Lecture No.

1
(The Electronic Structure of Atoms)

Lecturer: Prof. Allan N. Soriano, Ph.D. Ch.E.

Email: allannsoriano@yahoo.com
Content
• Atomic Models
• Quantum Mechanics
• Electronic Configuration
• Periodic Relations of Elements
 Atomic Models

 Democritus (400 BC)

 He theorized that matter could not be divided into
smaller and smaller pieces, and eventually the smallest
possible piece would be obtained.
 He named the smallest piece of matter “atomos”
meaning “not to be cut.”
 Atomic Models (Cont.)

 Aristotle (350 BC)

 He modified an earlier theory that matter was made
of four “elements”: earth, fire, water and air.
 He also rejected the idea of “atomism” of matter.

Fire

Earth Air

Water
 Atomic Models (Cont.)

 John Dalton (1800)

 He proposed a modern model based on experimentation.
Dalton’s Atomic Theory:
1. Elements are composed of extremely small particles called
atoms. All atoms of the same element are alike, and atoms
of different elements are different.
2. The separation of atoms and the union of atoms occur in
chemical reactions. In these reactions, no atom is created or
destroyed, and no atoms of one element are converted into
an atom of another element.
3. A chemical compound is the result of the combination of
atoms of two or more elements. A given compound always
contains the same kinds of atoms combined in the same
proportions.
 Atomic Models (Cont.)

Dalton’s Billiard Ball Model:

“Atoms are solids and indivisible.”

 Atomic Models (Cont.)

 J. J. Thomson (1900)
 He discovered electron and proposed a model of the
atom called “Plum Pudding Model.”

“Atoms were made

from a positively
charged substance
with negatively
charged electrons
scattered about.”
 Atomic Models (Cont.)

 Ernest Rutherford (1910)

 He proposed that atoms are mostly empty space and
negative electrons orbit a positive nucleus using the
“Gold Foil Experiment.”

The Gold Foil Experiment.

 Atomic Models (Cont.)

Rutherford’s Model:

“A nucleus exists in th
e center of the atom.”
“The nucleus contains
protons and neutrons
which together accou
nt for the mass.”
“Electrons, which occupy most of the total volume
of the atom, are outside the nucleus and move rapi
dly around it.”
 Atomic Models (Cont.)

 NeilsBohr (1913)
 He proposed an improved atomic model.

“Electrons move in defi

nite orbits around the
nucleus.”
“These orbits, or energ
y levels are located at
certain distances from
the nucleus.”

The Bohr’s Model.

 Atomic Models (Cont.)

Nuclear Bohr Model of Hydrogen Atom:

“Electrons normally
exist in the lower en
ergy state (ground st
ate).”
“When an electron ju
mps into higher ener
gy state it is said to
be in an exited
state.”
 Atomic Models (Cont.)

 Werner Heisenberg (1925)

 Theorized that it is impossible to know simultaneously
both the velocity and position of a particles
(Heisenberg Uncertainty Principle).
 The probable location of an electron is based on how
much energy the electron has.
 Atomic Models (Cont.)

Electron Cloud Model:

“Electron cloud is a spac

e in which electron are li
kely to be found.”
“Electrons whirl about th
e nucleus billion of time
s in 1 second.”
“They are not moving ar
ound in random pattern.
”
 Quantum Mechanics
THE WAVE NATURE OF LIGHT

 Electromagnetic Radiation
 Light travels through space in a wave motion.
 Quantum Mechanics (Cont.)
Definitions

Speed of light (c)

– equivalent to 2.998 x 108
m/sec.
c = λν

Wavelength (λ) – the distance between two Frequency (ν) – is the

similar points on two successive waves. It shoul number of waves that pass a
d be expressed in meters. (1nm = 10-9 m). given spot in a second, this is
the reciprocal of second (1/s =
Amplitude (a) – height of a crest or depth of hertz).
a trough.
Intensity (brightness) of Radiation – i
s proportional to the square of amplitude (a2).
 Quantum Mechanics (Cont.)

Colors of Visible Spectrum:

Color Wavelength, nm
Violet 400 – 450
Blue 450 – 500
Green 500 – 570
Yellow 570 – 590
Orange 590 – 620
Red 620 – 750

Sample Problem:
What is the frequency of red light with a wavelength of
700nm and violet light with a wavelength of 400nm?
 Quantum Mechanics (Cont.)

 Heinrich Hertz
 Generated electromagnetic waves with long wavelengths
larger than those of visible light and who demonstrated that
long wavelength radiation exhibits the same phenomena as
light does.

