreement about who deserves credit for being
the "father" of the periodic table, the German Julius Lothar Meyer or the
Russian Dmitri Ivanovich Mendeleev. Both chemists worked
independently, presented closely identical version of arranging the
elements based on their increasing properties. Meyer's 1864 textbook
included a rather abbreviated version of a periodic table used to classify
the elements. This consisted of about half of the known elements listed
in order of their atomic weight and demonstrated periodic
valence charges as a function of atomic weight. In 1868,
Meyer constructed an extended table which he gave to a
colleague for evaluation. Unfortunately for Meyer,
Mendeleev's table became available to the scientific community via
publication (1869) before Meyer's appeared (1870).

Dmitri Ivanovich Mendeleev (1834-1907) became a professor of general


chemistry at the University of St. Petersburg, he was unable to find an
appropriate textbook and thus began writing his own. That
textbook, written between 1868 and 1870, would provide a
framework for modern chemical and physical theory.

36
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Between 1868 and 1870, in the process of writing his book, The
Principles of Chemistry, Mendeleev created a table or chart as shown in
Figure 10 that listed the known elements according to increasing order of
atomic weights. When he organized the table into horizontal rows, a
pattern became apparent--but only if he left blanks in the table. If he did
so, elements with similar chemical properties appeared at regular
intervals--periodically--in vertical columns on the table.

Figure 4-15. Mendeleev’s table as published in 1869, with many gaps and uncertainties

Mendeleev was bold enough to suggest that new elements not yet discovered
would be found to fill the blank places. He even went so far as to predict the
properties of the missing elements. Although many scientists greeted Mendeleev's
first table with skepticism, its predictive value soon became clear. The discovery
of gallium in 1875, of scandium in 1879, and of germanium in 1886 supported the
idea underlying Mendeleev's table. Each of the new elements displayed properties
that accorded with those Mendeleev had predicted, based on his realization that
elements in the same column have similar chemical properties. The three new
elements were respectively discovered by a French, a Scandinavian, and a
German scientist, each of whom named the element in honor of his country or
region. (Gallia is Latin for France.)

From his table, Mendeleev developed his statement of the periodic law and
published his work On the Relationship of the Properties of the Elements to their
Atomic Weights in 1869. In 1906, Mendeleev came within one vote of being
awarded the Nobel Prize for his work.

At the time that Mendeleev developed his periodic table since the experimentally
determined atomic masses were not always accurate, he reordered elements
despite their accepted masses. For example, he changed the weight of beryllium

37
Unit IV. The Electronic Structure of the Atom and the Periodic Table

from 14 to 9. This placed beryllium into Group 2 above magnesium whose


properties it more closely resembled than where it had been located above
nitrogen. In all Mendeleev found that 17 elements had to be moved to new
positions from those indicated strictly by atomic weight for their properties to
correlate with other elements. These changes indicated that there were errors in
the accepted atomic weights of some elements (atomic weights were calculated
from combining weights, the weight of an element that combines with a given
weight of a standard.) However, even after corrections were made by
redetermining atomic weights, some elements still needed to be placed out of
order of their atomic weights. From the gaps present in his table, Mendeleev
predicted the existence and properties of unknown elements which he called eka-
aluminum, eka-boron, and eka-silicon.

Table 4.2 Comparison of the Properties Predicted by Mendeleev in 1869 for eka-Aluminum and
eka-Silicon with the Properties of Gallium (Discovered in 1875) and Germanium
(Discovered in 1886)
Property eka-Aluminum Gallium eka-Silicon Germanium
(predicted) (observed) (predicted) (observed)
atomic mass 68 69.723 72 72.64
element Metal metal dirty-gray metal gray-white metal
low mp mp = 29.8°C high mp mp = 938°C
ρρ = 5.9 g/cm3 ρρ = 5.91 g/cm3 ρρ = 5.5 g/cm3 ρρ = 5.323 g/cm3
oxide E2O3 Ga2O3 EO2 GeO2
ρρ = 5.5 g/cm3 ρρ = 6.0 g/cm3 ρρ = 4.7 g/cm3 ρρ = 4.25 g/cm3
Chloride ECl3 GaCl3 ECl4 GeCl4

Volatile mp = 78°C bp = 201°C bp < 100°C bp = 87°C

The elements gallium, scandium and germanium were found later to fit his
predictions quite well.

Mendeleev’s approach was ultimately adopted for several reasons: For one, he left
gaps for elements that had yet to be discovered. In doing so, he predicted the
elements gallium and germanium. He also placed atoms based principally on their
chemical properties, not atomic mass. As it turns out, organizing by chemical
family correctly sorts most of the elements by their atomic number; atomic mass
is not perfectly correlated with atomic number.

