CHEMISTRY FOR

ENGINEERS - LEC

2nd Semester AY 2020 - 2021

 QUANTUM THEORY
AND ELECTRONIC
STRUCTURE OF ATOM
 LEARNING OUTCOMES

❖ Describe waves in terms of frequency,

wavelength, and amplitude
❖ Use Planck’s equation to calculate the energy
of a photon from its wavelength or frequency
❖ Differentiate Bohr Model from Quantum
Mechanics model of an atom.
❖ Discuss the different quantum numbers
❖ Explain Pauli Exclusion Principle, Aufbau
Principle and Hund’s Rule
❖ Use the Pauli exclusion principle, Aufbau
principle and Hund’s rule to write electron
configurations for atoms and ions of main
group elements
 INC ANDESCENT AND
FLUORESCENT LIGHTS

• Electricity is supplied to “excite” a substance, and that

excitation somehow gives rise to light
• The filament in a standard incandescent light bulb is a length of
very thin tungsten wire. When an electric current is passed
through the filament, the resistance of the wire causes some
energy to be dissipated as heat. The tungsten is heated until it
is “white hot,” and it emits visible light Because the tungsten
wire is so thin, it heats up quickly to a high temperature. But it
is a metal that is behaving similarly to the blacksmith’s iron.
• The specific color of light emitted by either metal is related to
its temperature. The dull red color of the iron as it is first
heated suggests that, although warm, the piece is not yet
especially hot. The move toward orange as the piece remains in
the fire, or the white light from the tungsten filament suggests
higher temperatures.
 INC ANDESCENT AND
FLUORESCENT LIGHTS

• Fluorescent lights operate differently. Instead of heating a

metal, an arc of electricity travels through a gas. An arc occurs
whenever electricity passes through a medium that does not
conduct current very well. The discharge of static electricity
that sometimes occurs when you touch a light switch provides
a painful, personal example of an electric arc.
• Figure 6.2 illustrates the processes in a fluorescent light bulb.
In such a bulb, specific atoms such as mercury interact with the
electricity and become “excited.” This means that they are in a
state of higher than normal energy. To return to their normal
state, these excited atoms emit light. That light interacts with a
material, called a phosphor, that coats the inside surface of the
fluorescent tube. This phosphor then emits light of many
colors, giving rise to what we perceive as white light coming
from the bulb
 INC ANDESCENT AND
FLUORESCENT LIGHTS

• What happens when atoms get excited or relax?

• Why does the bulb need to use the phosphor? Could elements
other than mercury be used?
• All of these questions can be answered as we also establish
some of the foundation upon which to build a deeper
understanding of chemical bonding.
• Therefore, we proceed to learn how we view atoms in
modern chemistry and physics and how that understanding
provides the insight needed to light the world.
• Because the interaction of light with atoms played a crucial
role in the development of our model for the structure of
atoms, we begin with a look at the properties of light itself.
 ELECTROMAGNETIC SPECTRUM

• Visible light is a more accurate term for what we usually refer

to simply as light.
• The light that our eyes can detect comprises only a small
portion of the possible electromagnetic spectrum and
accounts for only a small part of the emission of most light
bulbs. Other familiar forms of electromagnetic radiation
include radio waves, microwaves, and X-rays. The origin of the
word electromagnetic lies in the nature of light.
• Historically, light has been described as a wave traveling
through space.
• One component is an electric field, and another is a magnetic
field (Figure 6.3).
• To understand the wave nature of light, then, we should
probably be familiar with the general features of waves.
 The Wave Nature of Light

• Many of the features of light that we encounter can be

explained as properties of waves.
• The central characteristics of a wave can be defined by
four variables: wavelength, frequency, velocity, and
amplitude.
• Figure 6.4 illustrates the definition of these terms.
• The wavelength of any wave is the distance between
corresponding points on adjacent waves. In the illustration,
for example, the wavelength (designated as λ and measured
in units of length) is defined as the distance between peaks.
We could also define the wavelength as the distance
between valleys, and the value would be the same.
• The amplitude is the size or height of the wave
The Wave Nature of Light
 The Wave Nature of Light

