4 th New England Association of Chem

Wh a t is an atom? The word atom,

meaning indivisible, has its origin in the Greek culture;
Democritus (460 B.c.) is given credit for the description
of nature as composed of atoms. The stimulus for the
idea is not exactly known, but some attribute it to his
teacher Leucippus.' Others point to the general atmos-
phere of speculation on subjects such as the origin of
matter which was then rife. Historians usually agree
that Democritus extended the prevailing thoughts of
his time, although he performed no experiment to prove
the existence of his fundamental par t i cl ehe only im-
agined it to exist. His reasoning is clear enough: A
piece of paper can be cut in half, and in half until it
cannot be cut in half again, no matter how sharp a tool
is used. There seems to be no reason why such an
atom cannot exist.
The genius of Democritus is not so much that he
postulated the existence of the atom but that he stated
for the first time that atoms moved within matter in
a void or vacuum. An analysis of how he developed
his idea gives us clues as t o what science is and how it
advances: He summarized the known beliefs of his
time; he made use of the known tool of scieucereason-
ing; he developed what we can call a model of the atom
and with this model he postulated the atom's properties.
Earlier philosophers had thought of the known elements
as fire, earth, air, and water and bad spoken of the fire
as moving out of one body into another. Democritus
thought that the diierent elements must have diierent
shapes. He reasoned that because water slipped easily,
its atom must be round and smooth. One can predict
that if smooth water is added to rough atoms, the rough
spots would be filled in and the rough atoms would be-
come smooth. We can see this work when we add
water to cupric sulfate crystals, but Democritus would
point t o the working artisans and say, "Stir rind, and
2 g,,
heat the indigo plants to smooth out the dye.
About a century later Aristotle, a student of Socrates
and Plato, developed a hypothesis that matter was con-
tinuous. Though he used much the same background
as Democritus had used, and even had the advantage of
knowing Democritus' theory, he reasoned differently.
With equal justification, he decided that matter could
Edgar N. Johnson
West Springfield High School
West Springfield, Moss.
not only be splir to the same point ns 1)rrnocrirus'ntorn
-
I I.I:ICESTKR, I ~XSRY, 'The Hiatorieal Rackground of Chemis-
Atoms, Fire, Waves, or What?
try," John Wiley and Sonq Inc., New York, 1956, p. 18
but could be split forever thereafter. Aristotle made
hi model more convincing by adding to it the concept
of opposites. Both Democritus and Aristotle were
aware of the continual struggle between opposites
(day and night, light and dark, wet and dry, etc.), but
it was Aristotle who included it in his explanation of
nature. He reasoned that sets of opposites, together
with prima materia, composed the material world. The
~ i m a materia was the force between the sets of oppo-
sites. Thus we may consider the following diagram
(Fig. 1) as the chemical model of Aristotle's theory and
essentially the one that was most respected for the next
2000 years!% The qualities of hot, cold, wet, and dry
could be imposed upon the prime matter in any amount,
by a continuous flow. For instance, if two dry sticks
are rubbed together they become hot and will produce
&e. When heat is taken from air which contains
moisture, the product is water. It is possible to add
fire to earth, driving out cold and giving a product which
will be a metal somewhere between water and earth.
Figure 1. ArirtoHe's chemical model.
The models of Aristotle and Democritus are products
of pure thought without any reference to validation by
experiment. As products of reason both are equally
reasonable. Aristotle's model was accepted almost
completely because it gave the best summary of the
previous thoughts and observations. It made predic-
tions better than Democritus' model.
READ, JOHN, "Through Alchemy to Chemistry," G. Bell and
Son, Ltd., London, 1957, p. 17.
Volume 37, Number 5, Muy 7 960 / 267
Two Centuries of Slow Progress
During t,he next 2000 years, chemistry advanced as
follows: Artisans began to use Aristotle's model to make
predictions, then tested the predictions. Some of them,
who called themselves "Alchemists" tried to find the cor-
rect amount of fire to add to earth to produce the metal
gold. The Chinese alchemists strove t,o make gold to
gain longevity, because gold did not rust. Western
alchemists wanted to replenish the treasuries of the
kings who had set up their laboratories. Most of these
alchemists were good experimenters; so their work re-
sulted in new products like gunpowder, alcohol, medi-
cal drugs, and special laboratory equipment,.