In 1895 Lord Rayleigh reported the discovery of a new gaseous


element named argon which proved to be chemically inert. This
element did not fit any of the known periodic groups. In
1898, William Ramsey suggested that argon be placed into the
periodic table between chlorine and potassium in a family with
Lord Rayleigh
helium, despite the fact that argon's atomic weight was greater than
that of potassium. This group was termed the "zero" group due to the zero valency
of the elements. Ramsey accurately predicted the future discovery and properties
neon.
Although Mendeleev's table demonstrated the periodic nature of the elements, it

38
Unit IV. The Electronic Structure of the Atom and the Periodic Table

remained for the discoveries of scientists of the 20th Century to explain why the
properties of the elements recur periodically.

In 1911 Ernest Rutherford published studies of the scattering of alpha particles


by heavy atom nuclei which led to the determination of nuclear charge. He
demonstrated that the nuclear charge on a nucleus was proportional to the atomic
weight of the element.

Also in 1911, Antonius van den Broek in a series of two papers


proposed that the atomic weight of an element was approximately
equal to the charge on an atom. This charge, later termed the
atomic number, could be used to number the elements within the
periodic table.
A. van de Broek

In 1913, Henry G. J. Moseley published the results of his


measurements of the wavelengths of the x-ray spectral lines of a
number of elements which showed that the ordering of the
wavelengths of the x-ray emissions of the elements coincided with
the ordering of the elements by atomic number. With the
Henry G. J. Moseley discovery of isotopes of the elements, it became apparent that
atomic weight was not the significant player in the periodic law as
Mendeleev, Meyers and others had proposed, but rather, the properties of the
elements varied periodically with atomic number.

The periodic table nowadays are constructed using atomic number as the basis for
ordering the elements and the PERIODIC LAW is stated thus: The physical and
chemical properties of the elements are the periodic functions of their atomic
numbers. The recurrence of the properties of elements is emphasized by the
arrangement of the elements in a table such as the elements with similar
properties are put together in a vertical column. This arrangement is called the
Periodic Table.

Figure 4-16 shows the periodic table as was constructed in the year 1930. The
heaviest known element that time was uranium. Take note that four elements,
atomic no. 43, 61, 85 and 87 were left blank for they were not yet known.

39
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Figure 4-16. The Periodic Table of the 1930s (Copyright © 2019 Zavalen.Info)

The question of why the periodic law exists was answered as


scientists developed an understanding of the electronic structure of
the elements beginning with Niels Bohr's studies of the organization
of electrons into shells through Gilbert Newton Lewis' discoveries of
Gibert N. Lewis
bonding electron pairs.

The last major changes to the periodic table resulted from Glenn
Seaborg's work in the middle of the 20th Century. Starting with his
discovery of plutonium in 1940, he discovered all the transuranic
elements from 94 to 102. He reconfigured the periodic table by
placing the actinide series below the lanthanide series. In 1951,
Glenn Seaborg Seaborg was awarded the Nobel Prize in chemistry for his work.
Element 106 has been named Seaborgium (Sg) in his honor.

40
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Figure 4-17. The Modern Periodic Table in current use

The modern periodic table of elements is based on Mendeleev's observations;


however, instead of being organized by atomic weight, the modern table is
arranged by atomic number (Z). As one moves from left to right in a row of the
periodic table, the properties of the elements gradually change. At the end of each
row, a drastic shift occurs in chemical properties. The next element in order of
atomic number is more similar to the first element in the row above it; thus a new
row begins on the table.

For example, oxygen (O), fluorine (F), and neon (Ne) (z = 8, 9 and 10,
respectively) all are stable nonmetals that are gases at room temperature. Sodium
(Na, Z = 11), however, is a silver metal that is solid at room temperature, much
like the element lithium (Z = 3). Thus sodium begins a new row in the periodic
table and is placed directly beneath lithium, highlighting their chemical
similarities.

When the present theory about the electronic structure of atoms was proposed, it
became clear that the basis for the arrangement of the elements in the periodic
table was the electron arrangements in atoms. Since the empirical bases of the
periodic table were the chemical properties of the elements, then it can be said
that the electron arrangement in atoms are related to the chemical behavior of the
elements.

The relationship between the position of the elements in the periodic table,
chemical properties, and electronic configuration is outlined below:

 Elements in a vertical column in the periodic table share many similar


chemical and physical properties. Columns in the periodic table are called
groups or family. The new numbering system of 1-18 was recommended
by the International Union of Pure and Applied Chemistry (IUPAC) as

41
Unit IV. The Electronic Structure of the Atom and the Periodic Table

shown in Figure 4-13. Group 1 are called alkali metals; group 2 – alkaline
earth metals; group 11 – coinage metals; group 17 – halogen or salt
formers.
 Elements belonging to the same group have similar electronic
configurations in their outermost main energy level. Electrons in the
outermost or main energy level are called valence electron while the inner
electrons are called core electrons.
 As one moves from left to right in a in a horizontal row, the chemical
properties of the elements slowly change. Rows in the periodic table are
called periods or series. The period number gives the outermost or main
energy level or the principal quantum number, n.

Consider group 1 elements electronic configuration, composed of hydrogen and


the alkali metals. You can see that all of the elements in the group have the
general valence electron configuration of ns1, where n is principal quantum
number of the main energy level.

