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ATOMS:

Dalton and Beyond


Start of Modern Era of Atoms:
Dalton’s Atomic Theory

John Dalton
(1766-1844)

British chemist,
lecturer, and
meteorologist
Dalton’s Atomic Theory (1803) - 1
1) All matter is made up of indivisible and
indestructible basic particles called atoms.

2) All atoms of a given element are identical,


both in mass and in properties. Atoms of
different elements have different masses
and properties.

3) Compounds are formed when atoms of


different elements combine in the ratio of
small whole numbers.
Dalton’s Atomic Theory (1803) - 2

4) Elements and
compounds are
composed of
definite
arrangements of
atoms.

Chemical change
occurs when the
atomic arrays are
rearranged.
Significance of Dalton’s Atomic
Theory
• Continued to break down earlier views of “elements”

• Bridged gap between lab data and hypothetical atom.


- way of calculating relative atomic weights.

• Explained Law of Definite Proportions [Proust


1799]
- All samples of a compound contain same
weight
proportions of constituent elements.

• Explained Law of Conservation of Mass


- “Initial Mass = Final Mass”
- Only reorganizing of unchangeable atoms
Dalton: inconsistencies uncovered…
1) The basic state of an element = one atom?
Perhaps… basic natural state of an
element may be a molecule made of
2 or more atoms.

2) Dalton: “Thou knows…no man can split the


atom.” No: radioactivity, atomic particles.

3) Atoms of given element have same mass and


properties? Not exactly: isotopes exist…
Thinking about Atoms…
Current Definitions: Matter
Classification
• Element:
- pure substance
- made of unique, (nearly) identical atoms
- cannot be broken down into simpler substances by
a
chemical reaction.

• Compound:
- pure substance
- made of atoms of at least 2 different elements
- can be broken down into simpler substances by a
chemical reaction.
Identification of Elements
• Physical properties
• Chemical properties
• Relative atomic weights (better
values)
• Flame test for solids/solutions
• Interaction with light:
line-absorption spectrum
line-emission spectrum
Flame Test for Element Identification

(From left) Sodium, potassium, lithium;


strontium, barium, potassium.
Spectroscopes: Seeing Atomic Light

Original 1859
Bunsen-
Kirchhoff
spectroscope

Typical setup
for viewing a
line-emission
spectrum
Elements: Ages of Discovery
Classification of the Elements:
Development of the Periodic
Table
• Dobereiner 1817: “Triads”, group properties
• Newlands 1863: row “Octaves”, group
properties

• Mendeleev 1869:
first-published “Period” definition (see next
slides)

• Meyer 1870:
2nd-published “Period” definition;
Dmitri
Mendeleev
(1834-1907)

“Creator of the
Periodic Table”

(probably formulated
periodic idea at same
time as Meyer)
(1869)
Periodic Table
for the
early notes
Mendeleev’s
Mendeleev’s
table, as orig.
published

• Formatted
sideways
compared to
modern table

• ? instead of a
name:
element was
predicted to
exist but not
known yet
Characteristics of Mendeleev’s Table
• Organized 60+ known elements…
- by similar properties in each vertical
family
(group)
- by valence = “combining number”
(split out elements with multiple
valence)

- by roughly increasing atomic weight


within
each horizontal row (moved 17
elements
based on properties rather than weight)
Comparison of
eka-silicon’s predicted
properties and known Group
4 properties

Eka:
“one
beyond”
1880s Revision
of
Mendeleev’s
Table
Contains “rare gases” and 3
elements unknown at time
of first version, though their
properties were predicted:

germanium (Ge),
formerly eka-silicon;
gallium (Ga),
formerly eka-aluminum;
scandium (Sc),
formerly eka-boron.
Modern Periodic Table Organization
• Elements are NOW placed in order of
increasing atomic number (# of + protons).
- Why? Gives absolute order...
atomic weights not characteristic
(different-mass atoms called isotopes
exist!)

• A relationship between nuclear charge and


arrangement of elements in the Table was
finally discovered in 1914 (Henry Moseley).

