Atoms Old and New: From Newton to Einstein

3quarksdaily /

by Paul Braterman

The transition to modern thinking

"It seems probable to me, that God in the beginning formed matter in solid,
massy, hard, impenetrable, movable particles even so very hard, as never to
wear or break in pieces; no ordinary power being able to divide what God Himself
made one in the first creation." So wrote Sir Isaac Newton in his 1704
work, Opticks. Apart from the reference to God, there is nothing here that
Democritus would have disagreed with. There is, however, very little that the
present-day scientist would fully accept. In this and later posts, I discuss how
atoms reemerged as fundamental particles, only to be exposed, in their turn, as
less than fundamental.

The scientific revolution and the revival of corpuscular theory - 15431687

In 1543, on his death-bed, Nicholas Copernicus received a copy of the first

edition of his book, On the Revolutions of the Heavenly Bodies, in which he
argued that the Sun, not the Earth, was thecentre of what we now call the Solar

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System. In 1687, Isaac Newton published his Mathematical Principles of Natural
Philosophy, commonly known as the "Principia". With hindsight, we can identify
the period between these events as a watershed in the way that educated people
in the West thought about the world, and number the political revolutions in
America and France, and the economic revolutions in agriculture and industry,
among its consequences.

Before this scientific revolution, European thinking about nature still followed that
of Aristotle. The Earth lay at the centre of the Universe. Objects on Earth moved
according to their nature; light bodies, for instance, containe, air or fire in their
makeup, and these had a natural tendency to rise. Earth was corrupt and
changeable, while the heavens were perfect and immutable, and the heavenly
bodies rode around the centre on spheres within spheres because the sphere
was the most perfect shape. By its end, Earth was one of several planets moving
round the Sun in elliptical orbits, the movements of objects were the result of
forces acting on them, the laws of Nature were the same in the heavens as they
were on Earth, and all objects tended to move in straight lines unless some force
deflected them from this path. The Universe ran, quite literally, like clockwork.
This mechanical world-view was to last in its essentials until the early 20th
century, and still remains, for better or worse, what many non-scientists think of
as the "scientific" viewpoint.

Left: manuscript where Galileo records his observations of

the motion of the moons of Jupiter, dethroning Earth from its special position as

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centre of celestial motion. Below right, Gallileo demonstrates the telescope to the
Doge of Venice, fresco by Bertini. Click to enlarge

In 1611, Galileo turned the newly-invented telescope on the

heavens, discovered sunspots, and moons round Jupiter, and realised that the
belief in a perfect and unchanging1 celestial realm was no longer sustainable.
Earlier, he had studied the motion of falling bodies. In work that he started in
1666, Newton showed how the laws of falling bodies on Earth, and the
movement of heavenly bodies in a Copernican solar system, could be combined
into a single theory. To use present-day language, the Moon is in free fall around
the Earth, pulled towards it by the same force of gravity as a falling apple. This
force gets weaker as we move away from Earth, according to the famous inverse
square law, which says that if we double the distance, the force falls to a quarter
of its value. Then with a certain amount of intellectual effort (involving, for
example, the invention of calculus), Newton was able to work out, from the
acceleration of falling bodies on Earth, and from the Earth-Moon distance, just
how long it should take the Moon to go round the Earth, and came up with the
right answer. He was also able to work out just how long it would take satellites
at different distances to go through one complete orbit. Of course, at that time,
Earth only had one satellite (the Moon), but six were known for the Sun (Mercury,
Venus, Earth, Mars, Jupiter, Saturn), and his theory correctly predicted how the
length of the year of these different planets would vary with their distance from
the Sun (the answer is a 2/3 power law; an eight-fold increase in distance gives a
fourfold increase in time). Celestial and terrestrial mechanics were united.

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 R: Image from Arcana Naturae Detecta,
1695, Leeuwenhoek's collected letters to The Royal Society. Click to enlarge

It was around this time that a Dutchman, Anthony van Leeuwenhoek, began an
extensive series of microscope studies, using single lens instruments of his own
devising. Among the first to observe spermatozoa, he also described bacteria,
yeast, the anatomy of the flea, and the stem structure of plants. He
communicated his results to the Royal Society in London. Formally established
around 1660, under the patronage of Charles II, this was and remains among the
most prestigeful of learned societies. Here they caught the attention of Robert
Boyle (of Boyle's Law for gases). Boyle tried to explain such properties of matter
as heat, and the pressure of gases, in terms of the mechanics of small particles,
or "corpuscles", and hoped that the other aspects of matter could be explained in
the same kind of way. This was, after all, simply an extension downwards of the
mechanical system that Newton had so successfully extended upwards. It is
instructive to consider how far this hope was fulfilled. Atoms and molecules are in
some ways similar in their behavior to small objects obeying the everyday laws of
mechanics, but in others they are very different, and it is these differences that
must be invoked if we are to understand the forces involved in the chemical
bonding.

