Atomic Structure

Atoms and Ions

 Michael Faraday
• Faraday discovered that ionic substances, such as NaCl
would not conduct electricity in the solid state, but would
conduct electricity when dissolved in water or molten
(melted).
• He proposed that atoms could become charged and move
toward oppositely charged electrodes
• He, and others, proposed that there may be a fundamental
particle of electricity. Stoney called it the electron.
 Crookes’ Tube
•William Crookes, in the late 1800s, discovered that if
electrodes, connected to a high voltage power supply, were
separated and placed in a vacuum tube, the tube would glow
with a yellow-green light.
•It was discovered that the light was a ray that came from the
cathode (negative electrode) and traveled to the anode
(positive electrode).
•The back end of the tube could be painted with a luminous
pigment and the path of the ray could be studied.
•The important work done with Crookes’ tube was performed
later by J.J. Thomson.
 Crookes’ Tube
(Cathode Ray Tube)
Crookes’ Tube (Cont.)
 Crookes’ Tube (Cont.)
(Detecting positive particles)
 Properties of Electrons
•The “ray” that Thomson studied was a beam of
electrons. He was able to determine that the electron:
•Was negatively charged
•Was affected by a magnetic field
•Had a mass/charge ratio that he measured and calculated
•Robert Millikan (an American) used an oil-drop
experiment to measure the charge on oil droplets falling
between charged plates. The charge on the droplets was
a whole number multiple of the charge on the electron.
 Millikan’s Oil Drop Experiment for
Determining the Charge on the Electron
 Calculation of the Properties of
the Electron
•Thomson found that the mass to charge ratio of
the electron was -5.686x10-12 kg/C
•Millikan found the charge on the electron was
-1.62 x 10-19 C. (C is the abbreviation for the
coulomb, a unit of charge.)
•Therefore the mass of the electron can be
calculated: mass = charge x mass/charge
•mass = (-1.602x10-19C)(-5.686x10-12 kg/C)
= 9.1 x 10-31 kg = 9.1 x 10-28 g
 How are negative and positive
charges arranged in the atom?
Thomson proposed a model of a spherical atom composed of
diffuse, positively charged matter or field, in which electrons
were embedded like “plum pudding.”

Thomson’s “Plum Pudding”

Model of the Atom
 X-Rays
•Roentgen discovered X-rays which could
penetrate opaque materials.
•He discovered X-rays while working with a
cathode ray tube.
•These rays seemed to be emitted from the
Cathode Ray tube itself and could be detected
in another room.
 Radioactivity
•Becquerel discovered radioactivity.
•He left some uranium crystals on top of
some photographic film which was covered
with opaque, black paper. When he
developed the film, he observed spots due to
rays coming from the uranium crystals. The
rays had penetrated the paper!
 Radioactivity and the Curies
•Pierre and Marie Curie:
–Marie named the effect observed by Becquerel
radioactivity.
–Radioactivity is the spontaneous emission of
radiation from certain unstable elements.
–Pierre and Marie discovered radium and
polonium, radioactive elements.
–They discovered much about radioactivity and
radioactive elements
 Radioactivity (continued)
•Marie and Pierre Curie and Becquerel shared
the Nobel Prize in Physics in 1903.
•Marie won the Nobel Prize in Chemistry in
1911.
•It is generally believed that both Curies died
as a consequence of radiation poisoning
•Their daughter, Irene, also won a Nobel prize
in 1935
 Properties of alpha (beta
(and gamma (rays