H 1s1
Li 1s2 2s1
Na 1s2 2s2 2p6 3s1
K 1s2 2s2 2p6 3s2 3p6 4s1
Rb 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s1
Cs 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s1
Fr 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d10 6p6 7s1

4-11. Learning Check


Write the electronic configuration of each of the elements in group 13.
B ___________________________________________________
Al ___________________________________________________
Ga ___________________________________________________
In ___________________________________________________
Tl ___________________________________________________

4-12. Learning Check


42 Using the data in Figure 4-13, give the required in formation in the
table below:
Element Period Number Number of n of outermost
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Blocks of Elements

As you have learned, the electron configurations of the elements define the
peculiar shape of the periodic table. Although the table was originally organized
on the basis of physical and chemical similarities between the elements within
groups, these similarities are ultimately attributable to orbital energy levels and
the Pauli principle, which cause the individual subshells to be filled in a particular
order. As a result, the periodic table can be divided into “blocks” corresponding to
the type of subshell that is being filled, as illustrated in Figure 4-15.

For example, the two columns on the left, known as the s block, consist of
elements in which the ns orbitals are being filled. The six columns on the right,
elements in which the np orbitals are being filled, constitute the p block. In
between are the 10 columns of the d block, elements in which the (n − 1) d
orbitals are filled. At the bottom lie the 14 columns of the f block, elements in
which the (n − 2) f orbitals are filled. Since two electrons can be accommodated
per orbital, the number of columns in each block is the same as the maximum
electron capacity of the subshell: 2 for ns, 6 for np, 10 for (n − 1) d, and 14 for (n
− 2) f. Within each column, each element has the same valence electron
configuration—for example, ns1 (group 1) or ns2np1 (group 13).

43
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Figure 4-18. The Periodic Table, Showing How the Elements Are Grouped According to the Kind
of Subshell (s, p, d, f) Being Filled with Electrons in the Valence Shell of Each
Element.

Take note that the valence electron of an atom gives the group of the element
while the main or outermost energy level gives the period of the element.

For s and p block elements, the number of valence electron gives the group
number of the element. The relationship between the group number, valence
electron configuration and number of valence electrons for s and p block elements
also called representative elements is summarized below:

Group Number 1 2 13 14 15 16 17 18

General valence
Electron configuration ns1 ns2 ns2np1 ns2np2 ns2np3 ns2np4 ns2np5 ns2np6

Number of valence 1 2 3 4 5 6 7 8
electron

Consider element P which has 15 atomic number:


What is the electronic configuration of P?
- 1s2 2s2 2p6 3s2 3p3
What is the valence electron configuration?
- looking at the electronic configuration, the valence electron
configuration is 3s2 3p3

44
Unit IV. The Electronic Structure of the Atom and the Periodic Table

To what group does P is located?


- 2 electron from s and 3 electrons from p, hence valence electron is 5.
Therefore P is located in group 15.
To what period does P belong?
- Since the highest energy level of P as shown in the electronic
configuration is 3, therefore P if found in period 3

4-13. Learning Check

Give the required information in the table below:

Element Valence electron n of the main Period Valence Group


configuration energy level number electron Number

P 3s2 3p3 3 3 5 15

Al

5s2 5p4

6 2

4 18
The d block comprise of groups 3-12, commonly referred to as the transition
elements. There are 10 groups of this block corresponding to the 10 electrons that
d subshell can be accommodate. For the transition elements, the valence electrons
are those in the ns and (n-1) d orbitals. The relationship between the group
number, valence electron configuration and number of valence electrons for d
block elements also called transition metals is summarized below:

Group Number 3 4 5 6 7 8 9 10 11 12

General valence ns2d1 ns2d2 ns2nd3 ns2nd4 ns2nd5 ns2nd6 ns2nd7 ns2nd8 ns2nd9 ns2nd10
Electron
configuration
Number of valence 3 4 5 6 7 8 9 10 1 2
electron

Consider element Pt which has 78 atomic number:

What is the electronic configuration of Pt?


- 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f14 5d8
What is the valence electron configuration?
- looking at the electronic configuration, the valence electron
configuration is 6s2 4f14 5d8
To what group does Pt is located?

45
Unit IV. The Electronic Structure of the Atom and the Periodic Table

-2 electron from s and 8 electrons from d, hence valence electron is


10. Therefore Pt is located in group 10.
To what period does Pt belong?
- Since the highest energy level of Pt as shown in the electronic
configuration is 6, therefore Pt if found in period 6.

4-14. Learning Check


Give the required information in the table below:

Element Valence electron n of the main Period Valence Group


configuration energy level number electron Number

Pt 6s2 4f145d8 6 6 10 10

Fe

5s2 4d4

4 4

6 2
The inner transition metals or the f block are composed of two rows. The first row
is called lanthanides which is also referred to as rare earth metals and the second
row is called the actinides. Each row composed of 14 elements which corresponds
to the maximum number of electrons that f sublevel can accommodate. The 4f for
lanthanides and 5f for the actinides.