• Speed, wavelength, frequency, and amplitude are characteristics that can

describe any wave. But because we are interested in light, it should help to
compare these quantities with some familiar properties of light.
• If someone asks you to compare two different lights, one of the things you
would probably consider is how bright each one appears. How does this relate
to the wave parameters we’ve defined?
• In the wave model for light, the amplitude determines the brightness of the
light: the larger the amplitude of the wave, the brighter the light will appear.
Another property that you would surely consider in comparing two lights is
color. In the wave model, both wavelength and frequency correspond to the
color of the light. How can these two seemingly different properties of the
wave both correspond to color?
• The answer can be seen in Equation 6.1. Because the speed of light must
remain constant, specifying either the frequency or the wavelength
automatically fixes the value of both of those properties of a light wave. So, we
could say that the frequency and the wavelength are simply two different ways
of expressing the same information.
 PROBLEM

Neon lights emit an orange-red colored glow.

This light has a wavelength of 670 nm. What is
the frequency of this light?
 PROBLEM - SOLUTION

Given: λ = 670 nm
Req’d: ν

Answer: ν = 4.5 x 1014 /s

 The Wave Nature of Light

• Generally, we think of a lamp as something emitting visible light. But for some
specific applications, bulbs are designed to produce radiation in different regions
of the electromagnetic spectrum.
• Heat lamps in fast food restaurants, for example, emit
infrared radiation to keep French fries warm. Compared with ordinary
incandescent bulbs, heat lamps are designed to emit a range of wavelengths
shifted toward the IR region. These bulbs appear red to our eyes because that is
the visible color that is adjacent to the infrared.
• Moving to the opposite end of the visible spectrum, lamps designed to emit
ultraviolet radiation are used both as “black lights,” causing various dyes to glow,
and in tanning beds. Our eyes do not detect ultraviolet light, but these
lamps appear purple because the range of wavelengths they emit overlaps the
violet end of the visible spectrum.
• Microwave ovens, radios, televisions, wireless telephones, and wireless
computer networks all function by exploiting other specific regions of the
electromagnetic spectrum.
 The Particle Nature of Light

• The wave model of electromagnetic radiation can explain many observed

properties of light. In the early 1900s, however, scientists developed more
sophisticated apparatus and carried out experiments that challenged the wave
model of light. One pivotal group of experiments involved the observation of
what came to be known as the photoelectric effect, in which light strikes a
piece of metal and causes electrons to be ejected.
• Figure 6.7 is a schematic diagram of a typical photoelectric effect experiment.
At the heart of the experiment is light shining on a piece of metal. If the metal
is enclosed in a container under vacuum so that there are very few surrounding
gas molecules to interfere, then we can detect electrons emitted from the
metal under certain conditions.
• Energy from the light is transferred to the electrons in the metal. If an electron
picks up enough energy, it can break free from the surface of the metal. The
more energy given to the electron, the faster it will travel after it leaves the
metal.
 The Particle Nature of Light

• After studying the photoelectric effect under several conditions, scientists made three
observations.
* A certain minimum frequency is required for electrons to be emitted.
* Kinetic energy is directly proportional to frequency.
* The number of electrons emitted from the surface was not dependent on
intensity.
• Scientists realized that frequency, not intensity, controlled whether or not electrons were
emitted. Under classical wave theory electrons would be ejected at any frequency as long
as it was intense enough, but this doesn’t happen. Since this dependency on frequency
couldn’t be classical physics, scientists had to turn to quantum theory.
• Despite elaborate efforts to make these observations of the photoelectric effect
conform to existing wave concepts, consistent explanations of light based solely on waves
ultimately failed. The only way to explain all of the experimental results was to invoke the
notion of wave-particle duality, which says that, in some situations, light is best described
as a wave, whereas in other cases, a particle description works better. It’s important to
realize that this does not mean that there are two different kinds of light! It simply means
that neither the wave model nor the particle model provides an accurate description of
all of the properties of light
 The Particle Nature of Light

• Albert Einstein proposed that light could be described as a collection of packets of

energy, called photons. Bright light has many photons, whereas dim light has few. The
energy of a photon of light has been shown to be proportional to its frequency, leading
to a simple equation:
 PROBLEM

The laser in a standard laser printer emits

light with a wavelength of 780.0 nm. What is
the energy of a photon of this light?
 PROBLEM