Particle Mass Charge

Alpha ( 4 amu +2

Beta( 0.000544 -1

Gamma (       

Method for Studying Emissions
 Rutherford set out to test
Thomson’s hypothesis
He bombarded gold foil with  particles. If
Thomson’s “plum pudding” hypothesis were
correct, the  particles would be expected to be
deflected only to a small extent, if at all,
because they should act as dense, positively
charged bullets and go right through the gold
atoms. The embedded electrons could not
deflect the particles any more than a bowling
ball would be deflected by ping pong balls.
Rutherford’s Alpha Scattering Experiment
used to Discover the Nucleus
A Surprising Result Was Observed
•Although most of the particles went
straight through the gold foil, a few of them
were deflected by the foil at various angles.
In fact some of the  particles bounced right
back at the source.
•Thomson’s “plum pudding” model did not
explain this. What model would explain it?
 Rutherford’s nuclear model
of the atom.
•Atoms consisted of a central nucleus which
had a positive charge and which had a very
small volume, but it also contained most of the
mass of the atom. Surrounding the nucleus
were electrons, which had very little mass, but
which occupied most of the volume of the
atom.
•What was in the nucleus?
Atomic Interpretation of
the Alpha Particle
Scattering Experiment
 We already knew the atom
contains electron(s)
•Goldstein discovered a positively charged particle
that had a charge equal to the electron, but of
opposite sign. It had a mass of 1 amu (1837 times
the mass of the electron. This particle is called the
proton.
•Rutherford concluded that the nucleus contained
protons. He could account for the charge of the
nucleus, but the mass of was too large for the
number of protons.
 In 1932, Chadwick discovered a
second nuclear particle, the
neutron
•Protons and neutrons make up most of the
mass of the atom and are in the nucleus.
•Electrons are very light and are flying around
outside the nucleus.
 Rutherford’s Nuclear Model
of the Atom
•Despite the success of Rutherford’s model at explaining
much of what was known about atomic structure, there were
problems.
•The biggest problem was an apparent violation of the laws of
physics. A charged particle, when accelerated, was known to
emit electromagnetic radiation. However, electrons,
according to Rutherford where orbiting in circular
(accelerating) orbits around the nucleus and did not emit
electromagnetic radiation.
•It was apparent that a more sophisticated model was needed.
 Electromagnetic Radiation
•Before we can explore our model of the atom
further, we need to look more closely at energy
•Chemistry is the study of matter and energy.
One type of energy is electromagnetic radiation.
Let us look more closely at the properties of
electromagnetic waves. Electromagnetic waves
consist of oscillating, perpendicular electric and
magnetic fields.
•The wavelength of radiation is the distance
between peaks in a wave. ()
•The frequency is the number of peaks that pass
a point in a second. ( )
Wavelength of Light
 A Simple Frequency and
Wavelength Formula
• c
• c/
• c
• is wavelength measured in length units (m,
cm, nm, etc.)
• is frequency measured in Hz (s-1).
• c is the velocity of light in vacuum
= 3.0 x108 ms-1
 Electromagnetic Spectrum
• Recognize common units for 
•  wavelength frequency
• meters (m) radio Hertz Hz s-1
• micrometers m (cycles per
(10-6 m) microwaves second)
• nanometers nm megahertz
• (10-9 m) light MHz (106 Hz)
• A angstrom (10-10 m)
 Electromagnetic Waves
• Describe electromagnetic radiation and give
examples of it in relation to the
electromagnetic spectrum.
Type  (nm)  (Hz)
• radio (Rf) 108 - 1012 104-109
• microwave 106-108 109-1012
• infrared (IR) 750-106 1012-1014
• visible (vis) 400-750 1014-1015
• ultraviolet (UV) 10-400 1015-1016
• X-rays,  rays 10-4-1 1016-1022
The Electromagnetic Spectrum
 Light Quanta and Photons
•Quantum- A packet of energy equal to hThe
smallest quantity of energy that can be emitted or
absorbed.
•Photon- A quantum of electromagnetic radiation.
•Thus light can be described as a particle (photon) or
as a wave with wavelength and frequency. This is
called wave-particle duality (one of the most
profound mysteries of science)
 Elemental Line Spectra

When certain elements are heated or

electronically excited, they emit light of
different colors. When the light is
separated into various colors by a
spectroscope, a line spectrum is observed.
Bright Line Emission Spectrum
from Excited Element
 Emission Spectrum
•Explain the emission line spectrum of light,
based on the Bohr model of the hydrogen
atom.
•Bohr explained the line spectrum by asserting
that the electrons in the atoms could be in certain
quantized energy levels.
•The spectrum arose due to transitions between
quantized energy levels. The energy of the
emitted light was equal to the difference in
energies of the levels.
 Bohr’s explanation of line spectra
•Bohr explained the line spectrum by asserting that the
electrons in the atoms could be in certain quantized
energy levels.
•The spectrum arose due to transitions between
quantized energy levels. The energy of the emitted
light was equal to the difference in energies of the
levels.
•Electrons in atoms can not have any energy. They can
only have certain amounts of energy. The electrons are
said to be quantized. The emission (bright) line
spectra are produced when electrons fall from a high
energy level (excited state) to a lower energy level.
 Energy of emission lines
photon = E = Ehigh-Elow
E = h = hc/
light = E/h
 = hc/E
Since Ehigh and Elow are discreet numbers, 
must be a discreet number. Therefore,
 and  must be discreet numbers, giving rise
to single frequencies and wavelengths of light.
Hence, the line spectra.
Emission Lines
 The Bohr Atom