You should understand that the valence electrons of the electrons in this block are
those in the ns and (n-2) d. Take note that the in each row, the elements wary in
their valence configuration, hence, they vary in the number of electrons in orbitals
in inner main energy levels.

Consider element Pm which has 61 atomic number:

What is the electronic configuration of Pt?


- 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p6 5s2 4d10 5p6 6s2 4f5

What is the valence electron configuration?


- looking at the electronic configuration, the valence electron
configuration is 6s2 4f5

To what group does Pm is located?

46
Unit IV. The Electronic Structure of the Atom and the Periodic Table

- 2 electron from s and 5 electrons from f, hence valence electron is 7.


Therefore Pm is located in group 7.

To what period does Pm belong?


- Since the highest energy level of Pm as shown in the electronic
configuration is 6, therefore Pm if found in period 6

4-15. Learning Check


Give the required information in the table below:

Element Valence electron n of the main Period Valence Group


configuration energy level number electron Number

Pm 6s2 4f5 6 6 7 7

Cf

7s2 5f4

6 10

7 5
Periodic Trends

Periodic trends are specific patterns on the variation of properties of elements in


relation to their position on the periodic table. Periodic trends, arising from the
arrangement of the periodic table, provide chemists with an invaluable tool to
quickly predict an element's properties. The word “periodic” means that within
each row, or period, the elements show a pattern of characteristics.These trends
exist because of the similar atomic structure of the elements within their
respective group families or periods, and because of the periodic nature of the
elements.

Properties, Structure, and Bonding of the Elements


In the periodic table, if you notice that along each period (from left to right), there
is a change in the nature of elements from metallic to nonmetallic. From right to
left across a period, metallic character increases because the attraction between
valence electron and the nucleus is weaker, enabling an easier loss of electrons.
Metallic character increases as you move down a group because the atomic size is
increasing. When the atomic size increases, the outer shells are farther away. The
principal quantum number increases and average electron density moves farther
from nucleus. The electrons of the valence shell have less attraction to the nucleus
and, as a result, can lose electrons more readily. This causes an increase in
metallic character.

47
Unit IV. The Electronic Structure of the Atom and the Periodic Table

As shown in table 4-3, the change in structure is from metallic to covalent


network to covalent molecular. Melting points are varied and do not generally
form a distinguishable trend across the periodic table. However, certain
conclusions can be drawn: Metals generally possess a high melting point while
Most non-metals possess low melting points. There is also corresponding change
in conductivity.

Table 4-3. A summary of the properties, structure and bonding of the elements
in periods 2 and 3 (Credit from Chem. A UPOU)

Period 2 Li Be B C N O F Ne
Period 3 Na Mg Al Si P S Cl Ar
No. of
valence 1 2 3 4 5 6 7 8
electrons
Type of Substance: Metals are written in bold letters, metalloids are in
outline, the rest are nonmetals

Structure Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
Metallic Covalent Covalent
network molecular

Coordinate Continuous Lattice points


lattice lattice occupied by
molecules/atoms

Bonding Metallic: Attraction Covalent: Intermolecular forces:


between positive Strong covalent Weak forces between
ions and mobile both between molecules
outer electrons atoms Intramolecular forces:
Strong covalent bonds
hold atoms together
Within the molecules

Conductivity Good Poor Except Nil


graphite which is
a good conductor

Melting point Li Be B C N O F Ne
(0C) 186 1278 2300 >3550 -210 -218 -223 -249
Na Mg Al Si P S Cl Ar
97.5 651 660 1420 44 113 -103 -189

48
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Atomic Size

The atomic radius of a chemical element is a measure of the size of its atoms,
usually the mean or typical distance from the nucleus to the boundary of the
surrounding cloud of electrons. Since the boundary is not a well-defined physical
entity, there are various non-equivalent definitions of atomic radius:

 covalent radius (rcov), the half-distance between the nuclei of two atoms
joined in a covalent bond
 van der Waals radius (rvdw), the half-distance between the nuclei of two
atoms of neighboring molecules
 metallic radius (rmet), for metallic elements, the half-distance between the
nuclei of two neighboring atoms in the solid metal
This distance is measured in picometers (pm) or Angstroms (Å), with 1 Å = 100
pm . Atomic
radius
patterns are
observed
throughout
the periodic
table.

49
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Figure 4-19. Atomic radii of the elements in the s and p orbital

Trend:
 Atomic radius increases down a group or family of elements.
 Atomic size gradually decreases from left to right across a period of
elements.

What are two factors that explains the trends of atomic size along a period and
down a group?

 The first factor that explains the increase in atomic size as you go down a
column of the periodic table is the principal quantum number, n, of the
valence electrons. The valence electrons occupy higher levels due to the
increasing quantum number, n. As a result, the valence electrons are
further away from the nucleus as ‘n’ increases. Electron shielding prevents
these outer electrons from being attracted to the nucleus; thus, they are
loosely held, and the resulting atomic radius is large.

