EARLY THEORIES OF THE ATOMIC STRUCTURE

What are the smallest building blocks of everyday objects? This question has interested man since
the age of the Greek philosophers. Philosophers from the earliest times have speculated about the
nature of the fundamental "stuff" from which the world is made. Most, like Aristotle, argued that
matter could be divided infinitely. However, one brilliant philosopher, Democritus (460-370 BC),
argued that there is a limit. He proposed that the smallest piece that any element (like aluminum)
can be divided into and still be recognized as that element is an atom, a word derived from the
Greek word atomos, meaning "indivisible or uncuttable."

The first clear atomic hypothesis for the existence of atoms was presented in 1803 by John Dalton
(1766-1844). He suggested that:
1. All matter is composed of extremely small particles called atoms.
2. Atoms cannot be created nor destroyed in a chemical reaction, atoms of different
elements are separated, joined, or rearranged. They are never changed into atoms
of another element.
3. All atoms of the same element are alike and different from those of any other
component.
4. A compound is a specific combination of more than one element atoms.

According to Dalton's atomic theory, atoms are the smallest particles of an element that retain the
chemical identity of the element. As noted in the postulates of Dalton's theory, an element is
composed of only one kind of atom. A compound, in contrast, contains atoms of two or more
elements. Dalton's theory explains several simple laws of chemical combination that were known
during his time. One of these laws was the law of constant composition: In a given compound,
the relative numbers and kinds of atoms are constant. This law is the basis of Dalton's Postulate 4.
Another fundamental chemical law was the law of conservation of mass (also known as the law
of conservation of matter): The total mass of materials present after a chemical reaction is the same
as the total mass present before the reaction. This law is the basis for Postulate 3. Dalton proposed
that atoms always retain their identities and that atoms taking part in a chemical reaction rearrange
to give new chemical combinations.

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Dalton reached his conclusion about atoms based on chemical observations in the macroscopic
world of the laboratory. Neither he nor those who followed him during the century after his work
was published had direct evidence for the existence of atoms. As scientists began to develop
methods for more detailed probing of the nature of matter, the atom, which was supposed to be
indivisible, begun to show signs of a more complex structure: We now know that the atom is
composed of still smaller subatomic particles. Before we summarize the current model of atomic
structure, we will briefly consider a few of the landmark discoveries that led to that model.

Cathode Rays and Electrons

During the mid-1800s, scientists began to study electrical discharge through partially evacuated
tubes (tubes that had been pumped almost empty of air). In 1897, J.J. Thomson (1856–1940)
(Prof of Physics at Cavendish Lab at Cambridge University) discovered the electron by
experimenting with the cathode ray tube. A cathode ray tube is made of glass containing two thin
pieces of metal, called electrodes, sealed in it as shown in Figure 1.1. When sufficiently high
voltage is applied across the electrodes, current starts flowing through a stream of particles moving
in the tube from the negative electrode (cathode) to the positive electrode (anode). Because they
are emitted from the cathode, they are called cathode rays or cathode ray particles. The flow of
current from cathode to anode was further checked by making a hole in the anode and coating the
tube behind anode with phosphorescent material zinc sulphide. When these rays, after passing
through anode, strike the zinc sulphide coating, a bright spot on the coating is developed.

Figure 1.1. In a cathode-ray tube, electrons move from the negative electrode (cathode) to the
positive electrode (anode).

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J. J. Thomson observed that the cathode rays had some interesting properties. First, their path can
be bent by placing a magnet near the cathode ray tube. Second, placing an electric charge near the
stream of rays also causes the path they follow to exhibit curvature. From these observations, he
concluded that the rays are electrically charged. The cathode rays were shown to carry a negative
charge because they were attracted to a positively charged plate and repelled by one that carried a
negative charge. From the study of the behavior of cathode rays in a magnetic field, Thomson was
able to determine that the mass of one of these particles was almost 2,000 times lighter than a
hydrogen atom. The negative particles in cathode rays are electrons, and Thomson is credited with
the discovery of the electron. Thus, it was determined that atoms contained electrons and since the
atom was neutral, it was suggested that besides electrons, an atom also contained positive charges.