As the alchemists found new substances, new ideas
developed concerning the prima materia. Each experi-
menter required new modifications of Aristotle's model
to fit the new substances that he had isolated, for the
original model could not satisfy all the necessary require-
ments. Thus, in about the eighth century, Geber pro-
posed a modification based upon a Tria Prima. The
three fundamental properties of his model were:
metallic, represented by mercury; loss of metallic,
represented by sulfur; and stability, typified by salt.
Thus he argued that copper had some sulfur in it to
give it the yellow color, but it was not pure enough.
High purity would result in tin, iron, and other metals.
The task of the alchemist was to get the black fire of
sulfur (sometimes referred to as the philosopher's stone)
into the earth in the correct ratio. Geber's theory re-
tained the principle of continuous matter, but he added
the concept that certain qualities can be imposed upon
matter. This gave a new challenge to the alchemist.
Two major difficulties with Geber's model were its
dependence on the continuous nature of matter and its
emphasis on spirit-like properties. In an extension of
it near the end of the seventeenth century, Stahl pro-
posed that all matter is composed of the spirit of
fire, called phlogiston, and of an ash called ~ a l x . ~ The
difference between various substances was dependent
upon the amount of phlogiston that each substance con-
tained. Stahl helped to revive the atomist viewpoint
that matter was discontinuous, for he reasoned that
phlogiston and calx were held together by forces
similar to those later thought of as "gravitational."
Therefore he had to assume atoms. This model met
with almost immediate acceptance by all chemists.
For the first time they could explain the action of fire.
The emphasis on spirit-like properties was eliminated
in favor of a theory requiring quantitative amounts of
phlogiston and calx. As a result, attention was focused
on combustion and reduction of metals, and corrosion
was recognized as a slow process of combustion. The
new model summarized previous knowledge and made
predictions for chemists to check. Stahl had generalized
from the known data, as had Aristotle, Geber, and
Democritus. But more significantly he took data and
observations from experiments, and generalized from
them. Stahl had experimental proof, not just armchair
philosophy. For example, if a stick is burning, the
phlogiston is leaving at such a rate that it is hot. When
iron gives off its phlogiston, red rust is the result. If
a FRENCE, SIDNEY, "The Dranxa of Chemistry," The Univer-
sity Society, New York 1937, p. 27.
268 / Journal of Chemical Educotion
either the burning stick or the iron is placed in a closed
container, the phlogiston will stop going off as soon as
the container becomes full of phlogiston. If a zinc calx
is heated with charcoal (a substance which contains a
lot of phlogiston) the product is metallic zinc.
Stahl's model was used for about a hundred years.
In this case, as in many other cases, this was much too
long, although the success of Stahl's model is demou-
strated by the growth of chemistry in the eighteenth
century. Motivated by it, practicing chemists made
great strides in an effort to catch and isolate phlogiston.
The result of their effort was the discovery and isolation
of many gases and a study of their properties. The
work of great phlogistouists such as Boyle, Cavendish,
Priestley, Black, and Scheele advanced chemistry.
In the 1770's Lavoisier was concerned with two prob-
lems of the phlogiston modeL4 How can all the reduc-
ing gases be the same phlogiston? How can one explain
the gain in weight in burning iron and the apparent loss
of weight in burning wood? Lavoisier could explain
the difficulties if combustion were considered to be the
combination of oxygen with other matter. Lavoisier's
model can best be described by the quantitative rela-
tionship: Matter plus oxygen yields material oxide.
Lavoisier's model was needed when the experimental
data extended beyond the scope of Stahl's model. It
was conceived in the author's mind with the clues pro-
vided by nature. The validity of the model arises
from its explanation of and its prediction of nature.