 Within a period or series of elements, from left to right, all electrons are
added to the same shell. However, at the same time, protons are being
added to the nucleus, making it more positively charged. The effect of
increasing proton number is greater than that of the increasing electron
number; therefore, there is a greater nuclear attraction. The increasing
positive charge leads to a larger effective nuclear charge, Zeff, “felt” by the
valence electrons which casts a tighter grip on them. This means that the
nucleus attracts the electrons more strongly, pulling the atom's shell closer
to the nucleus. As a result, the atomic radius decreases.

Take note that the shielding factor increases as the number of the inner
electrons increases. There would be more electrons to screen the outer
electrons from the nucleus.

4-16. Learning Check

Referring only to a periodic table, which atom is larger in each pair?


a. Mg or Ba
b. Al or Cl
c. C or Sn

Sizes of Ions

50
Unit IV. The Electronic Structure of the Atom and the Periodic Table

How does the size of an ion compare with the size of its parent atom? Ions may be
larger or smaller than the neutral atom, depending on the ion’s charge. A positive
ion called cation is formed by the removal of one or more electrons while a
negative ion, anion, is formed by gaining electrons from other atom.

Figure 4-20. Relative Sizes of Atoms and their Ions. The Neutral
Atoms are Colored Gray, Cations Red, and Anions Blue.
Trend:

 Same trend as in a neutral atom but the resulting cation is smaller than its
parent atom and a resulting anion is bigger than its parent atom

When an atom loses an electron to form a cation, the lost electron no longer
contributes to shielding the other electrons from the charge of the nucleus;
consequently, the other electrons are more strongly attracted to the nucleus, and
the radius of the atom gets smaller. Similarly, when an electron is added to an
atom, forming an anion, the added electron repels other electrons, resulting in an
increase in the size of the atom.

4-17. Learning Check

Predict which ion is bigger in each pair? Explain your answer.


a. Na+or Rb+
b. Al3+ or Cl-
c. Cl- or I-

51
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Ions that have the same number of electrons are called isoelectronic. Would they
have the same size?

To answer the question, you should take a look on the following information:

Ion O2- F- Na+ Mg2+ Al3+


Number of
electrons 10 10 10 10 10
Nuclear
charge +8 +9 +11 +12 +13
Size, pm 126 119 116 86 68

The ions have the same number of electrons but different nuclear charges
Analyze the trend, does ionic size decrease or decrease with increasing nuclear
charge?

You are right if you answer ionic size decreases as the nuclear charge increases.
For each isoelectronic ions, the higher the nuclear charge, the stronger the
electrons be attracted to the nucleus and therefore the smaller the ion.

Ionization Energy

Ionization energy (IE) is the energy required to remove an electron from a neutral
atom in its gaseous phase. In chemistry, it often refers to one mole of a substance
(molar ionization energy or enthalpy) and is reported in kJ/mol. In atomic physics,
the ionization energy is typically measured in the unit electron volt (eV). Large
atoms or molecules have low ionization energy, while small molecules tend to
have higher ionization energies.

Figure 4-20. Periodic Table Showing First Ionization Energy of Some Elements

52
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Trend:
 The ionization energy of the elements decreases as one moves down a
given group.
 The ionization energy increases as one crosses a period from left to right.

The factors that affect atomic size are the same factors that affect ionization
energy. As you go down the periodic table, it becomes easier to remove an
electron from an atom (i.e., IE decreases) because the valence electron is farther
away from the nucleus.

However, as you go across the periodic table and the electrons get drawn closer
in, it takes more energy to remove an electron; as a result, ionization energy
increases. The lower the IE, the more readily the atom becomes a cation. On the
hand, the higher the IE, the more likely it is the atom becomes an anion.
Generally, elements on the right side of the periodic table have a higher ionization
energy because their valence shell is nearly filled completely. Elements on the left
side of the periodic table have low ionization energies because of their willingness
to lose electrons and become cations. Thus, ionization energy increases from left
to right on the periodic table because the electrons are held tighter by the higher
effective nuclear charge. This is because additional electrons in the same shell do
not substantially contribute to shielding each other from the nucleus, however an
increase in atomic number corresponds to an increase in the number of protons in
the nucleus.

4-18. Learning Check

Based from the Figure 4-17, ionization energy of elements:


Do the elements that form anions have high or low ionization energy?
_________________
What kind of elements form anions, metals or nonmetals? _____________

Which atom in each pair has the larger IE?


a. Na or Rb
b. Li or Li+
c. P or Cl

Electron Affinity
The electron affinity (EA) of an atom is defined as the amount of energy released
when an electron is added to a neutral gaseous atom to form a negative ion, as
demonstrated by the following equation:

53
Unit IV. The Electronic Structure of the Atom and the Periodic Table

A(g) + e−→A−(g) ΔH ≡ EA

Electron affinity is measured for atoms in the gaseous state only, since in the solid
or liquid states their energy levels would be changed by contact with other atoms
or molecules. A molecule or atom that has a more positive electron affinity value
is often called an electron acceptor; one with a less positive electron affinity is
called an electron donor. Together they may undergo charge-transfer reactions.

