Episode 1: Discovering the Elements

Introduction[edit]
Only in the last 200 years have we known what an element is a substance that cannot be broken down
further by chemical reaction.
The Ancient Greeks, with no way of breaking open substances, could only base their ideas of the
elements on what they could see: Earth, Fire, Water and Air.
In the 16th century alchemists were busy trying to turn base metals like lead, into gold.
Paracelsus and the Tri Prima[edit]
It was the Swiss alchemist and surgeon Paracelsus who first challenged the Ancient Greek idea of four
elements.
In 1526 Paracelsus was in Basel, when the famous printer Frobenius was told he would have to have his
leg amputated in a life-saving operation. Instead of accepting the received wisdom, he called upon
Paracelsus who cured him in the unconventional way of using his alchemical knowledge. This established
him as a radical thinker, giving weight to his ideas, principal amongst which was the idea that the world
was actually made of three elements: the tria prima comprising salt, sulphur and mercury.
Paracelsus did not succeed in convincing the establishment instead he managed to enrage them by
burning their established medical texts, and eventually had to flee Switzerland for Germany.
It was, however, the alchemical pursuit for gold that led to the first breakthrough in the hunt for new
elements.
Hennig Brand and the Icy Noctiluca[edit]
In 1669 Brand was looking for a way of extracting gold from the human body, and struck upon the idea of
using urine, thinking that urine might contain some part of the life force vital to sustaining human life. To
get rid of the unimportant parts, primarily water, Brand boiled the urine for several days until he was left
with a thick paste. Finally, fragments of a substance emerged which burned brighter than any Medieval
candle available at the time, but which left the vessel it burnt in cold: Brand named this new
substance icy noctiluca cold night light.
Soon after its discovery, icy noctiluca toured the Royal Houses of Europe and in 1677 it came before
the Royal Society in London, then under the chairmanship of Charles II, where one of its members
decided to investigate.
In his book New Experiments and Observations Made Upon the Icy Noctiluca Robert Boyle describes an
experiment in which sulphur and phosphorus powders are mixed causing them to burn fiercely. This
discovery was the basis for the invention of the match.

Phosphorus, as icy noctiluca is now known, is used in everything from match heads to toothpaste and
ultimately in the Second World War bombs which destroyed the very city in which Brand discovered it
Hamburg.
Whilst Brand never discovered gold, his accidental discovery of the element now known as phosphorus
gave rise to the idea that elements could be hidden inside other substances.
Robert Boyle and The Sceptical Chemist[edit]
More than a decade earlier in 1661, a year after the Royal Society opened, Boyle deposited The
Sceptical Chemist in its vaults. This book is usually regarded as the turning point that signalled the
transition from alchemy to chemistry. The Sceptical Chemist was innovative in several ways: it was not
written in Latin, as had been the tradition for alchemical books, but in English; it dispensed with the
old alchemical symbols for various elements, using English names instead; and most crucially it was
actually published, as opposed to kept secret.
Boyle was willing to share his discoveries to allow others to build on his work and further the scientific
understanding of the elements. He wanted to put alchemy on a more scientific footing ditching the
metaphysical baggage it had brought with it from the previous century.
Unfortunately, this new age of chemical enlightenment was fraught with blind alleys.
Johann Becher and Phlogiston[edit]
In 1667 the German scientist Johann Becker proposed that fire was caused by an ethereal, odourless,
tasteless, colourless, weightless entity called phlogiston. The idea was that phlogiston causes things to
burn, reducing them to their pure form. For example, burning wood releases phlogiston, leaving the pure
form of wood ash, therefore wood is composed of ash (pure wood) and phlogiston.
Phlogiston was accepted as scientific truth, paralysing the scientific communitys ability to discover more,
true elements. One scientist even claimed to have isolated phlogiston.
Henry Cavendish and Inflammable Air[edit]
A major shareholder in the Bank of England with royal connections, Henry Cavendish was a painfully shy
character, who made the vital chemical contribution of discovering the first elemental gas.
He added some zinc to spirit of salt (hydrochloric acid) and collected the evanescence given off as
bubbles. The gas he collected was tasteless, odourless and colourless, and moreover it produced a
squeaky pop in the presence of a flame this led Cavendish to name the gas inflammable air, which he
believed to be one and the same as phlogiston.
Cavendish made an important observation, though little did he realise it, about burning phlogiston in air, a
dewy liquid was formed on the inside of the glassware: water. This should have had enormous
repercussions for the whole scientific community in the 1700s, who still believed water to be an elemental