Given: λ = 780.0 nm
Req’d: E

Answer: 2.547 x 10-19 J

 ATOMIC SPECTRA

• In the seventeenth century, Sir Isaac Newton showed that

visible (white) light from the sun can be broken down into
its various color components by a prism. The spectrum
obtained is continuous; it contains essentially all
wavelengths between 400 nm and 700 nm.
• Each element has a characteristics spectrum that can be
used to identify it. In the case of sodium, there are two
strong lines in the yellow region at 589.0 nm and 589.6 nm.
The line account for the yellow color of the sodium vapor
lamps used to illuminate highways
Line spectra for Sodium Atom
Continuous Spectrum
 ATOMIC SPECTRA

• When an atom emits light, it is releasing energy to the

surrounding world.
• When light is emitted, the atom goes from a higher energy
state to a lower energy state, and the emitted photon
carries away the energy lost by the atom. The fact that only
a few wavelengths of light are emitted from a particular
atom is direct evidence that the atom can exist in only a
few states with very specific energies.
 Bohr Model

• Electrons occupy stable orbits from which they cannot

deviate without first absorbing or emitting energy in the
form of light.
• For an electron to move from an inner orbit to an outer
orbit, as depicted in Figure 6.10, energy must be absorbed
E =hν.
• The new distribution or configuration of electrons consists
of a grouping that is not at the lowest possible energy and
is therefore referred to as an excited state.
• One of the most powerful driving forces in nature is the
tendency to move toward states of lower energy. So an
excited state of an atom cannot exist indefinitely. It will
return to the lowest energy state, or ground state, by
emitting radiation.
 Bohr Model

•
The energy absorbed or emitted
from the process of electron
promotion or demotion can be
calculated by the equation:
1 1
E = −RH ( nf2 - ni2 )
where RH is the Rydberg constant,
2.18  10−18 J, and ni and nf are the
initial and final energy levels of the
electron.
 QUANTUM MECHANICAL
MODEL OF AN ATOM

• Bohr’s theory for the structure of hydrogen

atom was highly successful. However, the
extension of Bohr’s idea to atoms with two or
more electrons gave, at best, only qualitative
agreement with the experiment. Calculated
energies and wavelengths for Helium atoms are
of the order of 5%.
• A new approach was required to treat electrons
in atoms and molecules.
 Wave Nature of Matter

• In 1924, a young French scientist Louis de

Broglie made a revolutionary suggestion.
• He reasoned that if light show the behavior of
particles (photons) as well as waves, then
perhaps an electrons, which Bohr has treated as
a particle, could behave like a wave. In the few
years, de Broglie postulate was confirmed
experimentally.
 Heisenberg Uncertainty

• Heisenberg showed that the more precisely the

momentum of a particle is known, the less precisely is its
position known:

• In many cases, our uncertainty of the whereabouts of an

electron is greater than the size of the atom itself!
Quantum Mechanics

Erwin Schrödinger
developed a mathematical
treatment into which both
the wave and particle
nature of matter could be
incorporated.
It is known as quantum
mechanics.
 Quantum Mechanical Model

• Energy is quantized .
• A quantum is the amount of energy needed to move
from one energy level to another.
• Since the energy of an atom is never “in between”
there must be a quantum leap in energy.
• In 1926, Erwin Schrodinger derived an equation that
described the energy and position of the electrons in
an atom
 Quantum Mechanics

• The wave equation is designated with a lower case

Greek psi (ψ).
• The square of the wave equation, ψ2 gives a
probability density map of where an electron has a
certain statistical likelihood of being at any given
instant in time.
 Quantum Numbers

• Solving the wave equation gives a set of wave

functions, or orbitals, and their corresponding
energies.
• Each orbital describes a spatial distribution of
electron density.
• An orbital is described by a set of three
quantum numbers : principal quantum number
n, secondary quantum number l and magnetic
quantum number ml
 1. Principal Quantum Numbers
(n)

• The principal quantum number, n, describes the

energy level on which the orbital resides.
• Energy level - represent a region in space
where you can find the electron
• The values of n are integers ≥ 0.
• Maximum number of electrons that an energy
level can hold is equal to 2n2
where n - energy level
1. Principal Quantum Numbers
(n)
 2. Secondary Quantum Numbers (l)

• This quantum number defines the shape of the

orbital.
• Allowed values of l are integers ranging from 0
to n − 1.
• We use letter designations to communicate
the different values of l and, therefore, the
shapes and types of orbitals

