Lesson 2.1
ATOMS: Dalton and Beyond

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 Models in science
Scientists use their experimental results
(and their imaginations)
to create models

A model is a representation of a complex natural

system that permits us to understand its behavior.

These models may be mental,

mathematical, or even physical.
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 Prior Examples?

Remember the models of planetary motion?

What were they trying to explain?

(These animated gifs were obtained from Dr. Stephen J. Daunt's Astronomy 161 web site at

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The University of Tennesee, Knoxville.)
 Early Greek atomists
Leucippus • There is only one type of
(~480 - 420
B.C.)
matter, found in tiny,
indivisible particles called
“atoms”
http://cont1.edunet4u.net/cobac2/down/down05.ht

ml

• All change is caused by

atoms moving through
empty space

• Atoms are therefore

Democritus (470 - 380 B.C.)
“fundamental”
www.livius.org/a/ 1/greeks/democritus.jpg 4
But an alternate model won out

http://astsun.astro.virginia.edu/~jh8h/Foundations/chapter2.html

Aristotle (384 – 322 BC)

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The mechanical philosophy of the 1600s

• Descartes, Boyle
and Newton

• A “clockwork”
universe

• Simplicity,
generality, and
precise predictions

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Would it work for chemistry as well?

Maybe chemistry would turn out to be as

“simple” as Newtonian physics

A few, simple objects

following simple, general, and
precise laws

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Start of the Modern Era of Atoms

John Dalton’s Atomic

Hypothesis (1803):
1. All matter is made up of
indivisible atoms.

2. Compounds are composed of

atoms in definite proportions.

3. Chemical change occurs when

atoms are rearranged
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Dalton’s Atomic Model of Compounds
• explained observation of
“constant proportions” as
based on atomic composition
of compounds

• used “Rule of greatest

simplicity” to guess at the
atomic structure of compounds

• estimated relative atomic

masses, based on his
hypothesized structures
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Meanwhile, many new elements being found

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How to make sense of all these
elements?
Scientists like “a place for
everything, and
everything in its place.”

And no more places and

things than necessary.

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 Dmitri
Mendeleev
(1834-1907)

“Creator of the
Periodic Table”
(but there were earlier attempts by
Dobereiner and Newlands, and
Meyer probably formulated the
periodic idea at same time as
Mendeleev)

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 Mendeleev’s
early notes
for the
Periodic Table
(1869)

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 Mendeleev’s
table, as originally
published
• Formatted
sideways
compared to
modern table

• ? instead of a
name: element
was predicted to
exist but not
known yet
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Characteristics of Mendeleev’s Table
• Organized 60+ known elements…
- by similar properties in each vertical family
(group)
- by roughly increasing atomic weight within
each horizontal row (moved 17 elements
based on properties rather than weight)

• Used to predict existence of new elements

(of 10, found 7; other 3 do not exist)

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Prediction of the properties of an unknown
Group 4 element below Silicon

Property Observed Predicted Observed Observed

for Si for eka-Si for Sn for Ge
Atomic 28 72 118 72.6
mass
Density 2.33 5.5 7.28 5.35
(g/cm2)
* Formula SiO2 Eka-SiO2 SnO2 GeO2
of oxide

Formula SiCl4 Eka-SiCl4 SnCl4 GeCl4

of
chloride

eka: “one beyond”

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An attempt to simplify the elements
William Prout (1815)
• hypothesized that the hydrogen
atom is fundamental

• all other elements made up of

hydrogen atoms

• his hypothesis was rejected by the

1830s (for ex. chlorine atom had
mass 35.4 times that of hydrogen)

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News flash: atoms aren’t fundamental
J. J. Thomson (1897)
• experimented with “cathode rays”

• “and then... made a bold speculative

leap. Cathode rays are not only
material particles, he suggested, but in
fact the building blocks of the atom:
they are the long-sought basic unit of
all matter in the universe.”
(http://www.aip.org/history/electron/jjrays.htm)

Schematic of actual
1897 apparatus
(vacuum inside):
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 Thomson’s conclusions
• “We have, in the cathode rays,
matter in a new state...a state
in which all matter...is of one
and the same kind; this matter
being the substance from which
all the chemical elements are
built up."

• “I can see no escape from the conclusion that [cathode rays]

are charges of electricity carried by particles of matter.”
but...
• “What are these particles? Are they atoms, or molecules, or
matter in a still finer state of subdivision? - J. J. Thomson
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Thomson’s “plum pudding” atom model*
Cathode rays
(electrons) are...

• tiny “corpuscles”
of negative charge

• surrounded by a
sort of “cloud” of
positive charge

* Never had plum pudding? Think of a blueberry muffin.

