The History of

Atomic Theory
Atomic Models
Who are these men?
 Democritus
• This is the Greek
philosopher Democritus
who began the search for a
description of matter more
than 2400 years ago.
– He asked: Could matter
be divided into smaller
and smaller pieces
forever, or was there a
limit to the number of
times a piece of matter
could be divided?

400 BC
Atomos
• His theory: Matter could
not be divided into smaller
and smaller pieces forever,
eventually the smallest
possible piece would be
obtained.
• This piece would be
indivisible.
• He named the smallest
piece of matter “atomos,”
meaning “not to be cut.”
Atomos
 To Democritus, atoms
were small, hard
particles that were all
made of the same
material but were
different shapes and
sizes.
 Atoms were infinite in
number, always moving
and capable of joining
together.
 This theory was ignored and
forgotten for more than 2000
years.
 Why?
• The eminent
philosophers of
the time,
Aristotle and
Plato, had a
more
respected, (and
ultimately Aristotle and Plato favored the earth, fire, air
wrong) theory. and water approach to the nature of matter.
Their ideas held sway because of their
eminence as philosophers. The atomos idea
was buried for approximately 2000 years.
 Dalton’s Model
• In the early 1800s,
the English Chemist
John Dalton
performed a number
of experiments that
eventually led to the
acceptance of the
idea of atoms.
Dalton’s Theory
• He deduced that all elements
are composed of atoms.
Atoms are indivisible and
indestructible particles.
• Atoms of the same element
are exactly alike.
• Atoms of different elements
are different.
• Compounds are formed by
the joining of atoms of two or
more elements.
 .

• This theory
became one of
the
foundations of
modern
chemistry.
Thomson’s Plum Pudding Model
• In 1897, the
English scientist
J.J. Thomson
provided the first
hint that an atom
is made of even
smaller particles.
 Thomson Model
• He proposed a
model of the atom
that is sometimes
called the “Plum
Pudding” model.
• Atoms were made
from a positively
charged substance
with negatively
charged electrons
scattered about, like
raisins in a pudding.
 Thomson Model
• Thomson studied
the passage of an
electric current
through a gas.
• As the current
passed through
the gas, it gave off
rays of negatively
charged particles.
 Thomson Model
Where did
they come
• This surprised from?

Thomson, because
the atoms of the
gas were
uncharged. Where
had the negative
charges come
from?
Thomson concluded that the
negative charges came from within
the atom.

A particle smaller than an atom had

to exist.

The atom was divisible!

Thomson called the negatively
charged “corpuscles,” today known
as electrons.

Since the gas was known to be

neutral, having no charge, he
reasoned that there must be
positively charged particles in the
atom.

But he could never find them.

 Rutherford’s Gold Foil Experiment
• In 1908, the English
physicist Ernest
Rutherford was hard
at work on an
experiment that
seemed to have little
to do with
unraveling the
mysteries of the
atomic structure.
• Rutherford’s experiment Involved firing a
stream of tiny positively charged
particles at a thin sheet of gold foil (2000
atoms thick)
– Most of the positively
charged “bullets” passed
right through the gold
atoms in the sheet of gold
foil without changing
course at all.
– Some of the positively
charged “bullets,” however,
did bounce away from the
gold sheet as if they had hit
something solid. He knew
that positive charges repel
positive charges.
• This could only mean that the gold atoms in the
sheet were mostly open space. Atoms were not a
pudding filled with a positively charged material.
• Rutherford concluded that an atom had a small,
dense, positively charged center that repelled his
positively charged “bullets.”
• He called the center of the atom the “nucleus”
• The nucleus is tiny compared to the atom as a whole.
Rutherford
• Rutherford reasoned
that all of an atom’s
positively charged
particles were
contained in the
nucleus. The negatively
charged particles were
scattered outside the
nucleus around the
atom’s edge.
 Bohr Model
• In 1913, the Danish
scientist Niels Bohr
proposed an
improvement. In his
model, he placed
each electron in a
specific energy
level.
Bohr Model
• According to Bohr’s
atomic model,
electrons move in
definite orbits
around the nucleus,
much like planets
circle the sun. These
orbits, or energy
levels, are located at
certain distances
from the nucleus.
Wave Model
The Wave Model
• Today’s atomic
model is based on
the principles of
wave mechanics.
• According to the
theory of wave
mechanics, electrons
do not move about
an atom in a definite
path, like the planets
around the sun.
 The Wave Model
• In fact, it is impossible to determine the exact
location of an electron. The probable location of an
electron is based on how much energy the electron
has.
• According to the modern atomic model, at atom has
a small positively charged nucleus surrounded by a
large region in which there are enough electrons to
make an atom neutral.
 Electron Cloud:
• A space in which electrons
are likely to be found.
• Electrons whirl about the
nucleus billions of times in
one second
• They are not moving around
in random patterns.
• Location of electrons
depends upon how much
energy the electron has.
 Electron Cloud:

