GENERAL CHEMISTRY (101)

MODERN ELECTRONIC THEORY OF ATOM

Atomic Theory through the Nineteenth Century

The earliest recorded discussion of the basic structure of matter comes from ancient Greek
philosophers, the scientists of their day. In the fifth century BC, Leucippus and Democritus argued
that all matter was composed of small, finite particles that they called atomos, a term derived from
the Greek word for “indivisible.” They thought of atoms as moving particles that differed in shape
and size, and which could join together. Later, Aristotle and others came to the conclusion that
matter consisted of various combinations of the four “elements”—fire, earth, air, and water—and
could be infinitely divided. Interestingly, these philosophers thought about atoms and “elements”
as philosophical concepts, but apparently never considered performing experiments to test their
ideas.

The Aristotelian view of the composition of matter held sway for over two thousand years, until
English schoolteacher John Dalton helped to revolutionize chemistry with his hypothesis that the
behavior of matter could be explained using an atomic theory. First published in 1807, many of
Dalton’s hypotheses about the microscopic features of matter are still valid in modern atomic
theory. Here are the postulates of Dalton’s atomic theory.

1. Matter is composed of exceedingly small particles called atoms. An atom is the smallest
unit of an element that can participate in a chemical change.
2. An element consists of only one type of atom, which has a mass that is characteristic of the
element and is the same for all atoms of that element. A macroscopic sample of an element
contains an incredibly large number of atoms, all of which have identical chemical
properties.

A pre-1982 copper penny (left) contains approximately 3 × 1022 copper atoms (several dozen are
represented as brown spheres at the right), each of which has the same chemical properties.

3. Atoms of one element differ in properties from atoms of all other elements.
4. A compound consists of atoms of two or more elements combined in a small, whole-
number ratio. In a given compound, the numbers of atoms of each of its elements are always
present in the same ratio.
Copper(II) oxide, a powdery, black compound, results from the combination of two types of
atoms—copper (brown spheres) and oxygen (red spheres)—in a 1:1 ratio.

5. Atoms are neither created nor destroyed during a chemical change, but are instead rearranged
to yield substances that are different from those present before the change

When the elements, copper (a shiny, red-brown solid, shown here as brown spheres) and oxygen
(a clear and colorless gas, shown here as red spheres) react, their atoms rearrange to form a
compound containing copper and oxygen (a powdery, black solid).

Dalton’s atomic theory provides a microscopic explanation of the many macroscopic properties of
matter. For example, if an element such as copper consists of only one kind of atom, then it cannot
be broken down into simpler substances, and if atoms are neither created nor destroyed during a
chemical change, then the total mass of matter present when matter changes from one type to
another will remain constant (the law of conservation of matter). Dalton's atomic theory was not
entirely correct because Dalton was unaware of the existence of both isotopes and nuclear
reactions.

Discovery of the Electron

Long before the end of the 19th century, it was well known that applying a high voltage to a gas
contained at low pressure in a sealed tube (called a gas discharge tube) caused electricity to flow
through the gas, which then emitted light. Researchers trying to understand this phenomenon found
that an unusual form of energy was also emitted from the cathode, or negatively charged electrode;
this form of energy was called a cathode ray.
A Gas Discharge Tube Producing Cathode Rays. When a high voltage is applied to a gas contained
at low pressure in a gas discharge tube, electricity flows through the gas, and energy is emitted in
the form of light

In 1897, the British physicist J. J. Thomson (1856–1940) proved that atoms were not the most
basic form of matter. He demonstrated that cathode rays could be deflected, or bent, by magnetic
or electric fields, which indicated that cathode rays consist of charged particles. More important,
by measuring the extent of the deflection of the cathode rays in magnetic or electric fields of
various strengths, Thomson was able to calculate the mass-to-charge ratio of the particles. These
particles were emitted by the negatively charged cathode and repelled by the negative terminal of
an electric field. Because like charges repel each other and opposite charges attract, Thomson
concluded that the particles had a net negative charge; these particles are now called electrons.
Most relevant to the field of chemistry, Thomson found that the mass-to-charge ratio of cathode
rays is independent of the nature of the metal electrodes or the gas, which suggested that electrons
were fundamental components of all atoms.