substance. Yet, if water could be made by burning inflammable air, then water is not an element, but
acompound.
However, it simply did not occur to Cavendish that water was a compound instead he assumed that the
airs contained a form of water, which phlogiston modified into liquid, elemental water.
Phlogiston had given the Ancient Greek idea of water as an element a brief reprieve, but the Greek
system was now under heavy scrutiny as the Royal Society commissioned its members to investigate the
invisible airs.
Joseph Priestley and Dephlogisticated Air[edit]
By the mid-1700s there were three known airs:

Common air the air we breathe;

Cavendishs inflammable air;

Fixed air.

It was this last air which caught the attention of Joseph Priestley, a Unitarian minister whose favourite
pastime was the investigation of airs specifically, fixed air, given off by the fermentation process in
breweries.
Priestleys passion for science led to an invitation to Bowood House, to tutor the children of Lord
Shelburne. This was an excellent opportunity, given that Priestley did not have the money of earlier
chemists like Boyle and Cavendish, and would still be free to pursue his own research.
In 1774 Priestley performed a hugely important experiment: he heated mercuric calc and collected the
gas given off. He discovered that this gas was able to relight the embers of a previously lit wooden splint.
He concluded that the splint was introducing phlogiston to the gas, only after which could it burn,
therefore the gas must be without phlogiston this led Priestley to name it dephlogisticated air.
In October 1775 Priestley accompanied Lord Shelburne on a trip to Paris where they were invited to dine
with the preeminent scientists of the time. It is here that Priestley met the French scientist Antoine
Lavoisier.
Antoine Lavoisier and the end of Phlogiston[edit]
Priestley told Lavoisier all the details of his experiments upon the production of dephlogisticated air.
Unlike Priestley, Lavoisier had one of the best equipped laboratories in Europe and now turned his
attention to the highly accurate measurement of the masses of substances before and after they were
heated.
Lavoisier weighted a sample of tin, then reweighed after he had heated it and found it had increased in
mass. This was an unexpected result given that the tin was thought to have released phlogiston during
the burning process. Lavoisier was struck with a ground-breaking thought maybe the tin had absorbed
something from the air, making it heavier, but if so, what?

To investigate this further, Lavoisier reran Priestleys experiment in reverse he heated some mercury in
a sealed container until it turned into mercuric calc and measured the amount of air absorbed. He then
heated the mercuric calc and measured the amount of air released and discovered the quantities were
the same. Lavoisier realised that something was absorbed from the air when mercury was heated to
make mercuric calc, and that same gas was released when the mercuric calc was heated. Lavoisier
concluded that this gas was unrelated to phlogiston, but was in fact a brand new element, which he
named oxygen.
Lavoisier had successfully dispensed with the need for the theory of phlogiston and recognised Priestleys
dephlogisticated air as the element oxygen. Despite the fact it was Priestleys original work that laid the
foundations for his discovery, Lavoisier claimed he had discovered oxygen; Priestley, after all, had failed
to recognise it as a new element.

Table from the English translation of Lavoisier's Trait lmentaire de chimie, 2 vols. Chez Cuchet, Paris
(1789). Translated from the French by Robert Kerr, Elements of Chemistry, 4th edition. William Creech,
Edinburgh: (1790).
Lavoisier went on to give science its first definition of an element: a substance that cannot be
decomposed by existing chemical means. He also set about drawing up a list of all the elements now