• Depending on their energy they are locked into a

certain area in the cloud.
• Electrons with the lowest energy are found in the
energy level closest to the nucleus
• Electrons with the highest energy are found in the
outermost energy levels, farther from the nucleus.
 Quantum Model
of the Atom

Electron Configuration & Orbitals

1s22s22p63s23p64s23d104p65s24d104p65s24d105p66s24f145d106p6…
 Quantum Numbers
• Four Quantum Numbers:
– Specify the “address” of each electron in an
atom
UPPER LEVEL

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 III. Quantum Numbers
• Used the wave equation to represent
different energy states of the electrons
• Set of four #’s to represent the location
of the outermost electron
• Here we go…
 Quantum Numbers

Principal Quantum Number ( n )

Angular Momentum Quantum # ( l )

Magnetic Quantum Number ( ml )

Spin Quantum Number ( ms )

 Relative Sizes 1s and 2s

1s 2s
Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 334
 Quantum Numbers
1. Principal Quantum Number ( n )

–Energy level 1s

–Size of the orbital

2s
–n2 = # of orbitals in
the energy level

3s
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 The Principal quantum number
The quantum number n is the principal quantum number.

– The principal quantum number tells the average

relative distance of the electron from the nucleus
– n = 1, 2, 3, 4 . . .
– As n increases for a given atom, so does the average
distance of the electrons from the nucleus.
– Electrons with higher values of n are easier to remove
from an atom.
– All wave functions that have the same value of n are
said to constitute a principal shell because those
electrons have similar average distances from the
nucleus.
 1s orbital imagined as “onion”

Concentric spherical shells

Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.

Shapes of s, p, and d-Orbitals

s orbital

p orbitals

d orbitals
Atomic Orbitals
 s, p, and d-orbitals

A B C
s orbitals: p orbitals: d orbitals:
Hold 2 electrons Each of 3 pairs of Each of 5 sets of
(outer orbitals of lobes holds 2 electrons lobes holds 2 electrons
Groups 1 and 2) = 6 electrons = 10 electrons
(outer orbitals of (found in elements
Groups 13 to 18) with atomic no. of 21
and higher)
Kelter, Carr, Scott, , Chemistry: A World of Choices 1999, page 82
Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.
 (a) Electron probability (b) Contour probability (c) Radial probability

Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.

 Y21s Y22s Y23s

r r r r r r
Distance from nucleus

(a) 1s (b) 2s (c) 3s

 Quantum Numbers

y y y

z z z

x x x

px pz py
 p-Orbitals

px pz py

Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 335

 y y y y

z z z z

x x x x

s px pz py

2s 2p (x, y, z) carbon

Mark Wirtz, Edward Ehrat, David L. Cedeno*

Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.
 Quantum Numbers
2. Angular Momentum Quantum # ( l )
–Energy sublevel
–Shape of the orbital

s p d
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f
 The azimuthal quantum number
Second quantum number l
is called the azimuthal quantum number

– Value of l describes the shape of the region of space

occupied by the electron

– Allowed values of l depend on the value of n and can

range from 0 to n – 1

– All wave functions that have the same value of both

n and l form a subshell

– Regions of space occupied by electrons in the same

subshell have the same shape but are oriented
differently in space

Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.