Atoms: Units of Elements
During the thirty years following the work of
Lavoisier, quantitative data were gathered concerning
the nature of matter. Prominent in this activity were:
Gay-Lussac, who showed that gases react in volume-
ratios of whole numbers; Berzelius, who developed
equivalent-weight relationships between substances;
Richter, who postulated the definite proportion by
weight relationship from his studies on oxides. Their
data were best summarized and generalized by an
English school teacher named Dalton. Early in the
nint:teenrh century hede~cribed n new modd b: ~wl upon
t he discontinuous nntureof mutter. IIr postulated:"
Chemical elements are composed of atoms.
Atoms can neither be created or annihilated.
Atoms of the same element are identical and have the same
mass.
Atoms of different elements have different mass.
Combinationrr occur between atoms in whole number ratios.
Notice that these postulates had been confirmed and
discovered, not by Dalton, but by many other chemists.
All except the second postulate can be attributed to an
individual or group that was studying that specific pos-
tulate. The second postulate formulates the law of
conservation of matter, a generalization not included in
any previous model. From it we can write chemical re-
actions and predict what the products will weigh. This
postulate also gives theoretical evidence for the law of
definite proportions. This generalization was as great
as Aristotle'sand Stahl's. Furthermore, Dalton'smodel
of the atom is based more upon experimental data than
' LEICE~TEE, op. eit., 143.
"Chyrnia No. 1: Annual Studies in the History of Chemistry,"
T. D. DAVIS, Editor, University of Pennsylvania, Philadelphia,
1948.
any of the previous models. Its usefulness may be
judged by its success in predicting from formula such
diverse items as the amount of iron recovered from
smelting processes, and the best method to prepare a
new element.
The Dalton model immediately challenged scien-
tists with important questions: How do atoms stay
united with their own kind or with other kinds of
atoms? (Newton's gravitational forces are inadequate).
What is the explanation of multiple proportions? Why
is the formula COz more correct than GO4?
The explanation of these questions and of others of a
more complex nature reached a climax after many con-
tributing discoveries in chemistry and physics. The
chemists were struggling to arrange the elements in
an order that would facilitate understanding and pre-
diction, while the physicists' emphasis was on explaining
the energies between atoms. The work of Dobereher,
Newlands, Meyer, and Mendeleev characterizes the
work of the chemists. It is the work of the physicists
that established the background which Bohr used to
develop an even more complete model of the atom.
Following is a list of the more significant discoveries
known to Bohr.
Faraday in 1844 suggested from the results of his studies of
conduction and of electroplating with chemical solutions, that
electricity was carried by atoms with 8 charge.
Crooks in 1874 developed znd used the cathode ray tube to
show that these rays were capable of exerting force. He con-
cluded that they were material-like.
J. J. Thomson in 1897 proved that the cathode ray eomisted
of negatively-charged particles with a mass ratio about ' / , ~ ~ ~ t h
that of the hydrogen atom. Thomson pictured the atom as a
solid mass with electrons imbedded in the mass. His model has
been called the "raisin bun" or "rice pudding" model.
Becquerel in 1896 showed that salts of uranium gave off a
radiation that penetrated matter and darkened a photographic
plate. He explained the phenomenon as radiation of X-rays,
similar to Thomson's electrons.
Rutherford in 1899, working with materials that the curie'^
had shown could be isolated, separated radiation into three types:
the positive or alpha particle, the negative or beta. particle, and
the neutral or gamma. wave. His careful experimentation
enabled him to show that the alpha particles were ionized helium
gas. Rutherford also showed that most alpha particles pene
trated gold foil hut thst a few were scattered by it. From these
experiments he extended Thomson's atom model to say that the
electrons arenot imbedded within the mass hut are separatedfrom
the nucleus with a void between. Rutherford's model helped
physicists to understand electricity, hut its greatest accomplish-
ment lay in its challenge to the scientist to find order in the ar-
rangement of the electrons.
Moseley in 1913 observed that X-rays produced a charac-
teristic frequency that varied from one element to the next in s.
regular shift. Moseley reasoned that each succeeding element
in the periodic table had one more electron than the previous
one.