In ionization energy, the electron concerned is an electron of the atom. In electron


affinity, the electron concerned is an additional electron from another atom.

To properly use electron affinities, it is important to keep track of the sign. For
any reaction that releases energy, the change in energy (ΔE) has a negative value,
and the reaction is called an exothermic process. Electron capture for almost all
non-noble gas atoms involves the release of energy and therefore is an exothermic
process.

Figure 4-21. Periodic Table Showing Electron Affinities of some Elements.

Trend:
 Electron affinity increases across a period
 Electron affinity decreases down a group

EA generally increases across a period in the periodic table, due to the filling of
the valence shell of the atom. For instance, within the same period, a Group-17

54
Unit IV. The Electronic Structure of the Atom and the Periodic Table

atom releases more energy than a Group-1 atom upon gaining an electron because
the added electron creates a filled valence shell and therefore is more stable.
A trend of decreasing electron affinity down the groups in the periodic table
would be expected, since the additional electron is entering an orbital farther
away from the nucleus. Since this electron is farther away, it should be less
attracted to the nucleus and release less energy when added. However, this trend
applies only to Group-1 atoms.

4-19. Concept Check

Predict which atom in each pair will have the highest magnitude of EA.

1. C or F
2. Na or S
3. As or Br

Electronegativity
Electronegativity can be understood as a chemical property describing an atom's
ability to attract or gain electrons. This property exists due to the electronic
configuration of atoms. Most atoms follow the octet rule, having the valence, or
outer shell comprise of 8 electrons. If you can still recall that elements on the left
side of the periodic table have less than a half-full valence shell, the energy
required to lose electron is less than to gain electrons. As a result, the elements on
the left side of the periodic table generally lose electrons when forming bonds.
Conversely, if the valence shell is more than half full, it is easier to pull electron
into the shell than to donate electrons to create a complete valence shell of 8
electrons.

55
Unit IV. The Electronic Structure of the Atom and the Periodic Table

Figure 4-19.Periodic Table Showing Electronegativity Values of Elements

Trend:
 Electronegativity values generally increase from left to right across the
period of the periodic table.

 Electronegativity generally decreases from top to bottom of a group

The increase of electronegativity across a period is due to an increase in nuclear


charge. Alkali metals have the lowest electronegativity values, while halogens
have the highest.

Conversely, electronegativity decreases down a group. This is because atomic


number increases down a group, and thus there is an increased distance between
the valence electrons and nucleus, or a greater atomic radius.

The noble gases possess a complete valence shell and do not usually attract
electrons. The lanthanides and actinides possess more complicated chemistry that
does not generally follow any trends. Therefore, noble gases, lanthanides, and
actinides do not have electronegativity values.

4-20. Learning Check

Which of the following elements in each pair would you predict to


have higher electronegativity?

a. Na or K d. K or Rb
b. S or Cl e. N or O
c. P or Si

Note that there is little variation among the transition metals. This is because their
metallic properties affect their ability to attract electrons as easily as the other
elements.

Feedback

A. Answer the following questions based on the given periodic table below with
the hypothetically assigned elements.
1 18
2 1 14 15 16 17 L
3
Y

56
Unit IV. The Electronic Structure of the Atom and the Periodic Table

3 4 5 6 7 8 9 10 1 12 H
1
T

A
M K

_____ 1. The inner transition metal.


_____ 2. The element with the biggest atomic size.
_____ 3. The element classified as alkali metal.
_____ 4. The element classified as alkaline earth metals.
_____ 5. The element classified as metalloid.
_____ 6. The transition element.
_____ 7. The element classified as halogen.
_____ 8. The lightest of the noble gasses.
_____ 9. Element with electronic configuration ending with f.
_____10. Element with four valence electron.
_____11. Element with electronic configuration ending in d.
_____12. Element with seven valence electrons.
_____13. Element with eight valence electron.
_____14. Element with one occupied main energy level.
_____15. Element with the highest electronegativity.
_____16. Element of smallest atomic size.
_____17. Element with -1 valence or oxidation number.
_____18. Element with the lowest ionization energy.
_____19. Element the highest electron affinity.
_____20. Element with most metallic property.