Electromagnetic
Radiation
(Spectra).
 Quantum Mechanics (Cont.)

THE PARTICLE NATURE OF LIGHT

 Max Plank
 Proposed the quantum theory of radiant energy.
 Suggested that radiant energy could be absorbed or
given off only in definite quantities called quanta.
E = hv = hc / λ
h – Plank’s constant (6.626 x 10-34 J-s)
 Albert Einstein
 Proposed that Plank’s quanta were discontinuous bits of
energy called photons.
 Quantum Mechanics (Cont.)

Sample Problem:
Consider a violet light with a wavelength of 400nm.
(a) Calculate the energy, in joules, of one photon
of this light.
(b) Calculate the energy in kilojoules of one mole
of such photons.
 Quantum Mechanics (Cont.)

ATOMIC SPECTRA
 Isaac Newton
 Showed that visible (white light) from the sun can be
broken down into its various component by a prism.
Definitions
Continuous Spectrum – spreading out Absorption Spectrum – when
into a wide range band of the white light. continuous radiation (white light)
passes through a substance, certain
Emission Spectrum – When an element wavelengths of radiation may be
absorbs sufficient energy (from a flame or absorbed. These wavelengths are
electric arc), it emits radiant energy in the form characteristics of a substance that
of light. When this radiation is passed through absorbs the radiation and pattern of
a prism, it separates into a component wave these lines are referred to as an
length. absorption spectrum.
 Quantum Mechanics (Cont.)

“Every element has its own unique line spectrum, t

herefore these spectra are characteristics of an ato
m’s electronic structure .”
 Quantum Mechanics (Cont.)

Bohr’s Theory:
1. The electron of the hydrogen atom can exist only in certain
circular orbits (energy levels or shell).
2. The electron has a definite energy characteristic of the orbit
in which it is moving.
3. When an electron of an atom is as close to the nucleus, it is
in the condition of the lowest energy called the ground state.
When an atoms are heated in an electric arc or Bunsen
burner, electron absorbs energy and jump to outer levels,
which are higher energy states (excited state).
4. When an electron falls back to a lower level, it emits a
definite amount of energy. The energy difference between
the high-energy state and low-energy state is emitted in the
form of a quantum of light.
 Quantum Mechanics (Cont.)

E = -RH / n2
Where: E – energy of the electron
RH – Rydberg Constant (2.180 x 10-18 J)
n – energy level
ΔE = hν = Ehi – Elo
hv = -RH[(1/nhi2) – (1/nlo2)]
v = [RH/h] [(1/nlo2) – (1/nhi2)]
Sample Problem:
What are the frequency and wavelength of the line
in the hydrogen spectrum that corresponds to an
electron transition from n=3 level to n=2 level?
 Quantum Mechanics (Cont.)

The Relationship
between Electron
Transitions of a
Hydrogen Atom
and the Spectral
Lines.
 Quantum Mechanics (Cont.)

The Relationship between Electron Transitions of a Hydro

gen Atom and the Spectral Lines:

 Since electron transitions to n=1 level (Lyman series) release more energy
than those to the n=2 level (Balmer series), the wavelength s of the lines in
Lyman series are shorter than those of the Balmer series.

 Balmer series occur in visible region.

 The lines in the Lyman series occur in the ultraviolet region.
 The lines of the Paschen series (n=3) occur at wavelengths longer than
Balmer series. It appears in the infrared region.
 Quantum Mechanics (Cont.)

QUANTUM MECHANICAL MODEL

 Louis De Broglie
 He reasoned that if light could show the behavior of
particles (photons) as well as waves, then perhaps an
electron, which Bohr had treated as particle, could behave
like a wave. (Dualistic Nature of Light).
 Erwin Schrödinger
 Formulated wave equation that relates the energy of the
electron to its position in the atom.
 Solutions of these equations give rise to quantum
numbers.
 Quantum Mechanics (Cont.)

QUANTUM NUMBERS – set of numbers that describes an

electron orbital

1. First Quantum Number ( Principal ) – (n) – indicates the

main energy level by the electron. It defines the total energy
of the electrons and has values from (1 to 7).

2. Second Quantum Number ( Azimuthal ) – (l) – it describes

the way the electron moves around the nucleus or the shape
of the probability distribution. The values range from 0 to (n-
1).
 Quantum Mechanics (Cont.)

n l Spectral Lines
1 0 s type (sharp)
2 0 s
1 p type (principal)
3 0 s
1 p
2 d type (diffuse)
4 0 s
1 p
2 d
3 f type (fundamental)
Quantum Mechanics (Cont.)
 Quantum Mechanics (Cont.)