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If electrons exist, how big are they?
• Thomson calculated the mass-to-charge ratio for cathode
ray particles: it was over 1000 times smaller than for a
charged hydrogen atom

• This fact suggested:

- either cathode rays carried a huge charge,
- or they had very small mass

• Robert Millikan measured the charge of a cathode ray

particle in 1910. From that he could calculate the mass:
~1800 times lighter than a hydrogen atom
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More pieces of the atom
Ernest Rutherford
(1871-1937)

nuclear physicist,
Thomson’s student,
New Zealander teaching
in Great Britain

Gold Leaf Experiment

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Rutherford’s Experiments (1910-11)
(done by undergrad Ernest Marsden/physicist Hans Geiger)

• Fired beam of positively-charged alpha particles at

very thin gold foil.
• Alpha particles caused flashes of light when they hit
the zinc sulfide screen
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Rutherford’s Experiment: prediction
By Thomson’s model,

mass and + charge of gold

atom are too dispersed to
deflect the positively-charged
alpha particles,

so...

particles should shoot straight

through the gold atoms.

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Rutherford’s Experiment:
prediction
Alpha particles will pass
through like this …

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Rutherford’s experiment: what
actually happened

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 What’s going on?
Most alpha particles went
straight through, and
some were deflected,
BUT
a few (1 in 20,000) reflected
straight back to the source!

“It was quite the most incredible event that has ever happened
to me. It was almost as incredible as if you had fired a fifteen inch
shell at a piece of tissue paper and it came back and hit you.”
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 Rutherford’s Model of the Atom
Expt. Interpretation:
• gold atom has small,
dense, positively-charged
nucleus surrounded by
“mostly empty” space +
in which the electrons
must exist.

• Positively charged
particles called “protons”
• like tiny solar system
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The Nucleus Repels Alpha Particles

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How much of an atom is empty space?
Most of it!

In fact, if the nucleus of an atom

were the size of a marble, the +
innermost electrons would be
how far away?

• One-half inch
• Six inches
• Eighteen inches
• One-half mile

(click for the right answer)

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But wait – there’s more!

James Chadwick
(1932)

Discovered a neutral
(uncharged) particle in the nucleus.
Called it the “neutron”

Atom “split” by John Cockcroft and

Ernest Walton, using a particle
accelerator, in late 1932

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Properties of Subatomic Particles

Property Mass (amu), Relative

Particle Mass (g) Charge
Electron 0.00055 -1
9.110 x 10-28
Proton 1.00728 +1
1.673 x 10-24
Neutron 1.00866 0
1.675 x 10-24

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 Now we understand why the
elements come in periods of 8
• The order of the elements is determined by their atomic number (= the number of protons)

• The atomic mass of the elements is determined by the number of protons and neutrons. A
given element can have different number of neutrons, and therefore different atomic masses.

• The chemical properties of the elements are determined by the number of electrons in their
outer (valence) shells

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Why do 2 Group I atoms combine
with 1 oxygen (R2O)?

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So: is this what atoms are like?

No! Electrons moving through

the electrical field generated
by the protons in the nucleus
would radiate away energy and
spiral down into the nucleus

Calculations soon showed that a

“Rutherford atom” would last
less that one minute.

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A new understanding of the atom

It had long been know that

when chemical elements
are heated, they gave off
light of a particular
wavelength (or color)

Sodium Potassium Lithium

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Spectroscopes: Seeing Atomic Light

Original 1859
Bunsen-
Kirchhoff
spectroscope

Typical setup
for viewing a
line-emission
spectrum

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Spectroscopy can identify elements on
distant stars

Hydrogen

Helium

http://heasarc.gsfc.nasa.gov/docs/xmm_lc/edu/lessons/student-worksheet-spectragraph2.html

Helium was discovered in a spectrograph of the

Sun in 1868 and not on Earth until 27 years later.
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 Niels Bohr
(1885-1962)

Danish physicist

Bohr wondered why

hydrogen emitted spectral
lines, and not just a
continuous band of light
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Hydrogen’s Emission “Fingerprint”

Observation:
when hit with electricity
hydrogen gives off light
of specific wavelengths,
NOT continuous range!

The line-emission spectrum

of hydrogen gas
(the bands visible to humans)
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 Weakness of Rutherford’s Model

Rutherford's model couldn't explain why

unique colors were obtained by atoms of different

elements
 Bohr’s Model of Atom (1913)
H's electron

r1
r2 The first three allowed energy levels,
at distances r1, r2, and r3 from nucleus.
r3

H's nucleus containing 1 proton

• Circling electron maintains orbit ONLY at specific
distances from nucleus
• Only way electron could exist for long time without
giving off radiation
• Bohr’s model enabled him to predict the number and
wavelength of hydrogen’s emission lines
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 Electron orbits are distinct
(“quantized”) in Bohr’s model

Trefil & Hazen. The Sciences: An integrated approach. 2nd ed. Fig. 7-6.