In 1904, Thomson suggested that an atom consisted of a uniform positive sphere of matter on
which electrons were embedded, as shown in Figure 1.2. This became to be known as the “plum
pudding” model of the atom because it resembled plums embedded in a pudding. Somehow, an
equal number of positive and negative particles were held in this material. An important feature of
this model is that the mass of the atom is assumed to be uniformly distributed over the atom. Of
course, we now know that this is an incorrect view of the atom but the model did account for
several features of atomic structure.

Figure 1.2. J. J. Thomson's "plum-pudding" model of the atom.

Radioactivity

One of the first and most important clues to an understanding of the nucleus occurred with the
discovery of the phenomenon later known as radioactivity in early 1896 by the French physicist

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Henri Becquerel. In 1896 the French scientist Henri Becquerel (1852-1908) was studying a
uranium compound when he discovered that it spontaneously emits high-energy radiation.
Becquerel discovered that uranium salt crystals emit an invisible radiation that can darken a
photographic plate even if the plate is covered to exclude light. The radiation emitted by the
crystals did not require external stimulation; this spontaneous emission of radiation was called
radioactivity. At Becquerel's suggestion Marie Curie and her husband, Pierre, began experiments
to isolate the radioactive components of the compound.

Further study of the nature of radioactivity, principally by the British scientist Ernest Rutherford,
revealed three types of radiation: alpha (α), beta (β), and gamma (γ) radiation. Each type differs in
its response to an electric field, as shown in Figure 1.3. The paths of both α and β radiations are
bent by the electric field, although in opposite directions; γ radiation is unaffected.

Figure 1.3. The behavior of alpha (α), beta (β), and gamma (γ) rays in an electric field.

Alpha (α) radiation

An alpha particle consists of two protons and two neutrons. They have the same structure as a
helium nucleus, so we can write it down as 42𝐻𝑒. Remember that a proton or neutron is about 1,800
times larger than an electron, so an α particle with two neutrons and two protons is huge.
Additionally, since this helium nucleus has two protons and no electrons, it’s positively charged.
Radionuclides that are rich in protons desire to undergo α decay to decrease their positive charge.
The decay process for alpha particles is:

𝐴 𝐴−4
𝑍𝑋 → 𝑍−2𝑌 + 42𝐻𝑒

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where A is the mass number, Z is the atomic number, X is called the parent nucleus and Y is called
the daughter nucleus. For example:

238 234
92𝑈 → 90𝑇ℎ + 42𝐻𝑒

226 222
88𝑅𝑎 → 86𝑅𝑛 + 42𝐻𝑒

Beta (β) radiation

In many ways, β radiation is the opposite of α radiation. β radiation is usually just the emission of
an electron, and so it’s negatively charged whereas α particles are positively charged; however,
there’s one form of β decay known as β+ decay, or sometimes positron decay, where a radionuclide
emits a positively charged electron known as a positron. A β particle (when formed) leaves behind
a nucleus with an extra proton, because it’s created when a neutron decomposes. This neutron
decomposition results in a photon (particle of light) and an electron (or β particle). So now the
atomic number increases by 1 (instead of decreasing by 2 like α decay). The beta-negative decay
process is:
𝐴
𝑍𝑋 → 𝐴
𝑍+1𝑌 + −10𝑒

For example:

234 234
90𝑇ℎ → 91𝑃𝑎 + −10𝑒

The emission of an electron from the nucleus is surprising because we know that the nucleus is
composed only of protons and neutrons. This can be explained by noting that the emitted electron
is created in the nucleus by a process in which a neutron is transformed into a proton:

1
0𝑛 → 11𝑝 + −10𝑒

Positron emission is most common in lighter elements with a low neutron-to-proton ratio. For
example, positron emission from a sodium nucleus looks like this:

22
11𝑁𝑎 → 22
10𝑁𝑒 + 01𝑒

These particles don’t last long before finding a negatively charged electron. As soon as these
lovebirds meet, they run into one another at full blast and completely annihilate.

