Atomic Theory I

The Early Days

by Anthony Carpi, Ph.D.

Joseph John Thomson ; Until the final years of the nineteenth century,
the accepted model of the atom resembled that
Born 1856-12-18 , Cheetham Hill, Manchester, UK;
Died 30 August 1940 (aged 83) , Cambridge, UK of a billiard ball - a small, solid sphere. In
He was awarded a Nobel Prize in 1906, "in recognition
1897, J. J. Thomson dramatically changed the
of the great merits of his theoretical and experimental
modern view of the atom with his discovery of
investigations on the conduction of electricity by gases."
the electron. Thomson's work suggested that
the atom was not an "indivisible" particle as John Dalton had suggested but, a jigsaw puzzle made of
smaller pieces.
Thomson's notion of the electron came from his work with a nineteenth century scientific curiosity: the
cathode ray tube. For years scientists had known that if an electric current was passed through a vacuum
tube, a stream of glowing material could be seen; however, no one could explain why. Thomson found
that the mysterious glowing stream would bend toward a positively charged electric plate. Thomson
theorized, and was later proven correct, that the stream was in fact made up of small particles, pieces of
atoms that carried a negative charge. These particles were later named electrons.
After Eugen Goldstein’s 1886 discovery that atoms had positive charges, Thomson imagined that atoms
looked like pieces of raisin bread, a structure in which clumps of small, negatively charged electrons
(the "raisins") were scattered inside a smear of positive charges. In 1908, Ernest Rutherford, a former
student of Thomson's, proved Thomson's raisin bread structure incorrect.
Rutherford performed a series of experiments with radioactive alpha particles. While it was unclear at
the time what the alpha particle was, it was known to be very tiny. Rutherford fired tiny alpha particles
at solid objects such as gold foil. He found that while most of the alpha particles passed right through
the gold foil, a small number of alpha particles passed through at an angle (as if they had bumped up
against something) and some bounced straight back like a tennis ball hitting a wall. Rutherford's
experiments suggested that gold foil, and matter in general, had holes in it! These holes allowed most of
the alpha particles to pass directly through, while a small number ricocheted off or bounced straight back
because they hit a solid object.
In 1911, Rutherford proposed a revolutionary view of the atom. He suggested that the atom consisted of
a small, dense core of positively charged particles in the center (or nucleus) of the atom, surrounded by a
swirling ring of electrons. The nucleus was so dense that the alpha particles would bounce off of it, but
the electrons were so tiny, and spread out at such great distances, that the alpha particles would pass
right through this area of the atom. Rutherford's atom resembled a tiny solar system with the positively
charged nucleus always at the center and the electrons revolving around the nucleus.

Interpreting Rutherford's Gold Foil Experiment

The positively charged particles in the nucleus of the atom were called protons. Protons carry an equal,
but opposite, charge to electrons, but protons are much larger and heavier than electrons.

1
In 1932, James Chadwick discovered a third type of subatomic particle, which he named the neutron.
Neutrons help stabilize the protons in the atom's nucleus. Because the nucleus is so tightly packed
together, the positively charged protons would tend to repel each other normally. Neutrons help to
reduce the repulsion between protons and stabilize the atom's nucleus. Neutrons always reside in the
nucleus of atoms and they are about the same size as protons. However, neutrons do not have any
electrical charge; they are electrically neutral.
Atoms are electrically neutral because the number of protons (+ charges) is equal to the number of
electrons (- charges) and thus the two cancel out. As the atom gets larger, the number of protons
increases, and so does the number of electrons (in the neutral state of the atom). The illustration linked
below compares the two simplest atoms, hydrogen and helium.
Simulated hydrogen and helium atoms
Atoms are extremely small. One hydrogen atom (the smallest atom known) is approximately 5 x 10-8
mm in diameter. To put that in perspective, it would take almost 20 million hydrogen atoms to make a
line as long as this dash -. Most of the space taken up by an atom is actually empty because the electron
spins at a very far distance from the nucleus. For example, if we were to draw a hydrogen atom to scale