Deflection of Cathode Rays by an Electric Field. As the cathode rays travel toward the right, they
are deflected toward the positive electrode (+), demonstrating that they are negatively charged.

Subsequently, the American scientist Robert Millikan (1868–1953) carried out a series of
experiments using electrically charged oil droplets, which allowed him to calculate the charge on
a single electron. With this information and Thomson’s mass-to-charge ratio, Millikan determined
the mass of an electron:

Mass / Charge x Charge = Mass

Radioactivity

The second line of investigation began in 1896, when the French physicist Henri Becquerel (1852–
1908) discovered that certain minerals, such as uranium salts, emitted a new form of energy.
Becquerel’s work was greatly extended by Marie Curie (1867–1934) and her husband, Pierre
(1854–1906); all three shared the Nobel Prize in Physics in 1903. Marie Curie coined the term
radioactivity (from the Latin radius, meaning “ray”) to describe the emission of energy rays by
matter. She found that one particular uranium ore, pitchblende, was substantially more radioactive
than most, which suggested that it contained one or more highly radioactive impurities. Starting
with several tons of pitchblende, the Curies isolated two new radioactive elements after months of
work: polonium, which was named for Marie’s native Poland, and radium, which was named for
its intense radioactivity. Pierre Curie carried a vial of radium in his coat pocket to demonstrate its
greenish glow, a habit that caused him to become ill from radiation poisoning well before he was
run over by a horse-drawn wagon and killed instantly in 1906. Marie Curie, in turn, died of what
was almost certainly radiation poisoning.

Radium bromide illuminated by its own radioactive glow. This 1922 photo was taken in the dark
in the Curie laboratory.

Building on the Curies’ work, the British physicist Ernest Rutherford (1871–1937) performed
decisive experiments that led to the modern view of the structure of the atom. While working in
Thomson’s laboratory shortly after Thomson discovered the electron, Rutherford showed that
compounds of uranium and other elements emitted at least two distinct types of radiation. One was
readily absorbed by matter and seemed to consist of particles that had a positive charge and were
massive compared to electrons. Because it was the first kind of radiation to be discovered,
Rutherford called these substances α particles. Rutherford also showed that the particles in the
second type of radiation, β particles, had the same charge and mass-to-charge ratio as Thomson’s
electrons; they are now known to be high-speed electrons. A third type of radiation, γ rays, was
discovered somewhat later and found to be similar to the lower-energy form of radiation called x-
rays, now used to produce images of bones and teeth.

Effect of an Electric Field on α Particles, β Particles, and γ Rays. A negative electrode deflects
negatively charged β particles, whereas a positive electrode deflects positively charged α particles.
Uncharged γ rays are unaffected by an electric field. (Relative deflections are not shown to scale.)

These three kinds of radiation—α particles, β particles, and γ rays—are readily distinguished by
the way they are deflected by an electric field and by the degree to which they penetrate matter.
As illustrated above, α particles and β particles are deflected in opposite directions; α particles are
deflected to a much lesser extent because of their higher mass-to-charge ratio. In contrast, γ rays
have no charge, so they are not deflected by electric or magnetic fields.

Below illustration shows that α particles have the least penetrating power and are stopped by a
sheet of paper, whereas β particles can pass through thin sheets of metal but are absorbed by lead
foil or even thick glass. In contrast, γ-rays can readily penetrate matter; thick blocks of lead or
concrete are needed to stop them.

Relative Penetrating Power of the Three Types of Radiation. A sheet of paper stops comparatively
massive α particles, whereas β particles easily penetrate paper but are stopped by a thin piece of
lead foil. Uncharged γ rays penetrate the paper and lead foil; a much thicker piece of lead or
concrete is needed to absorb them.
The Atomic Model

Once scientists concluded that all matter contains negatively charged electrons, it became clear
that atoms, which are electrically neutral, must also contain positive charges to balance the
negative ones. Thomson proposed that the electrons were embedded in a uniform sphere that
contained also the positive charge and most of the mass of the atom.