A. MULTIPLE CHOICE. Choose the correct answer on the given choices of the
following questions.

1. Which one of the following does not increase while moving down the
group of the periodic table ?
a. Atomic radius
b. Metallic character
c. Valence electrons
d. Shells in the atoms

2. The Newlands Law of Octaves for the classification of elements was


found to be applicable only up to the element :

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

a. Potassium
b. Calcium
c. Cobalt
d. Thorium

3. An element X forms an oxide X2O3. In which group of Modern periodic


table is this element placed?
a. Group 2
b. Group 3
c. Group 5
d. Group 13

4. The following elements are written with their atomic number. The element
having the largest atomic is :
a. Na – 11
b. Mg – 12
c. K – 19
d. Ca – 20

5. Where would you locate the element with electronic configuration 2,8 in
the modern periodic table?
a. Group 8
b. Group 18
c. Group 10
d. Group 16

6. Which of the following statements is not correct about the trends when
going from left to right across the periods of the periodic table ?
a. The elements become less metallic in nature
b. The number of valence electrons increases
c. The atoms lose their electrons more easily
d. The oxides become more acidic

7. The elements A, B, C, D and E have atomic numbers 9, 11 , 17,12, and 13


respectively . The pair of elements which belongs to the same group of the
periodic table is
a. A & B
b. B & D
c. A & C
d. D & E

8. Who was the first scientist to notice the periodicity of the elements?
a. Alexandre-Emile Béguyer de Chancourtois
b. Dmitri Mendeleev
c. O.J. Simpson
d. Henry Moseley

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

9. Of the atoms below, __________ is the most electronegative.


a. Si
b. Cl
c. Rb
d. S

10. Who classified the known elements into eight groups?


a. John Newlands
b. Dmitri Mendeleev
c. Alexandre-Emile Béguyer de Chancourtois
d. Erwin Schrödinger

11. How did Newlands classify the elements?


a. By properties
b. By weight
c. By mass
d. By what element was best

12. Who created the modern version of the periodic table?


a. Dmitri Mendeleev
b. Erwin Schrödinger
c. Alexandre-Emile Béguyer de Chancourtois
d. Andre the Giant

13. How did Henry Moseley re-sequence the periodic table?


a. By nuclear charge
b. By atomic weight
c. By atomic height
d. None of the above

14. Who found a relationship between the X-ray wavelength of an element


and its atomic number?
a. Henry Moseley
b. Dmitri Mendeleev
c. John Newlands
d. Boris Yeltsin

15. Who was the first person to discover an element?


a. Aristotle
b. Hennig Brand
c. Jimmy Neutron
d. Dmitri Mendeleev

16. What is the law of triads?

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

a. When ordered by atomic weight, the element between two in a


threesome is an average of the other two
b. When ordered by atomic mass, the element between two in a
threesome is an average of the other two
c. Elements in threes, organized by weight, always have the exact
same properties.
d. There are only three elements

17. Who discovered the Law of Triads?


a. Johann Dobereiner
b. Jean Baptiste Dumas
c. Leopold Gmelin
d. Randy Jackson

18. How did Dmitri Mendeleev arrange the elements in his periodic table?
a. Atomic mass corresponding to relative molar mass
b. Atomic weight corresponding to relative molar mass
c. Atomic mass corresponding to relative molar weight
d. Atomic weight corresponding to relative molar weight

19. What elements did Lothar Meyer's periodic table include?


a. Roughly half of those known
b. All of them
c. Three of them
d. None of them

20. The periodic law states that


a. similar properties recur periodically when elements are arranged
according to increasing atomic number
b. similar properties recur periodically when elements are arranged
according to increasing atomic weight
c. similar properties are everywhere on the periodic table
d. elements in the same period have same characteristics

Summary of the Unit

 Atomic emission spectra are produced when excited electrons return to the
ground state.
 The emitted light corresponds to energies of the specific electrons.
 Atoms of individual elements emit light at only specific wavelengths,
producing a line spectrum rather than the continuous spectrum of all
wavelengths produced by a hot object.

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

 Niels Bohr explained the line spectrum of the hydrogen atom by assuming
that the electron moved in circular orbits and that orbits with only certain
radii were allowed.
 The Bohr model postulates that electrons orbit the nucleus at fixed energy
levels.
 Orbits further from the nucleus exist at higher energy levels.
 When electrons return to a lower energy level, they emit energy in the
form of light.
 Lines in the spectrum were due to transitions in which an electron moved
from a higher-energy orbit with a larger radius to a lower-energy orbit
with smaller radius. The orbit closest to the nucleus represented the
ground state of the atom and was most stable; orbits farther away were
higher-energy excited states. Transitions from an excited state to a lower-
energy state resulted in the emission of light with only a limited number of
wavelengths. Bohr’s model could not, however, explain the spectra of
atoms heavier than hydrogen.
 Louis de Broglie proposed that all particles could be treated as matter
waves with a wavelength
 Erwin Schrödinger proposed the quantum mechanical model of the atom,
which treats electrons as matter waves.
 The Heisenberg uncertainty principle states that we can't know both the
energy and position of an electron. Therefore, as we learn more about the
electron's position, we know less about its energy, and vice versa
 Electrons have an intrinsic property called spin, and an electron can have
one of two possible spin values: spin-up or spin-down. Any two electrons
occupying the same orbital must have opposite spins.
 The Schrödinger wave equation replaced the Bohr ideas about electron
location with an uncertainty factor. The location of the electron can only
be given as a probability that the electron is somewhere in a certain area.
 Quantum numbers provide important information about the energy and
spatial distribution of an electron.
- The principal quantum number n can be any positive integer that
describes the relative distance of valence electrons to the nucleus.
- The azimuthal quantum number l can have integral values
between 0 and n − 1; it describes the shape of the electron
distribution.
- The magnetic quantum number ml can have 2l + 1 integral values,
ranging from −l to +l, and describes the orientation of the electron
distribution.
- Spin quantum number (ms) designates the direction of the electron
spin and may have a spin of +1/2, represented by↑, or –1/2,
represented by ↓.