•Bohr was able to accurately predict the

energy levels of the one-electron atom,
hydrogen.
•He suggested that multi-electron atoms would
have electrons placed in the energy levels
described by his theory.
•A certain maximum number of electrons
could be in each level.
 Electrons in Energy Levels
•The maximum number of electrons in any
energy level is 2n2
•Level 2n2 maximum number of
electrons
•1 2(1)2 2
•2 2(2)2 8
•3 2(3)2 18
•4 2(4)2 32
 Bohr Diagrams
•Illustrations of electrons in energy levels are
called Bohr Diagrams.
•The electrons in the outer levels are called
valence electrons.
•The valence electrons are those involved in
chemical bonding.
•Examples of Bohr diagrams are shown on
the next slide:
Bohr Diagrams
 Valence Electrons
The outer electrons in an atom can be represented
with dots in the Lewis electron dot symbol. Each outer
electron is represented by a dot around the atomic
symbol:
Sodium has one valence electron, hence one dot:
Na •

Sodium ion has lost its valence electron, no dots:

Na+
 Lewis Symbols
•Chlorine has 7 valence electrons, hence 7
dots:

:
• :Cl.

:
•Chloride ion gains an electron to form Cl -
•It will have 7+1=8 electrons:
:

• :Cl:
:

•Other elements are done the same way

Lewis Dot Structures for Main
Group Elements are Determined
form the Group Number
•Group IA elements (alkali metals) have 1
valence electron: 1 dot Na
•Group IIA elements (alkaline earths) have 2
valence electrons: 2 dots Ca:
•Group VIII elements (noble gases) have eight
dots, an octet: :Ne:
•He, has only 2 electrons, 2 dots: He:
 Bohr’s Model was improved
upon in the 1920’s with the
Quantum Mechanical Model.
•Since Bohr’s model only worked for the hydrogen
atom, a more sophisticated model was needed.
•The next breakthrough was made by Louis de Broglie,
who suggested that electrons, like photons have wave
properties
•De Broglie thought that Bohr’s energy levels were
created by the wave properties of the electron
 De Broglie
suggested an
electron
could only
have a path
that allowed
a whole
number of
wave
patterns
 Other Contributors to the
Quantum Mechanical Atom
•Schrödinger used de Broglie’s ideas to create
some powerful wave equations to describe the
electron.
•Heisenberg used probability and matrices to
describe the electron. He stated a controversial
Uncertainty Principle. The path of an electron
can not be determined. It is uncertain. Thus a
specific “orbit” for an electron can not be
known.
 Evolving
Theories of the
Atom
 In addition to the energy levels of
Bohr, there are sub-levels
•Bohr’s energy levels were assigned a principal quantum
number, n, which could values of 1, 2, 3… This quantum
number, n designates the energy level and size of the
region in space the electrons might be found.
• Within an energy level there are sublevels or subshells,
designated s, p, d, and f. These subshell designations tell
the shape of the region in space the electrons might be
found.
Charge Cloud
Representatio
ns of “s”
Orbitals
Shapes of
“p”
Orbitals
px, py, and pz
Orbitals

A p subshell
contains 3 p
orbitals, each lies
perpendicular to
the others on the
X-Y-Z axes
s, p, d, and f Orbitals
 Orbitals
•Each orbital has its own set of quantum
numbers.
•Each orbital can contain 2 electrons, one
with spin +1/2 the other with spin -1/2
•The quantum number and energy levels can
be described with an orbital diagram.
•A summary of an orbital diagram is called
an electron configuration.
 Energies of Orbitals in Multi-
Electron Atoms
•Several factors affect the energy of electrons in
multi electron atoms:
–Nuclear charge
–Electron repulsions
•Additional electrons in the same orbital
(shielding)
•Additional electrons in inner orbitals
–Orbital shape (ml)
–spin (ms)
–Pauli Exclusion Principle: No two electrons in the
same atom can have the same set of four quantum
numbers.
 Aufbau Principle

•Electrons arrangements are “built-up” by filling

various energy levels, starting with lower
energies, filling orbitals two at a time. They go
into the orbitals one with spin +1/2, the other with
spin - 1/2.
•An orbital diagram is useful in showing this
arrangement.
Orbital Diagrams
 Electronic
Configurations
By adding electrons
to the diagram,
lowest energy to
highest,
remembering Hund’s
rule and the quantum
rule that no orbital
can hold more than
two electrons, an
elcetronic
configuration can be
created
Electron Configurations can be
Determined From the Position in
the Periodic Table:
•Elements in group 1(1A) end in ns1.
•Elements in group 2 (2A): end in ns2
•Elements in group 13 (3A) end in ns2np1
•Elements in group 14 (4A): end in ns2np2
•Elements in group 15 (5A) end in ns2np3
•Elements in group 16 (6A) end in ns2np4
•Elements in group 17 (7A) end in ns2np5
•Elements in group 18 (8A) end in ns2np6
Periodic Table Family Filling
Diagram
Periodic Table Orbital Block
Diagram