33 elements replaced the ancient four. His list was grouped into four categories: gases, non-metals,
metals and earths.
On top of this, Lavoisier created a classification system for the ever increasing array of chemicals being
discovered. As mentioned, dephlogisticated air became oxygen, inflammable air became hydrogen,
but the nomenclature of compounds was also put on a more logical footing as oil of vitriol became
sulphuric acid, philosophical wool became zinc oxide and astringent mars saffron became iron oxide.
Unfortunately, whilst Lavoisier had rid the world of the phlogiston paradigm, he introduced two new
erroneous elements now known to be pure energy: lumire and calorique; light and heat.
In revenge for his sympathies with the revolutionaries in France, Priestleys home in England was
targeted by arsonists in 1791, luckily he escaped thanks to a tip-off, but decided to flee to America.
Lavoisiers contributions to science were cut short in 1794 by the revolutionaries, who arrested him on
grounds of being an enemy of the French people, and had him guillotined.
Humphry Davy and Potash[edit]
In 1807, the Professor of Chemistry at the Royal Institution in London was the Cornishman Humphry
Davy. He was investigating crystalline salts ofpotash because he was unconvinced potash was an
element, but by the end of the previous century, Lavoisier had been unable to break it down further.
Since then however, the first electric battery had recently been invented (rows of metal plates and
cardboard soaked in saltwater). Although scientists were aware that the production of a continuous
electric current was due to some property of the metals, Davy believed that a chemical reaction was
taking place. If that was true, then maybe the reverse was also true: an electric current could cause a
chemical reaction.
Davy heated the potash until it was liquid, then introduced two electrodes and passed a current through
the molten potash. A lilac flame was observed, the result of successfully breaking down potash into its
constituent elements one of which, was the previously never before seen element potassium.
Davy went on to add six new elements to Lavoisiers list, as well as confirming that substances
like chlorine and iodine were also elements. By the time of his death in 1829 the idea of the elements
was firmly established, 55 separate elements had been discovered, and the world had a new
science: Chemistry.
Episode 2: The Order of the Elements[edit]
Introduction[edit]
At the beginning of the 19th century only 55 of the 92 naturally occurring elements had been discovered.
Scientists had no idea how many more they might find, or indeed if there were an infinite number of
elements. They also sought to answer a fundamental question, namely: is there a pattern to the
elements?

John Daltons Atoms[edit]

Dalton's atomic symbols, from his own books.

Scientists had recently discovered that when elements combine to form compounds, they always do so in
the same proportions, by weight. John Dalton thought that for this to happen, each element had to be
made of its own unique building blocks, which he called atoms.
Dalton suggested that everything in the universe was made of atoms, and that there are as many kinds of
atoms as there are elements, each one with its own signature weight. Based on these ideas, working
completely alone, Dalton attempted to impose some order on the elements by drawing up a list, where
each element was represented by an alchemical-looking symbol, ordered by atomic weight.
Although Dalton did not get all his atomic weights correct, he was pointing science in the right direction.
Sadly, in the early 1800s few scientists accepted the idea that elements had different weights.
Jns Jacob Berzelius Pursuit of Atomic Weights[edit]
The Swedish scientist Berzelius was one of the few scientists who strongly believed in the idea of atomic
weights, and thought that knowing as much as possible about their weights was vitally important. When
he heard of Daltons theory, he set about the gargantuan task of measuring the atomic weight of every
single known element without any proof that Daltons atoms actually existed.
This was even more challenging than it first seems once you consider the fact that very little of the
chemical glassware necessary for such precise measurements had been invented. Berzelius had to
manufacture much of it himself.