Thomson’s Model of the Atom. In this model, the electrons are embedded in a uniform sphere of
positive charge.

In a single famous experiment, however, Rutherford showed unambiguously that Thomson’s

model of the atom was incorrect. Rutherford aimed a stream of α particles at a very thin gold foil
target and examined how the α particles were scattered by the foil. Gold was chosen because it
could be easily hammered into extremely thin sheets, minimizing the number of atoms in the target.

A Summary of Rutherford’s Experiments. (a) A representation of the apparatus Rutherford used

to detect deflections in a stream of α particles aimed at a thin gold foil target. The particles were
produced by a sample of radium. (b) If Thomson’s model of the atom were correct, the α particles
should have passed straight through the gold foil. (c) However, a small number of α particles were
deflected in various directions, including right back at the source. This could be true only if the
positive charge were much more massive than the α particle. It suggested that the mass of the gold
atom is concentrated in a very small region of space, which he called the nucleus.

Rutherford’s results were not consistent with a model in which the mass and positive charge are
distributed uniformly throughout the volume of an atom. Instead, they strongly suggested that both
the mass and positive charge are concentrated in a tiny fraction of the volume of an atom, which
Rutherford called the nucleus. It made sense that a small fraction of the α particles collided with
the dense, positively charged nuclei in either a glancing fashion, resulting in large deflections, or
almost head-on, causing them to be reflected straight back at the source.

Although Rutherford could not explain why repulsions between the positive charges in nuclei that
contained more than one positive charge did not cause the nucleus to disintegrate, he reasoned that
repulsions between negatively charged electrons would cause the electrons to be uniformly
distributed throughout the atom’s volume. Today it is known that strong nuclear forces, which are
much stronger than electrostatic interactions, hold the protons and the neutrons together in the
nucleus. For this and other insights, Rutherford was awarded the Nobel Prize in Chemistry in 1908.

A Summary of the Historical Development of Models of the Components and Structure of the Atom.
The dates in parentheses are the years in which the key experiments were performed.
The historical development of the different models of the atom’s structure is summarized in
Rutherford who established that the nucleus of the hydrogen atom was a positively charged
particle, for which he coined the name proton in 1920. He also suggested that the nuclei of elements
other than hydrogen must contain electrically neutral particles with approximately the same mass
as the proton. The neutron, however, was not discovered until 1932, when James Chadwick (1891–
1974, a student of Rutherford; Nobel Prize in Physics, 1935) discovered it. As a result of
Rutherford’s work, it became clear that an α particle contains two protons and neutrons, and is
therefore the nucleus of a helium atom.

The Evolution of Atomic Theory, as Illustrated by Models of the Oxygen Atom.

Rutherford’s model of the atom is essentially the same as the modern model, except that it is now
known that electrons are not uniformly distributed throughout an atom’s volume. Instead, they are
distributed according to a set of principles described by Quantum Mechanics.

The model of the atom has evolved over time from the indivisible unit of Dalton to the modern
view we have today.

Summary

The ancient Greeks proposed that matter consists of extremely small particles called atoms. Dalton
postulated that each element has a characteristic type of atom that differs in properties from atoms
of all other elements, and that atoms of different elements can combine in fixed, small, whole-
number ratios to form compounds. During any chemical change, atoms are neither created nor
destroyed. Atoms are the ultimate building blocks of all matter. The modern atomic theory
establishes the concepts of atoms and how they compose matter.

Atoms consist of negatively charged electrons around a central nucleus composed of more massive
positively charged protons and electrically neutral neutrons. Radioactivity is the emission of
energetic particles and rays (radiation) by some substances. Three important kinds of radiation are
α particles (helium nuclei), β particles (electrons traveling at high speed), and γ rays (similar to x-
rays but higher in energy).