Early modern theory - 1780-1840

Between 1780 and 1840, chemistry underwent a revolution, that transformed it

into the kind of science that we would recognise today. It is no accident that this
was the same period as the beginning of the industrial revolution in Europe.
Materials were being mined, and iron and steel produced and worked, on a larger
scale than ever before. By the end of the period, mineral fertilisers were already

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in large scale use to feed the growing population. Demand for machinery led to
improvements in engineering, and this in turn made possible improvements in the
precision of scientific instruments. Much of the new interest in chemistry grew out
of mining, mineralogy, and metallurgy, while improvements in manufacture and
glass-blowing led to the precision balance, and to new apparatus for handling
gases.

Here I will summarise some of the most important discoveries, as seen from our
present point of view, and using today's language. This means running the risk of
creating a misleading impression of smoothness and inevitability. Inevitability,
perhaps yes; the world really is what it is, and once certain questions had been
asked, it was inevitable that we would eventually find the right answers.
Smoothness, no; the very concept of atoms, let alone bonding between atoms,
remained controversial in some circles way into the 20th century. Outsiders
sometimes criticise scientists for taking their theories too seriously, but more
often they are reluctant to take them seriously enough.

Overall, mass is conserved; the mass of the products of a reaction is always the
same as the mass of the reactants. This is because atoms are not created or
destroyed in a chemical reaction.2 Single substances can
be elements or compounds, and the enormous number of known compounds can
be formed by assembling together the atoms of a much smaller number of
different elements. We owe our distinction between elements and compounds to
Lavoisier ("The banker who lost his head"). Boyle had come close a hundred
years earlier, but was so taken with the transformations of matter that he rejected
the notion that its fundamental constituents were immutable.3

The combustion of carbon (its reaction with oxygen) gives a gas, the same gas
as is formed when limestone is heated. But there is no chemical process that
gives carbon on its own, or oxygen on its own, by reaction between two other
substances. So we regard carbon and oxygen as elements, whereas the gas

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formed by burning carbon (what we now call carbon dioxide) is a compound of
these two elements. The production of this same gas, together with a solid
residue, by the heating of limestone, shows that limestone is a compound
containing carbon, oxygen, and some other element.4 To us, using today's
knowledge, limestone is calcium carbonate, and decomposes on heating to give
carbon dioxide and calcium oxide. In Lavoisier's time, there was no way of
breaking down calcium oxide into simpler substances, so he considered it to be
an element.

A short philosophical digression (and every scientist has a working philosophy,

whether they realise it or not): Lavoisier could make as much progress as he did
because he had introduced an operational definition of an element, referring not
to some inner essence but to observationally defined properties. And implicit in
this was the principle of fallibilism; conclusions are always in principle revisable in
the light of further observation, as the example of calcium oxide shows.

Air is a mixture, and burning means reacting with one of its components, which
we call oxygen. Metals in general become heavier when they burn in air. This is
because they are removing oxygen from the air, and the weight (more strictly
speaking, the mass) of the compound formed is equal to that of the original metal
plus the weight of oxygen. (Mass is an amount of matter; weight is the force of
gravity acting on that matter. Atoms are weightless when moving freely in outer
space, but not massless.)

Different elements combine with different amounts of oxygen; these relative

amounts are a matter of experiment. In modern language, when some typical
metals (magnesium, aluminium, titanium, none of which were known when
Lavoisier was developing his system) react with oxygen, they form oxides with
the formulas MgO, Al2O3, TiO2.

About one fifth of the air is oxygen, and if we burn anything in a restricted supply
of air, the fire will go out when the oxygen has been used up. Nothing can burn in

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(or stay alive by breathing) the remaining air. Some materials, like wood and
coal, appear to lose weight when they burn, but this is because they are in large
measure converted to carbon dioxide and water vapour, which are gases, and
we need to take the weight of these gases into account.

It was also shown during this period that the relative amounts of each element in
a compound are fixed (Law of Definite Proportions). For instance, water always
contains 8 grams of oxygen for each gram of hydrogen. Moreover, when the
same elements form more than one different compound, there is always a simple
relationship between the amounts in these different compounds (Law of Multiple
Proportions). Thus hydrogen peroxide, also a compound of hydrogen and
oxygen, contains 16 grams of oxygen for each gram of hydrogen. Similarly, the
gas (carbon dioxide to us) formed by burning carbon in an ample supply of
oxygen contains carbon and oxygen in the weight ratio 3:8, but when the supply
of oxygen is restricted, another gas (carbon monoxide) is formed, in which the
ratio is 3:4. Carbon monoxide is intermediate in composition between between
carbon and carbon dioxide, but it is not intermediate in its properties. For a start,
it is very poisonous; it sticks to the oxygen-carrying molecules in the blood even
more strongly than oxygen itself, thus putting them out of action. It is formed
when any carbon-containing fuel, not just carbon itself, burns in an inadequate
supply of air, That is why car exhaust fumes are poisonous, and why it is so
important to make sure that gas-burning appliances are properly vented. It is also
one of the components of cigarette smoke, which helps explain why cigarettes
cause heart disease and reduce fitness.

