Chapter Four Atomic Structure

As in other fields, the early Greeks contributed to the modern atomic theory. Democritus (460-
370 BC) postulated that “the universe consists of empty space and an almost infinite number of
indivisible and invisible particles” which differ in form, position and arrangement. These
elementary particles were called atoms. The developments in the field of chemistry in the 19th
century led to the distinction between atoms and molecules. A collection of atoms of one type
which cannot be decomposed into simpler units by any chemical transformation is called an
element. The elements can be combined in many ways to form compounds. The smallest particle
preserving the characteristics of the compound is called the molecule and the smallest particle
similarly preserving the characteristics of the element is called the atom. The size of the atom or
the molecule is so small that only indirect evidence for their existence can obtained. The interest
in atomic structure was renewed with the discovery of electrons in low pressure gas discharge
experiments towards the end of the 19thcentury. Since electrons came from atoms it was
surmised that any model for the structure of atoms should have electrons in it. Since electrons are
negative in charge and atoms are neutral, it was concluded that the atoms also continued
positive charge to neutral, it was concluded that the atoms also contained positive charge to
neutralize the electronic charge. Then two questions arose-how many electrons are there in an
atom, and how are these electrons and positive charges arranged within an atom? Rutherford,
based on his alpha-particle experiment, proposed a new model for an atom in which he said that
the positive charge and most of the atomic mass are concentrated in a very small central region
which came to be called later, the nucleus, about which the electrons are grouped in some sort of
configuration, Rutherford’s model suffered from many disadvantages because it did not say
anything about the location or movement of the electrons or the nucleus. It gave no explanation
on how these electrons could remain in equilibrium about the nucleus. If, as in planetary motion,
electrons were assumed to be moving in an orbit, then classical theory would lead to loss of
energy through radiation which would cause the electron to spiral towards the nucleus and finally
fall into the nucleus.

Protons
• positively charged 1.60217653 × 10-19 Coulomb
• A diameter of about 1.65×10-15 m
• Mass of 1.6726×10-27 kg
• About 1840 times the mass of an electron
Neutrons-discovered by Chadwick in 1932
• Not charged
• A diameter of about 1.65×10-15 m
• Mass of 1.6749 x 10-27 kg

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 Atomic number and Mass number

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J.J. Thomson

Thomson’s “Plum Pudding” Model He discovered the electron in 1897 before the nucleus
was discovered Later discoveries invalidated this model. the atoms of the elements consist of a
number of negatively electrified corpuscles enclosed in a sphere of uniform positive
electrificationJ.J. Thomson proposed that atoms were composed of an amorphous positively
charged plum pudding with embedded electrons. The absorption and emission of light could
then be accounted for by these electrons having certain natural frequencies of harmonic
oscillation

Rutherford’s famous gold foil experiment:

showed that the positive charge of the atom must be concentrated in a tiny, yet heavy volume he
called the nucleus almost all of the mass of the atom is in the nucleus very light electrons
surround this nucleus the volume that an atom occupies is mostly empty space

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 Gold Foil Experiment
In 1909, Hans Geiger and Ernest Marsden performed an experiment, under the direction of
Ernest Rutherford to test Thomson’s model of the atom. They used a radioactive source that
emitted alpha particles (charge = +2) in a tightly collimated beam, onto a gold foil. They then
looked at the angle through which the alpha particles are scattered

The alpha particle being relatively heavy (compared to an electron), should pass through an
amorphous positively charged (but dilute) object with little deflection. What they actually saw
was very large deflections (occasionally) and relatively large deflections more often. The only
way to explain this was that the positively charged “nucleus” of the atom.

There are several ways to show the expected results with the Thomson model. He uses
conservation of energy. He shows using momentum and force, that the expected maximum
deviation is quite small. Notice that the angle depends on the force (~1/r2) and the time spent
under the force (~r), finally depending on the radius of the positively charged object as 1/r

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Rutherford Model To explain the experimental results, Rutherford needed that the radius of
positive charge that was responsible for scattering the alpha particles was roughly 10,000 times
smaller than the atomic radius. His calculation of the radius was simple, and his interpretation
was correct – his alpha particles weren’t high enough energy to reach the gold nucleus

A positive and heavy charge with a small radius, and electrons surrounding it and they stay
separated from each other. They must be orbiting

since they are accelerating, they must radiate This will lose energy, causing them to fall closer to
the positive core.

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 Bohr Model
In 1913 Rutherford's post-doctoral student, Niels Bohr, proposed a new model of the atom. It
pre-dated de-Broglie waves by about 11 years, so he didn’t yet know about matter waves, but he
hypothesized that the electron angular momentum was quantized as

Since it was quantized, there must be a lowest angular momentum, and hence, a lowest energy
for the electron. This meant that the electrons couldn’t radiate at just any energy and if the
electron was in its lowest energy, it couldn’t radiate at all. It also could explain emission and
absorption spectra, since electrons would only emit when changing energy from one quantized
state to another

Atomic spectra

Emission Lines About the same time, people were using flame emission spectroscopy to see that
different materials emitted light of specific frequencies when heated to high enough temperatures that
they became heated gase

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 Emission Lines

Another way to do this is to pass an electric current through a gas, thermally heating it and seeing the
spectra of light emission using a diffraction grating

Absorption & Emission

The other aspect that was noticed is that spectra emitted by an heated element was the same as
the spectra of absorption when continuous light was passed through the same cool element (as
agas). This confirmed that the spectra were a property of the element

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Hydrogen Energy Levels

In 1885,Johann Balmer discovered a pattern for the visible emission spectra of hydrogen.

His formula was: Later, Rydberg reformulated the Balmer formula as:

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