 A Cross Section of an Atom
n0
Rings of Saturn p+

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

The first ionization energy level has only one sublevel (1s).
The second energy level has two sublevels (2s and 2p).
The third energy level has three sublevels (3s, 3p, and 3d).

Although the diagram suggests that electrons travel in circular orbits,

this is a simplification and is not actually the case.
Corwin, Introductory Chemistry 2005, page 124
 Quantum Numbers

• Orbitals combine to form a spherical shape.

2s
2px
2py 2pz

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 Quantum Numbers
Principal n=1 n=2 n=3
level

Sublevel s s p s p d

Orbital px py pz px py pz dxy dxz dyz dz2 dx2- y2

• n = # of sublevels per level

• n2 = # of orbitals per level
• Sublevel sets: 1 s, 3 p, 5 d, 7 f
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 Maximum Capacities of Subshells
and Principal Shells

n 1 2 3 4 ...n
l 0 0 1 0 1 2 0 1 2 3

Subshell
designation s s p s p d s p d f

Orbitals in
subshell 1 1 3 1 3 5 1 3 5 7

Subshell
capacity 2 2 6 2 6 10 2 6 10 14

Principal shell
capacity 2 8 18 32 ...2n2

Hill, Petrucci, General Chemistry An Integrated Approach 1999, page 320

 Quantum Numbers
3. Magnetic Quantum Number ( ml )
–Orientation of orbital
–Specifies the exact orbital within each sublevel

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 The magnetic quantum number

Third quantum is ml, the magnetic quantum number

– Value of ml describes the orientation of the region
in space occupied by the electrons with respect to
an applied magnetic field
– Allowed values of ml depend on the value of l
– ml can range from –l to l in integral steps
ml = l, -l + l, . . . 0 . . ., l – 1, l
– Each wave function with an allowed combination of
n, l, and ml values describes an atomic orbital, a
particular spatial distribution for an electron
– For a given set of quantum numbers, each principal
shell contains a fixed number of subshells, and
each subshell contains a fixed number of orbitals
Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.
 d-orbitals

Zumdahl, Zumdahl, DeCoste, World of Chemistry 2002, page 336

Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.
Principal Energy Levels 1 and 2
 Quantum Numbers
4. Spin Quantum Number ( ms )
–Electron spin  +½ or -½
–An orbital can hold 2 electrons that spin in
opposite directions.

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 Electron Spin: The Fourth Quantum Number

• When an electrically charged object spins, it produces a magnetic moment

parallel to the axis of rotation and behaves like a magnet.

• A magnetic moment is called electron spin.

• An electron has two possible orientations in an external magnetic field,

which are described by a fourth quantum number ms.

• For any electron, ms can have only two possible values, designated + (up)
and – (down), indicating that the two orientations are opposite and the
subscript s is for spin.

• An electron behaves like a magnet that has one of two possible

orientations, aligned either with the magnetic field or against it.

Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.

Copyright © 2006 Pearson Benjamin Cummings. All rights reserved.
 Quantum Numbers
• Pauli Exclusion Principle Wolfgang Pauli

– No two electrons in an atom can have the same 4

quantum numbers.
– Each electron has a unique “address”:

1. Principal #  energy level

2. Ang. Mom. #  sublevel (s,p,d,f)
3. Magnetic #  orbital
4. Spin #  electron

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 Allowed Sets of Quantum Numbers for Electrons in Atoms
Level n 1 2 3
Sublevel l 0 0 1 0 1 2
Orbital ml 0 0 1 0 -1 0 1 0 -1 2 1 0 -1 -2
= +1/2
Spin ms
= -1/2
 Electron Orbitals:

Electron
orbitals

Equivalent
Electron
shells

(a) 1s orbital (b) 2s and 2p orbitals c) Neon Ne-10: 1s, 2s and 2p

1999, Addison, Wesley, Longman, Inc.

 What sort of covalent bonds
are seen here?

H H H H O O O O

(a) H2 (b) O2

H
O H O H H O H H C H
H H
H H

(c) H2O (d) CH4