Planck in 1900 postulated that radiation of all energies is
emitted or absorbed in discrete bundles of energy called quanta.
In 1905 Einstein explained the photoelectric effect by assum-
ing that the energy absorbed by an emitted electron is measured
in quantized units, therefore is independent of the intensity of
the incident light.
Bohr's "Working Model'' of the Atom
In 1915 Niels Bohr working with Rutherford at the
University of Manchester, conceived an order in the
electrons outside the nucleus of Rutherford's model.
His efforts were centered on explaining the spectra of
the elements, for Rydberg had developed a set of
empirical rules to predict them. Bohr attempted to
explain these results and those of Balmer and others by
postulating:
The hydrogen atom consists of one negative electron revolving
in any one of a. large number of possible orbits about B central
massive, singly-charged positive nucleus. The particles will
not obey Newtonian mechanics.
The only orbits permitted are those in which the angular
momentum of the electron is equal to whole number ratios of
nh
Planck's constant. mvr = -
2"
No radiation is emitted as long as the electron remains in a
given orbit, hut when an electron changes orbits a radiation is
emitted of a frequency which is equal to the ratio of its energy
divided by Phnek's constant. u = E/h
This model includes no prediction of the process of radiation.
Bohr gives credit for each of the first three postulates
to various scientists who made the discoveries or to
the many who were trying to explain spectra. This was
the prevailing problem of the day for every young and
ambitious physicist. Bohr's contributing postulate was
the definition of the limitation of the model. Bohr real-
ized as no one else did that only a portion of nature was
explained by the model. He was concerned with t,he
energy and orbits of the electrons about the nucleus,
but he could not explain the reason why or how the
process of radiation occurs. No one has since. With
this model we can calculate the wavelength and fre-
quency of the emitted light to agree with the experi-
mental data of Rydberg, Balmer, and Paschen. But
as a good model should, Bohr's model predicted spectra
lines in the ultraviolet and infrared region. These
spectral lines were later verified.
Chemists immediately used the model to show the
relationship of electrons to the periodic arrangement
and to valence. G. N. Lewis of the University of
California visualized a model which placed the electrons
at the corners of a cube in order to help predict proper-
ties of the element. Using Moseley's method of assign-
ing order to the elements by the number of electrons and
using Bohr's model of the permissible orbits, Lewis
postulated a model that has been most useful t o the
chemist in predicting formulas of compounds and ex-
plaining ion formation. Models such as this help
chemists predict the properties of elements.
Bohr's model was limited because it did not predict
accurately the spectral lines for the elements heavier
than lithium. Many attempts were made to patch up
the model to make it work for other elements. It be-
came necessary for each element to have its own cor-
rection factor to make the prediction agree with ex-
periment. The use of elliptical orbits instead of cir-
cular orbits is one successful modification. A very
useful model uses circular and elliptical orbitals with
a maximum of two electrons per orbital-still grouped
at energy levels as Bohr calculated. The situation re-
minds us of the similar situation involving modifications
to the Aristotle models.
Matter and Waves
DeBroglie in 1924 pointed out two major improve-
ments in the classical description of the spectrum of
light from metals. The first was that the particles of
matter behaved as waves of energy, second, that the
orbits of Bohr confined the particle to a definite location.
From these developments DeBroglie postulated a model
Volume 37, Number 5, MOY 1960 / 269
of the electron as a wave, the length of which stretched
around the nucleus. (Fig 2).'
Figure 2. DeSroglie'r eleclron model.
The wave amplitude represents the probabiity of
finding the electron at that location. DeBroglie's wave
equation h = "/,, represents a very useful model in
working with diffraction of X-rays. The diagrams
shown are misleading as no visualization can be made of a
wave that extends to space. But the model serves to
give some information dealing specifically with wave
diffraction of particles through a crystal. However De-
Broglie does not give a better description of the electron.
I t was left to Schrodinger to develop a model useful to
the chemist's predictions.
Schrodinger based his model of the atom on the pos-
tulates of DeBroglie. He predicted that the wave-
length is associated with the movement of a particle.