3. Third Quantum Number ( Magnetic ) – (m l ) – it defines the

possible orientation of the electrons in space. The values are
from –l through 0 to +l.
l ml Number of orbitals (2l + 1)
0 0 1
1 -1, 0, +1 3
2 -2, -1, 0, +1, +2 5

4. Fourth Quantum Number ( Spin ) – (m s) – it takes into

account the spinning of the electron around its own axis as it
moves about the nucleus. The spin is either clockwise or
counterclockwise. The values are +1/2 (clockwise) and -1/2
(counterclockwise).
 Quantum Mechanics (Cont.)

Concepts:

 Hund’s Rule
 When filling a set of degenerate energy levels, the
electron enter the orbitals singly, with spins in the same
direction (same as s number), until the set is half filled,
before they pair up with opposite spins.
 Pauli’s Exclusion Principle
 Each electron within a given atom must have a
unique set of the four quantum numbers.
 Quantum Mechanics (Cont.)

 Aufbau’s Principle
 Electrons will
successively occupy
the available orbitals
on order of
increasing energy.
Quantum Mechanics (Cont.)

Example:
Write the
possible set of
quantum
numbers for the
electrons in:
(a) 3s
(b) 3d
(c) 4f
 Quantum Mechanics (Cont.)

Atomic Orbital Shapes:

s and p Orbitals

d Orbitals
 Electronic Configuration
 Electronic Configuration
 Refers to the arrangement of electrons in energy levels.

 Methods of Writing
1. Orbital method
2. Shell method
3. Arrow Rectangular method
4. Core Method
 Electronic Configuration (Cont.)

Example (neutral atom):

Write the electronic configuration using the four
methods of the following elements:
(a) Br
(b) Ca

Example (monoatomic ions):

Give the electronic configuration of:
(a) V4+
(b) Cl
 Quantum Mechanics (Cont.)

Related Concepts:

 Magnetism

 Paramagnetic – substances that contain net

unpaired electrons and are attracted by a magnet.
Ex. Li
 Diamagnetic – substances that do not contain net
unpaired electrons and are slightly repelled by a
magnet.
Ex. Mg
 Periodic Relations of Elements
 Periodic Classifications of Elements
 Elements may be classified according to their electronic
configurations.
1. The Noble Gases – They are also known as Inert Gases or
Group O elements. They are colorless monoatomic gases,
which are chemically unreactive and diamagnetic. They have
outer configurations of ns2np6 (except for Helium).
2. The Representative Elements – These elements are found in
the A families of the periodic table. They exhibit a wide range of
chemical behavior and physical characteristics. The chemistry of
these elements depends upon the valence electrons.
 Periodic Relations of Elements (Cont.)

3. The Transition Elements – They are found in the B families

of the periodic table. All of these elements are metals and
most of them are paramagnetic and form highly colored,
paramagnetic compounds.
4. The Inner-Transition Elements – These elements are
found at the bottom of the periodic table, but they belong to
the 6th and 7th periods after the elements of group IIIB. All
inner-transition elements are metal and are paramagnetic.
Their compounds are also paramagnetic and colored.
 Periodic Relations of Elements (Cont.)

 Periodic Variation in Physical Properties

1. Atomic Radius – one-half the distance between the nuclei of
the two atoms in an elemental substance.

TREND:

LEFT  RIGHT decreases

TOP  BOTTOM increases
 Periodic Relations of Elements (Cont.)

2. Ionic Radius – one-half the distance between the nuclei of a

metal and a non-metal.
 positive ions are smaller than
the metal atoms from which they
are formed
 negative ions are larger than
the nonmetal atoms from which
they are formed

TREND:
LEFT  RIGHT decreases*
* this happens when comparing both
metals and non-metals but by TOP  BOTTOM increases
comparing the metals and non-metals, nonmetals
have larger ionic radius than metals.
 Periodic Relations of Elements (Cont.)

3. Ionization Energy – the minimum energy required to

remove an electron from a gaseous atom in its ground state.

LEFT  RIGHT increases

TREND:
TOP  BOTTOM decreases

4. Electron Affinity – measure of the energy change when

electron is added to a neutral atom to form a negative ion.

LEFT  RIGHT increases

TREND:
TOP  BOTTOM decreases
END of Lecture No. 1