and used a 1-cm proton (about the size of this picture - ), the atom's electron would spin at a
distance of ~0.5 km from the nucleus. In other words, the atom would be larger than a football field!
Atoms of different elements are distinguished from each other by their number of protons (the number
of protons is constant for all atoms of a single element; the number of neutrons and electrons can vary
under some circumstances). To identify this important characteristic of atoms, the term atomic number
(z) is used to describe the number of protons in an atom. For example, z = 1 for hydrogen and z = 2 for
helium.
Another important characteristic of an atom is its weight, or atomic mass. The weight of an atom is
roughly determined by the total number of protons and neutrons in the atom. While protons and neutrons
are about the same size, the electron is more that 1,800 times smaller than the two. Thus the electrons'
weight is inconsequential in determining the weight of an atom - it's like comparing the weight of a flea
to the weight of an elephant. Refer to the animation above to see how the number of protons plus
neutrons in the hydrogen and helium atoms corresponds to the atomic mass.
Anthony Carpi, Ph.D. "Atomic Theory I: The Early Days," Visionlearning Vol. CHE-1 (2), 2003.
http://www.visionlearning.com/library/module_viewer.php?mid=50

Lyman series
Lyman series (′lī·mən ′sir·ēz) (spectroscopy) A group of lines in the ultraviolet spectrum
of hydrogen covering the wavelengths of 121.5-91.2 nanometers.

Lyman series
In physics, the Lyman series is the series of transitions and resulting emission lines of the hydrogen
atom as an electron goes from n ≥ 2 to n = 1 (where n is the principal quantum number referring to
the energy level of the electron). The transitions are named sequentially by Greek letters: from n = 2 to n
= 1 is called Lyman-alpha, 3 to 1 is Lyman-beta, 4 to 1 is Lyman-gamma, etc. The series is named after
its discoverer, Theodore Lyman.

History
The first line in the ultraviolet spectrum of the Lyman series was discovered in 1906 by Harvard
physicist Theodore Lyman, who was studying the ultraviolet spectrum of electrically excited hydrogen
gas. The rest of the lines of the spectrum were discovered by Lyman from 1906-1914.

2
The spectrum of radiation emitted by hydrogen is non-continuous. Here is an illustration of the first
series of hydrogen emission
lines:
Historically, explaining the
nature of the hydrogen
spectrum was a considerable
problem in physics. Nobody
could predict the wavelengths
of the hydrogen lines until 1885
when the Balmer formula gave
an empirical formula for the
visible hydrogen spectrum.
Within five years Johannes
Rydberg came up with an
empirical formula that solved
the problem, presented first in
1888 and in final form in 1890. Rydberg managed to find a formula to match the known Balmer series
emission lines, and also predict those which were not yet discovered. Different versions of the Rydberg
formula with different simple numbers were found to generate different series of lines.

The Lyman series

The version of the Rydberg formula which generated the Lyman series was:

Where n is a natural number greater or equal than 2 (i.e. n = 2,3,4,...).

Therefore, the lines seen in the image are the wavelengths corresponding to n=2 on the left, to n=∞ on
the right (there are infinitely many spectral lines, but they become very dense as they approach to n=∞,
so only some of the first lines and the last one appear).
The wavelengths (nm) in the Lyman series are all ultraviolet:
n 2 3 4 5 6 7 8 9 10 11 ∞
Wavelength (nm) 121.6 102.5 97.2 94.9 93.7 93.0 92.6 92.3 92.1 91.9 91.15

Explanation and derivation

In 1913, when Niels Bohr produced his Bohr model theory, the reason why hydrogen spectral lines fit
Rydberg's formula was explained. Bohr found that the electron bound to the hydrogen atom must have
quantized energy levels described by the following formula:

According to Bohr's third assumption, whenever an electron falls from an initial energy level(Ei) to a
final energy level(Ef), the atom must emit radiation with a wavelength of:

There is also a more comfortable notation when dealing with energy in units of electronvolts and
wavelengths in units of angstroms:

3
Replacing the energy in the above formula with the expression for the energy in the hydrogen atom
where the initial energy corresponds to energy level n and the final energy corresponds to energy level
m:

where R is the same Rydberg constant of Rydberg's long known formula.

For the connection between Bohr, Rydberg, and Lyman, one must replace m by 1 to obtain:

which is Rydberg's formula for the Lyman series. Therefore, each wavelength of the emission lines
corresponds to an electron dropping from a certain energy level (greater than 1) to the first energy level.