Schrodinger was familar with the mathematical descrip-
tion associated with a variation of the wave amplitude
throughout space. This description is given by a second
order differential equation as shown by Hamilton
nearly a century ago. Thus Schrodinger's model of an
atom is represented by:
where m is the mass of the electron; E, the total energy
of the electron; P, the potential energy; h, Planck's
constant; x, y, and z, rectangular coordinates that locate
the electron in three dimensions; a2 refers to mathe-
matical process to solve for J., a quantity called the wave
function or the probability amplitude.
The Schrodinger equation yields three solutions for
each of the infinite number of states in which an elec-
tron can be located. This is no more mysterious than
the algebraic equation, x2 - 32 - 4 = 0, which yields
results of x = -4 and 1.
The solution of the Schrodinger equation yields
expressions in terms of quantum numbers. These
values can be referred to as: n representing the proba-
bility density of the electron, 1 representing the angular
momentum of the electron, and m representing the ori-
entation of the angular momentum. There are two pre-
vailmg interpretations of this model. One is that the J.
can represent the probability of finding the electron at
a given location. The second interpretation is that of
picturing the electron spread out as a fog, with the den-
sityof the fog varying and reaching a maximum at Bohr's
energy levels. Schrodinger's model will do all the work
that Bohr's model could do and more. The model al-
lows the chemist to predict the stability of any com-
pound, including the 105th combined with the 121st.
Schrodinger proposed his model in 1926 and used it
"LANCHARD, C. H., ET ~~.,"Intmduction to Modern Physics,"
Prentice-Hall, Ine., Englewood Cliffs, 1958, p. 179.
to give predictions of spectra. But as measurements
became more accurate, at many positions in the spec-
trum where one line was expected, more than one was
found. This was accounted for by assigning a number
called spin to the electron. Pairs of electrons could
have opposite spins. It turned out this was a poor
notation, for how can a fog spin? The visualization in
itself is bad. D i c in 1931 gave theoretical reasons
for the inclusion of a fourth variant in the Schrodinger
equation. Dirac treated the wave relativistically.
Thus he did not change the model, but expanded
it t o include a solution yielding four conditions for the
electron, the n, 1, m, and s values. Pauli interpreted
these values to develop the same periodic arrangement
of the elements that previous chemists had arranged
without theoretical reason. This part of the solution
in itself is a model helpful in predicting chemical bind-
ing and properties of the elements.
No model is all-inclusive in its description of nature.
As models of the atom developed from Democritus
to Dirac, they have been postulated from creative
thought based upon observations of nature. As scien-
tists strove for more accuracy, we have come to a more
diicult description with which to visualize a model for
nature. The description has evolved from wordy sen-
tences to the more definite but more abstract mathe-
matical descriptions. The present models are not to
be visualized. They extend science beyond the com-
mon-sense experience and observations of the non-spe-
cialist.
It now must be asked with good intentions, "What
are the limitations of Dirac's model?" The answer is
that it works to an accuracy of eight or more significant
figures with the electron, but it makes poor predictions
of the happenings in the nucleus. %'hat is the more
general model?" Some say Heisenberg has the solu-
tion. Heisenberg postulated in 1926:
To every observable there corresponds an operator (an opera-
tor is a procedure in matrix algebra and an observable is any
number that can be observed.)
The only possible values which are the measurement of an ob-
sewable whose operator is P me the eigen-values (little p ) for
the expression:
PJ.i = pJ.i
(when you make an obsewation, the obsewatiou is restricted
before you make it.)
When a system ia in state J., the expected mean of a sequence
of measurements of the ohsewable whose operator ia P is given
by the expression:
If J. is given now, its value at a later time is a solution of the
expression :
Heisenberg's model is not meant to be visualized.
It is meant to give specific solutions to specific prob-
lems. The answers will not be definite but will give
probability values. It is the challenge to the present
generation to develop this model.
Notice that scientists started with a feud over the
continuous or discontinuous nature of matter. Present
models avoid this and claim matter to be both continu-
ous and discontinuous, stating that matter is both par-
ticle-like and wavelike.
270 / Journol of Chemical Edumtion