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 Bohr's Model of the Atom

Niels Bohr (1913):

-studied the light produced when atoms were excited by heat or

electricity

Rutherford's model couldn't explain why unique colours were

obtained by atoms of different elements

Bohr proposed that electrons are in orbits & when excited jump to a higher orbit.

When they fall back to the original they give off light
 Bohr's Model of the Atom

Bohr's model:

-electrons orbit the nucleus like planets orbit the sun

 Bohr's Model of the Atom

Bohr's model:

-electrons orbit the nucleus like planets orbit the sun

-each orbit can hold a specific maximum number of electrons

 Bohr's Model of the Atom

Bohr's model:

-electrons orbit the nucleus like planets orbit the sun

-each orbit can hold a specific maximum number of electrons

orbit maximum #
electrons
1 2
2 8
3 8
4 18
 Bohr's Model of the Atom

Bohr's model:

-electrons orbit the nucleus like planets orbit the sun

-each orbit can hold a specific maximum number of electrons

-electrons fill orbits closest to the nucleus first.

 Bohr's Model of the Atom

e.g. fluorine:

#P =

#e- =

#N =
 Bohr's Model of the Atom

e.g. fluorine:

#P = atomic #

=9

#e- =

#N =
 Bohr's Model of the Atom

e.g. fluorine:

#P = 9

#e- = # P

=9

#N =
 Bohr's Model of the Atom

e.g. fluorine:

#P = 9

#e- = 9

#N = atomic mass - # P

= 10
 Bohr's Model of the Atom

e.g. fluorine:

#P = 9

#e- = 9 9P

10N

#N = 10

draw the

nucleus with

protons

& neutrons
 Bohr's Model of the Atom

e.g. fluorine:

#P = 9

#e- = 9 9P

10N

#N = 10

how

many electrons can

fit in the

first orbit?
 Bohr's Model of the Atom

e.g. fluorine:

#P = 9

#e- = 9 9P

10N

#N = 10

how

many electrons can

fit in the

first orbit?
 Bohr's Model of the Atom

e.g. fluorine:

#P = 9

#e- = 9
9P

10N
#N = 10

how many electrons are left?

 Bohr's Model of the Atom

e.g. fluorine:

#P = 9

#e- = 9
9P

10N
#N = 10

how many electrons are left? 7

 Bohr's Model of the Atom

e.g. fluorine:

#P = 9

#e- = 9
9P

10N
#N = 10

how many electrons are left? 7

how many electrons fit in the

second

orbit?
 Bohr's Model of the Atom

e.g. fluorine:

#P = 9

#e- = 9
9P

10N
#N = 10

how many electrons are left? 7

how many electrons fit in the

second

orbit? 8
 Bohr's Model of the Atom

e.g. fluorine:

#P = 9

#e- = 9
9P

10N
#N = 10
 Bohr's Model of the Atom

try these:

hydrogen

boron

magnesium
 Bohr's Model of the Atom

try these:

hydrogen

1P

0N
 Bohr's Model of the Atom

try these:

5P
boron 6N
 Bohr's Model of the Atom

try these:

12P

12N

magnesium
But why should electrons behave this way?

Louis de Broglie (1927)

Particle/Wave Duality of electrons

Thus I arrived at the following general idea which has guided

my researches: for matter, just as much as for radiation, in
particular light, we must introduce at one and the same
time the corpuscle concept and the wave concept. In
other words, in both cases we must assume the existence of
corpuscles accompanied by waves.
De Broglies Nobel Prize speech, 1927. http://www.spaceandmotion.com/Physics-Louis-de-Broglie.htm
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Electrons can be thought of as standing
waves …

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 Electrons as waves

Only at certain distances from the

nucleus would the electron
complete an integer number of
wavelengths in its movement
around the nucleus

When the mathematics was worked out, these

distances agreed exactly with those assumed by
Bohr for the hydrogen atom.

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The position of electrons can’t be
predicted precisely
Werner Heisenberg (1927)

The “Uncertainty Principle”

• There’s an upper limit to how precisely an electron’s

position and momentum can be known

• The more precisely one is known, the less precisely

the other can be known
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Electrons move in “probability
clouds”, not circular orbits
• The exact path of an
electron can’t be
predicted

• If we know the
electron is somewhere
in the atom, it’s
velocity is uncertain
by ~7,300 km/s (~ 16
million mph)!

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 Newtonian certainty cannot be
obtained in the subatomic world

“I cannot believe that God “Albert, stop telling God

plays dice with the what to do.”
universe.” 71