 The arrangement of atoms in the periodic table results in blocks


corresponding to filling of the ns, np, nd, and nf orbitals to produce the

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

distinctive chemical properties of the elements in


the s block, p block, d block, and f block, respectively.

 Below is the summary of the general periodic and group trends:

Atomic Radius
- Definition: A measure of a neutral atom’s size based on the radius of
its volume as a sphere
- Increases going down because there are more energy levels of
electrons and therefore more shielding
- Increases going left because as you move across a period right-to-left,
an atom loses a positively charged proton and therefore its electrons
become slightly less tight and compact
Ionic Radius
- Definition: Same as atomic radius, but for the size of a charged ion,
not a neutral atom
- Increases for anions (-) because they gain an electron, which leads
to more shielding
- Decreases for cations (+) because they lose an electron, which
means less shielding
First Ionization Energy
- Definition: The amount of energy needed to remove an outer electron
from an atom and make it into an ion
- Increases going right because there are more protons in the
nucleuspulling in electrons, so it requires more energy to remove an
outer electron
- Increases going up because there are fewer energy levels and less
shielding, so the outer electrons are more tightly held by the nucleus
Metallic Character/Metallic Reactivity
- Definition: The tendency of an atom to lose an electron (a key
characteristic of metals is they lose electrons to become cations)
- Increases going left because metals are on the left side of the periodic
table and they have fewer protons in their nucleus that are holding in
the atom’s electrons
- Increases going down because there is more shielding, so outer
electrons are easier to lose
Non-Metal Reactivity/Electron Affinity
- Definition: The tendency of an atom to gain an electron (a key
characteristic of non-metals is they gain electrons to become anions)
- Increases going right because non-metals are on the right side of the
periodic table and they have more protons in their nucleus that attract
outer electrons
- Increases going up because there are less electron energy levels and
therefore a greater attraction to the nucleus for electrons
Electronegativity

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

- Definition: The tendency of an atom to attract a shared electron in a


chemical bond
- Increases going right because there are more protons in the nucleus
attracting outer electrons
- Increases going up because there are fewer energy levels of electrons
shielding/repelling new outer electrons

Student Reflection on Learning

After using and studying this module, did you meet your expectations on what to
learn in this module? How well you used the instruction given in the module?
How would you used your learnings in this module in your everyday life? What
would you like to learn more?

References:

Bucat, R.B., (ed). 1983. Elements of Chemistry. Australia: Australian Academy of


Science.
Cracolice, Mark, Peters, Edward, Introductory Chemistry, 4th ed. Brooks/Cole
Cengage Learning, Belmont, Calif., 2007.
(Farmington, 2008)2004. "Molecular Geometries." Chemistry
Foundations and Applications. Volume 3. Prentice Hall, 2008, p. 362-421.
Fleming, D.G., Manz, J., Sato, K., and Takayanagi, T. (2014). Fundamental
change in the nature of chemical bonding by isotopic
substitution. Angewandte Chemie International Edition, 53(50): 13706–
13709.
Nivaldo J. Tro, Chemistry: A Molecular Approach, 1st ed. Upper Saddle
River: Pearson
Padolina, Ma. Cristina A. 1990. Chemistry A: Fundamental Concepts of
Chemistry. UPOU
Pauling, L. (1931). The nature of the chemical bond. Application of results
obtained from the quantum mechanics and from a theory of paramagnetic
susceptibility to the structure of molecules. Journal of the American
Chemical Society, 53(4): 1367-1400.
Petrucci, Ralph H. General Chemistry: Principles and Modern Applications.

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Unit IV. The Electronic Structure of the Atom and the Periodic Table

Upper Saddle River, NJ: Pearson/Prentice Hall, 2007. Print.


Zumdahl, Steven S., and Susan Arena. Zumdahl. Chemistry. Boston: Houghton
Mifflin, 2007. Print.

https://chem.libretexts.org/Bookshelves/
Physical_and_Theoretical_Chemistry_Textbook_Maps/
Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/
Chemical_Bonding/Fundamentals_of_Chemical_Bonding

http://limestone.k12.il.us/teachers/rhebron/Chem_HO/C04_Naming_Writing.html

https://chem.libretexts.org/Courses/University_of_Illinois%2C_Springfield/UIS
%3A_CHE_267_-_Organic_Chemistry_I_(Morsch)/Chapters/
Chapter_01%3A_Structure_and_Bonding/1.12%3A_Polarity_of_Molecules
ll, 2008, p. 362-421.

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