• In 1860s, Mendeleev could NOT have


predicted
Discovery of Atomic Structure;
Sub-atomic Particles
• Thomson: 1897 electron mass-to-charge
ratio

• Millikan: 1909 electron charge

• Rutherford: 1910-11 mass & charge of


nucleus

• Chadwick: 1932 neutron

• Bohr: 1913 electron energy levels

• Gell-Mann/Zweig: 1964 quark theory


Joseph John
Thomson
(1856-1940)

British physicist
and mathematician

Nobel Prize in 1906


(existence of electrons)

1897: calc’d electron’s mass-to-charge


ratio in cathode-ray experiment
Thomson’s Cathode-Ray Experiment
Known before:
• atoms are normally neutral
(neither positive nor
negative charge)

• When cathode rays are


made, remaining atoms are
positively charged (ions)

Schematic of
actual 1897
apparatus
(vacuum inside):
Cathode-Ray Experiment:
Thomson (1897)
• Undeflected => Point
1

• Rays can be attracted


to + plate (hit Point 3)
or deflected by
magnetic field (hit
Point 2).
Vacuum tube w/fluorescent
end coating, electrodes, and
• Rays have negative high-voltage passing through.
charge, which can’t be
Thomson’s Cathode-ray Results

• Calculated mass-to-charge ratio (using


math and known field strengths) and energy
of ray particles

• Mass-to-charge ratio for cathode rays was


over 1000 times smaller than that of a
charged hydrogen atom (a proton),
suggesting
– either cathode rays carried huge charge,
– or they were amazingly light relative to
their charge => supported in future
Thomson’s conclusions/questions
•“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?
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.


Robert Millikan (1868-1953)
U.S. physicist

Nobel Prize in 1923


(charge of
electron: 1909
oildrop expt.)

With Thomson’s
result, this
allowed Millikan’s experimental apparatus.
calculation of
electron mass.
Millikan’s Oil-Drop Experiment (1909)
• Spray oil... droplets go
thru plate’s hole
• Hit air molecules with X-
rays... knock off
electrons.
• Electrons on oil drops…
now, charged.
• Adjust voltage... a drop is
held stationary.
• Use drop’s mass, voltage Diagram of apparatus -
to calculate drop’s charge electrical field between
(always whole multiple of plates is adjustable.
1.60 x 10-19 C).
Ernest
Rutherford
(1871-1937)

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

Nobel Prize in 1908


1910-11: Gold foil experiments
(radioactive decay)
Rutherford’s Experiments (1910-11)
(done by undergrad Ernest Marsden/physicist Hans
Geiger)

• Fired beam of alpha particles at very thin gold


foil.
• Alpha particles = positive-charged helium
ions,
mass 4 amu [He+2]
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.
Rutherford’s Experiment:
prediction
pass through
like this …
Rutherford’s
experiment: what
actually happened
Rutherford’s results, response in
amazement
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.”
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.
• like tiny solar system

Also, calculated nuclear mass as mass of positively-charged


protons. Protons only half of actual mass:
suggests neutral particles of same mass as proton?
How the Nucleus Repels Alpha
Particles

+
How much of an atom is empty
space?

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

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

In fact, if the nucleus of an atom


were the size of a large room,
the outermost electrons (far
edge of the electron cloud)
would be in: +
• The room next door
• The far side of campus
• Downtown Olean
• New York City

(click for the right answer)


James Chadwick
(1891-1974)

Rutherford student
English nuclear
physicist

Nobel prize in 1935


(existence of neutron)
Chadwick’s subatomic particle:
neutron
• Made rays of different atomic
particle

• Not deflected by electric fields,


so no charge (neutral) => neutron

• Collide neutron with different-


weight gases...measure their
deflections
=> calculate neutron mass:
Actual 1932 apparatus:
similar to + proton’s
Alpha particles from
polonium source (right)
hit beryllium target (left), • Neutrons penetrate and split
making new rays various heavy atoms, b/c not
repelled by nucleus (unlike
alpha)
Known Properties of Subatomic
Particles
Property Mass (amu), Relative
Particle Mass (g) Charge
Electron 0.00055 -1
9.1093897 x 10-28
Proton 1.00728 +1
1.6726231 x 10-24
Neutron 1.00866 0
1.6749286 x 10-24
Niels Bohr
(1885-1962)

Danish physicist

Revised Rutherford’s
model of atom (1913)
Bohr Looks at Emission Spectrum:
Hydrogen’s 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)
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


Hypotheses:
• Circling electron maintains orbit ONLY at specific
distances from nucleus (containing protons and
neutrons).
• Only way electron could exist for long time w/o giving off
radiation.
• Electron is more stable as distance r from nucleus