Orbitals - a region in space with a particular shape where one

or 2 electrons can be found
An orbital can hold a maximum number of two electrons.
 3. Magnetic Quantum Numbers (ml)

• Describes the three-dimensional orientation

of the orbital.
• Values are integers ranging from -l to l:
−l ≤ ml ≤ l.
• Therefore, on any given energy level, there
can be up to 1 s orbital, 3 p orbitals, 5 d
orbitals, 7 f orbitals.
• Orbitals with the same value of n form a
shell.
• Different orbital types within a shell are
subshells.
3. Magnetic Quantum Numbers
(ml)
S orbital

• Value of l = 0.
• Spherical in shape.
• Radius of sphere
increases with increasing
value of n.
 p orbital

• Value of l = 1.
• Dumb bell in shape
• Have two lobes with a node between them.
d orbital

• Value of l is 2.
• Four leaf or
clover in shape
• Four of the five
orbitals have 4
lobes; the other
resembles a p
orbital with a
doughnut around
the center.
f orbital

• Value of l is 3.
 4. Magnetic Spin Numbers (ms)

• In the 1920s, it was

discovered that two
electrons in the same
orbital do not have exactly
the same energy.
• The “spin” of an electron
describes its magnetic field,
which affects its energy.
 4. Magnetic Spin Numbers (ms)

• This led to a fourth

quantum number, the spin
quantum number, ms.
• The spin quantum number
has only 2 allowed values:
+1/2 and −1/2.
 PROBLEM

Given the following sets of quantum numbers,

indicate those that could not occur and explain
your answer.

a. 1, 0, 0 , ½

b. 1, 1, 0, -1/2

c. 4, 2, -2, 0
 PROBLEM - ANSWERS

Given the following sets of quantum numbers, indicate those

that could not occur and explain your answer.

a. 1, 0, 0 , ½ - valid set of quantum numbers

b. 1, 1, 0, -1/2 - not valid l = 1 : when n=1 , l =0

c. 4, 2, -2, 0 - not valid ms= 0 : ms = +1/2 or -1/2

 PAULI EXCLUSION PRINCIPLE AND
ELECTRON CONFIGURATION

• The Pauli exclusion principle states that no two

electrons in an atom may have the same set of four
quantum numbers.
• (Loosely speaking, this is the wave equivalent of saying that
two particles cannot occupy the same space.) If two
electrons have the same values for n, l, and ml, then they
must have different spin quantum numbers (ms). The major
consequence of this principle is that no more than two
electrons can occupy any orbital. If two electrons occupy
the same orbital, they must be spin paired, one with spin up
and the other with spin down.
 Electronic Configuration

• Is the distribution of the electrons among

its sublevels
• Arrangement of electrons in sublevels
• The electrons may be distributed using the
AUFBAU PRINCIPLE or building up
principle. “All possible orbitals available to
an electron, it will occupy the one with the
least energy”

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d,
6p, 7s, 5f, 6d, and
7p
 E L E C T RO NIC
C O N F IGURATION
 Orbital Diagram

• Each box represents one

orbital.
• Half-arrows represent the
electrons.
• The direction of the arrow
represents the spin of the
electron.
Hund’s Rule

“For degenerate
orbitals, the lowest
energy is attained
when the number of
electrons with the
same spin is
maximized.”
 PROBLEM

Sulfur may be an important element in emerging

lighting technology. What is the electron
configuration of a sulfur atom? Orbital diagram?

How about your sulfur ion, S2- ?

 PROBLEM - SOLUTION

Sulfur has 16 electrons, so we can place two in 1s, two in

2s, six in 2p, two in 3s, and four in 3p to get 16. The
electron configuration is
1s22s22p63s23p4

S2- 1s22s22p63s23p6
 REFERENCES

Hill, John W. (2013). Chemistry for Changing Times. New York:

Prentice Hall

Masterton, William, et al. General Chemistry. Philippines:

Cengage Learning Asia Pte Ltd

Stoker, H. Stephen (2016). General Chemistry. Andover:

Cengage Learning Asia Pte Ltd.

Zumdahl, Steven S. (2015). Introductory Chemistry: A

Foundation. USA: Cengage Learning Asia Ptd Ltd., USA