The Mystery of Emission-Line Spectra

If we pass light through a prism or diffraction grating, we can see the intensity as a function of
wavelength.

The type of spectrum we see depends on the nature of the source.

 Solids, liquids, and dense gases emit light of all wavelengths, without any gaps. We call this a
continuous spectrum.

 Thin gases emit light of only a few wavelengths. We call this an emission or bright line
spectrum.

 If there is a source of light behind it, a thin gas will absorb light of the same wavelengths it
emits. We call this an absorption or dark line spectrum.

4
Scientists in the nineteeth century quickly figured out that each element generates its own unique set of
wavelengths of emission or absorption. For example, compare spectra of :
hydrogen:

helium:

carbon:

But why? Was there any underlying reason for each element to generate a unique spectrum? Johannes
Balmer studied the optical spectrum of hydrogen and found a pattern in the wavelengths of its emission
lines.

Expressed in nanometers, the wavelengths are

374.9 377.0 379.7 383.4 388.8 396.9 410.1 433.9 486.0 656.1
Balmer found that a simple formula reproduced these wavelengths:
n2
 (n)  364,5 nm . , n 3,4,5, . . .
n2 - 4
Curious. As a reward for his insight, this set of visible lines in the hydrogen spectrum are called the
"Balmer series".
Within a short period of time, other scientists found similar patterns in other portions of the
electromagnetic spectrum.
Paschen, in the infrared, measured lines with wavelengths
866.2 874.8 886.0 901.2 922.6 954.3 1004.6 1093.5 1281.4 1874.5
which matched the series
n2
 (n)  820,5 nm . , n 4,5,6, . . .
n2 - 9
and Lyman, in the ultraviolet, a series of lines with wavelengths
91.9 92.1 92.3 92.6 93.0 93.7 94.9 97.2 102.5 121.5
5
corresponding to the series
n2
 (n)  91,1 nm . , n 2,3,4, . . .
n2 - 1
In fact, scientists soon realized that hydrogen's spectrum could be broken down into a large number of
series, each of which had wavelengths obeying a formula like:
n2
 ( n , k )  ( limit ) . , n k 1 , k  2 , k  3 , . . .
n2 - k 2

The Lyman series corresponds to k = 1 with a limit of 91.1 nm, the Balmer series to k = 2 with a
limit of 364.5 nm, and so forth.
But what did it all mean? Why were there regular patterns in these emission line wavelengths? Other
elements didn't have such nice, regular patterns -- look at mercury, for example – so what is special
about hydrogen?

Another curious feature of the hydrogen spectrum appears if one writes down the frequencies of the
emission lines, rather than the wavelengths. In the Lyman and Balmer series, we have ( in units of
14
10 Hz ) .

Lyman lines: 31.899 31.498 30.760 29.165 24.609

Balmer lines: 7.533 7.292 6.891 6.152 4.557

Can you find pairs of frequencies which, when added together, yield another observed frequency?
This is called the Ritz recombination principle, after the scientist (Ritz) who first noticed it.
Again, why are there such simple patterns in the spectrum of hydrogen? What does it all mean?

Of course, even if scientists didn't understand exactly why each element had its own pattern of emission
and absorption features, they were quick to use the information. One can
 figure out the chemical composition of an object
 determine an object's radial velocity
 measure how fast an object is spinning
and much, much more ....

6
 J. J. Thomson on the Electron
Amer. Inst. Physics - 800k audio,
live recording of J. J. Thomson
speaking about the electron.
On the Structure of the Atom
,Thomson's 1904 paper describing
atomic structure.
Joseph John Thomson ;
Born 1856-12-18 , Cheetham Hill, Manchester, UK;
Died 30 August 1940 (aged 83) , Cambridge, UK
He was awarded a Nobel Prize in 1906, "in recognition
of the great merits of his theoretical and experimental
investigations on the conduction of electricity by gases."

Nuclear Constitution of Atoms

Text of Rutherford's 1919 lecture on
nuclear structure.

7
Joseph John Thomson
Born 1856-12-18
Cheetham Hill, Manchester, UK Died 30 August 1940 (aged 83)
Cambridge, UK