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Gamma (γ) Decay

A nucleus that undergoes radioactive decay is often left in an excited state; the nucleus can then
undergo a second decay. Gamma rays are not particles but high-energy electromagnetic radiation.
Gamma rays carry excess energy from the nucleus. There is no change in the atomic structure
before and after the emission of gamma rays, unlike the other two particles where new atoms are
formed. γ radiation doesn’t cause the nucleus to decay into a different element. Instead of the
nucleus being converted to another element like in α and β radiation, now the entire nucleus just
sheds energy. Gamma radiation has no mass because there are no protons left, and it has no
electricity. γ radiation travels at the speed of light — because it is light!

Half-life

Half-life is the time it takes for half of the unstable nuclei in a sample to decay or for the activity
of the sample to halve or for the count rate to halve. Count-rate is the number of decays recorded
each second by a detector, such as the Geiger-Muller tube. The illustration below (Figure 1.4)
shows how a radioactive sample is decaying over time.

Figure 1.4. Half-life for radium 226 is 1620 years. In one half-life 𝑡1⁄ the number decreases to
2

half of its original value.

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Radioactive decay reduces the number of radioactive nuclei over time. In one half-life 𝑡1⁄ the
2

number decreases to half of its original value. Half of what remains decay in the next half-life, and
half of those in the next, and so on. This is an exponential decay, as seen in the graph of the number
of nuclei present as a function of time.

In 1910, Ernest Rutherford (Prof. of Physics at Victoria University in Manchester, UK; 1871-
1937) did some experiments on Thomson’s plum pudding model. Recall that the plum pudding
model of the atom pictures the positive charge as being diffused throughout the atom and the
electrons as point charges scattered evenly among the positive charge. The members of his lab
fired a beam of positively charged particles called alpha particles at a very thin sheet of gold foil
(figure below). The results were unexpected: Almost all the alpha particles passed directly through
the foil without deflection, but some were deflected by large angles, and some were even reflected
toward the source. Although the explanation for these results was not immediately obvious, the
findings were inconsistent with Thomson’s model.

By 1911, Rutherford was able to explain these observations. On the basis of the observations,
Rutherford drew the following conclusions regarding the structure of atom:

i. Most of the space in the atom is empty as most of the α–particles passed through the foil
undeflected.
ii. A few positively charged α– particles were deflected indicating that the positive charge of
the atom is not spread throughout the atom as Thomson had presumed. The positive charge
and most of the mass in a given atom were concentrated in a small volume within the atom,

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 which he called the nucleus. Thus, the alpha (α) particles that were reflected back toward
the source were those that had made direct hits upon the centers of positive charge, and
those that were deflected at large angles were those that had had near misses.

To explain his observations, Rutherford developed a new model of the structure of the atom.
According to Rutherford, the nucleus is surrounded by electrons that move around the nucleus at
a very high speed in circular paths called orbits. Thus, Rutherford’s model of the atom resembles
the solar system in which the nucleus plays the role of the sun and the electrons of revolving
planets. Because of this, it is often referred to as the planetary model of the atom. However, when
a body is moving in an orbit, it undergoes acceleration (even if the body is moving with a constant
speed in an orbit, it must accelerate because of changing direction). So an electron in the planetary
model describing planet like orbits is under acceleration.

According to the electromagnetic theory of Maxwell, charged particles when accelerated should
continuously lose energy by emitting electromagnetic radiation (This feature does not exist for
planets since they are uncharged). Hence, as the electron loses energy, it should spiral into the
positively charged nucleus. This spiraling does not occur since hydrogen atoms are stable. Thus,
the Rutherford model cannot explain the stability of an atom. Since the motion of electrons in
orbits leads to the instability of the atom, then why not consider electrons as stationary around the
nucleus? If the electrons were stationary, electrostatic attraction between the dense nucleus and the
electrons would pull the electrons toward the nucleus. Another serious drawback of the Rutherford
model is that it says nothing about how the electrons are distributed around the nucleus and the
energies of these electrons. So, how can we explain this apparent violation of the laws of physics?

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