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 Left: Dalton's table of the elements, with relative weights,
based on H = 1. The correct value for oxygen is 16. Dalton's value is based on
an assumed formula HO for water, together with experimental error; likewise for
other elements. Click to enlarge

All these facts can be explained if the elements are combined in molecules that
are made out of atoms, the atoms of each element all have the same mass,5 and
each compound has a constant composition in terms of its elements. For
instance, each molecule of water contains two atoms of hydrogen and one of
oxygen (hence the formula H2O); hydrogen peroxide is H2O2; carbon dioxide is
CO2; carbon monoxide is CO; and the masses of atoms of hydrogen, oxygen,
and carbon are in the ratio 1:16:12. Using these same ratios, we can also explain
the relative amounts of the elements in more complicated molecules, such as
those present in octane (a component of gasoline), C8H18, and sucrose (table
sugar), C12H22O11. Why C8H18 and not C4H9, which would have the same atomic
ratio? This can be inferred from the density of the vapour, using Avogadro's
hypothesis (see below).

Thus, by the early 19th century, chemists were in the process of developing
consistent sets of relative atomic weights (sometimes known as relative molar
masses). However, there was more than one way of doing this. For instance,
John Dalton, the first to explain chemical reactions in terms of atoms, thought
that water was HO and that the relative weight of hydrogen to oxygen was one to
eight. This uncertainty even led some of the most perceptive to question whether

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atoms were real objects, or merely book-keeping devices to describe the rules of
chemical combination.

Evidence from the behavior of gases (to around 1860)

A French chemist, Joseph Gay-Lussac, noticed that the volumes of combining

gases and of their gaseous products, were in simple ratios to each other. In
1811, the Italian Count Amadeo Avogadro explained this by a daring hypothesis,
that under the same conditions of temperature and pressure equal volumes of
gases contain equal numbers of molecules. We now know this to be (very nearly)
true, except at high pressures or low temperatures.

Avogadro's Hypothesis, as we still call it, gives us a way of directly comparing the
relative weights of different molecules, and of inferring the relative weights of
different atoms. For example, if we compare the weights of a litre of oxygen and
a litre of hydrogen at the same temperature and pressure, we find that the
oxygen gas weighs sixteen times as much as the hydrogen. (This is not a difficult
experiment. All we need to do is to pump the air out of a one litre bulb, weigh it
empty, and then re-weigh it full of each of the gases of interest in turn.) But
Avogadro tells us that they contain equal number of molecules. It follows
thateach molecule of oxygen weighs sixteen times as much as each molecule of
hydrogen.

One litre of hydrogen will react with one litre of chlorine to give two litres of the
gas we call hydrogen chloride. Thus, by Avogadro's Hypothesis, one molecule of
hydrogen will react with one molecule of chlorine to give two molecules of
hydrogen chloride. So one molecule of hydrogen chloride contains half a
molecule of hydrogen, and half a molecule of chlorine. It follows that the
molecules of hydrogen and of chlorine are not fundamental entities, but are
capable of being split in two. Making a distinction between atoms and molecules
that is obvious to us now but caused great confusion at the time, each molecule
of chlorine, must contain (at least) two separate atoms.6 By similar reasoning,

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since 2 litres of hydrogen react with 1 litre of oxygen to give 2 litres of steam,
water must have the familiar formula H2O, and not HO as Dalton had assumed
for the sake of simplicity.

Avogadro's hypothesis was put forward in 1811, but it was not until 1860 or later
that his view was generally accepted. Why were chemists so slow to accept his
ideas? Probably because they could not fit it into their theories of bonding. We
now recognise two main kinds of bonding that hold compounds together - ionic
bonding and covalent bonding. Ionic bonding takes place between atoms of very
unlike elements, such as sodium and chlorine, and was at least partly understood
by the early 19th century, helped by the excellent work of Davy and Faraday in
studying the effect of electric currents on dissolved or molten salts. They showed
that sodium chloride contained electrically charged particles, and inferred,
correctly, that the bonding in sodium chloride involved transfer of electrical
charge (we would now say transfer of electrons) from one atom to another. But,
as we have seen, Avogadro's hypothesis implies that many gases, hydrogen and
chlorine for instance, each contain two atoms of the same kind per molecule,
which raises the question of what holds them together. These are examples of
what we now call covalent bonding or electron sharing, a phenomenon not
properly understood until the advent of wave mechanics in the 1920s.

Physicists, meanwhile, were developing the kinetic theory of gases, which treats
a gas as a collection of molecules flying about at random, bouncing off each
other and off the walls of their container. This theory explains the pressure
exerted by a gas against the walls of its container in terms of the impact of the
gas molecules, and explains temperature as a measure of the
disorganised kinetic energy (energy of motion) of the molecules. The theory then
considers that this energy is spread out in the most probable (random) way
among large numbers of small colliding molecules. It can be shown that
molecules of different masses but at the same temperature will then end up on
average with the same kinetic energy, and it is this energy that at a fundamental

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level defines the scale of temperature. This is a statistical theory, where
abandoning the attempt to follow any one specific molecule allows us to make
predictions about the total assemblage.

The kinetic theory explains the laws (Boyle's law, Charles' law) describing how
pressure changes with volume and temperature. Avogadro's hypothesis can also
be shown to follow from this treatment. Many other physical properties of gases,
such as viscosity (which is what causes air drag) and heat capacity (the amount
of heat energy needed to increase temperature), are quantitatively explained by
the kinetic theory, and by around 1850 the physicists at least were fully
persuaded that molecules and, by implication, atoms, were real material objects.

Structural chemistry, 1870 on

Right; kinds of isomer. The nature of optical isomers was established by Pasteur.
Simple rotamers, such as the pair shown, readily interconvert at room
temperature, giving an equilibrium mixture. The other kinds shown generally do
not

Chemists were on the whole harder to convince than the physicists, but were
finally won over by the existence of isomers, chemical substances whose
molecules contain the same number of atoms of each element, but are
nonetheless different from each other, with different boiling points and chemical
reactivity is. This only made sense if the atoms were joined up to each other in
different ways in these different substances. So atoms were real, as were
molecules, and the bonding between the atoms in a molecule controlled its
properties. This is what we still think today.

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Einstein and Lucretius The piece of evidence that finally convinced even the
most skeptical scientists came from an unexpected direction, from botany. In
1827, a Scottish botanist called Robert Brown had been looking at some grains
of pollen suspended in water under the microscope, and noticed that they were
bouncing around, although there was no obvious input of energy to make them
do so. This effect, which is shown by any small enough particle, is still known
as Brownian motion. Brown thought that the motion arose because the pollen
grains were alive, but it was later discovered that dye particles moved around in
the same way. The source of the motion remained a mystery until Albert Einstein
explained it in 1905. (This was the same year that he developed the theory of
Special Relativity, and explained the action of light on matter in terms
of photons). Any object floating in water is being hit from all sides by the water
molecules. For a large object, the number of hits from different directions will
average out, just as if you toss an honest penny a large number of different times
the ratio of heads to tails will be very close to one. But if you toss a coin a few
times only, there is a reasonable chance that heads (or tails) will predominate.
and if you have a small enough particle there is a reasonable chance that it will
be hit predominantly from one side rather than the other. Pollen grains are small
enough to show this effect. But this is only possible if the molecules are real
objects whose numbers can fluctuate; if they were just a book-keeping device for
a truly continuous Universe, the effects in different directions would always
exactly cancel out. And if molecules are real, then so are atoms. It is just as
Lucretius said, looking at dust in the air two thousand years earlier:

So think about the particles that can be seen moving to and fro in a sunbeam, for
their disordered motions are a sign of underlying invisible movements of matter.

1 In fact (see earlier post), the Arabs had already recognized the variability of the
star Algol

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2 We cheat. There are, of course, processes (radioactive decay, nuclear fusion)
where the number of atoms of each kind is not conserved because one element
is transformed into another. We simply decide to call these physical processes,
so that our statement remains true by definition. Nonetheless, it is useful,
because it is usually pretty obvious whether a process should be called
"chemical" or "physical", on other grounds, such as whether or not it involves the
formation of new bonds between atoms.

3 The Architecture of Matter, S. Toulmin and J. Goodfield, Hutchinson, 1962

4 In present-day notation,

C + O2 = CO2 and CaCO3 = CaO + CO2

5 This is not quite true. Most elements are a mixture of atoms of slightly different
mass but very similar properties. The relative atomic masses of the elements as
they occur in nature are an average of the masses of these chemically
identical isotopes

6 So we can write the reactions as H2 + Cl2 = 2HCl and 2H2 + O2 = 2H2O

An earlier version of some of this material appeared in my From Stars to

Stalagmites, World Scientific. Leeuwenhoek material via Buffalo Library. Dalton's
table of elements and their symbols via Chemogenesis. Isomers image by
Vladsinger via Wikipedia

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