Berzelius experiences with glass-blowing had an additional bonus, in 1824 he discovered that one of the
constituents of glass was a new element silicon. Having already discovered three other elements prior
to silicon: thorium, cerium and selenium, Berzelius spent the next ten years obsessively measuring more
than two thousand chemical compounds in pursuit of accurate atomic weights for the elements.
Eventually Berzelius had remarkably accurate atomic weights for 45 elements; his value for chlorine was
accurate to within 0.2% of the value we know today.
However, by the time Berzelius had produced his results, other scientists were now measuring atomic
weights and getting conflicting results. In fact, scientists were looking for all sorts of patterns throughout
the elements.
Johann Dbereiners Triads[edit]
One such pattern hunter was German chemist Johann Dbereiner. He believed the key to understanding
the elements lay not with their atomic weights but with their chemical properties. He noticed that one
could often single out three elements that exhibited similar properties, such as the alkali metals, which he
called triads.
The problem was that Dbereiners triads only worked for a few of the elements and got scientists no
further than atomic weights.
Dmitri Mendeleev moves to St Petersburg[edit]
In 1848 a huge fire destroyed the factory of the widow Maria Mendeleeva. Facing destitution she decided
to embark on the 1,300 mile journey from Western Siberia to St Petersburg walking a significant portion
of the route so her son Dmitri Mendeleev could continue his education in the capital of the Russian
Empire.
At the time the scientific community was grappling with the problem of how to bring order to the 63
elements that were now known. Mendeleev was still a student when he attended the worlds first
international chemistry conference convened to settle the confusion surrounding atomic weights.
Stanislao Cannizzaros Standard for Measuring Atomic Weights[edit]
Sicilian chemist Stanislao Cannizzaro was still convinced that atomic weights held the key to the order of
the elements and had found a new way of measuring them. Cannizzaro knew that equal volumes of
gases contain equal numbers of particles, therefore instead of working with solids and liquids and all the
unreliability that entails, he proposed measuring the densities of gases to measure the weights of
individual gaseous atoms.
Whereas Berzelius results had failed to convince anyone, Cannizzaros method set an agreed standard
for measuring atomic weights accurately. Chemists soon found that even with accurate atomic weights,
the elements still seemed unordered, but then, a solitary English chemist made a curious discovery.

John Newlands Octaves[edit]

Visualization of John Newlands' Law of Octaves.

In 1863 John Newlands noticed that when ordered by weight, every eighth element seemed to share
similar properties, such as carbon and silicon in the sequence: carbon, nitrogen, oxygen, fluorine, sodium,
magnesium and silicon. He called this a Law of Octaves.
Three years later, in 1866, he presented his ideas to the Chemical Society, unfortunately for Newlands,
the musical analogy was not well received the audience suggesting he might as well have ordered the
elements alphabetically.
Today, Newlands Octaves are known as the Law of Periodicity, and Mendeleev was thinking along the
same lines.
Mendeleevs Periodic Table[edit]
By 1869 Mendeleev had been trying to find an order for the elements for a decade. One day he struck
upon the idea of making up a pack of cards with the elements names on and began playing a game he
called chemical solitaire. He began laying out the cards, over and over, just to see if he could form a
pattern where everything fitted together.
To date, chemists had tried to group elements in one of two ways:

By their atomic weights (Berzelius and Cannizzaros Atomic Weights);

By their chemical properties (Dbereiners Triads and Newlands Octaves).

Mendeleevs genius was to combine those two methods together. However, the odds were stacked
against him little more than half the known elements had been discovered: he was playing with an
incomplete deck of cards.
He stayed up for three days and nights then, finally, on 17 February 1869, he fell asleep and dreamt of all
63 known elements laid out in a grand table.

Dmitri Mendeleev's periodic table from 1871 with gaps (-) left for new elements.
Mendeleevs table reveals the relationship between all the elements in their order:

Atomic weights increase reading from left to right;

Triads and Octaves are visible reading down the columns.

Notice carbon and silicon are in Group IV and the volatile gases fluorine, chlorine and bromine are in
Group VII.
Mendeleev was sufficiently confident in the layout of his table that he was willing to leave gaps for
unknown elements to make the pattern fit believing other elements would later be discovered that filled
the gaps.

After Calcium (Ca, weight 40) he left a gap, predicting a metallic element slightly heavier than
calcium;

After Zinc (Zn, weight 65) he left a gap, predicting a metal with a low melting point and atomic
weight 68;

Immediately after that gap, he left a further gap, predicting another metal, dark grey in colour.

So, for Mendeleev to be vindicated, the gaps needed to be filled, and luckily, in 1859, new
instrumentation had been developed for discovering elements.

Bunsens Burner and Kirchhoffs Spectrometer[edit]

Robert Bunsen knew that when certain elements burned in the flames of his burner they each turned the
flame a different colour. Copper burned green, strontium red and potassium lilac Bunsen wondered if
every element had a unique colour.
Bunsen was joined in his research by Gustav Kirchhoff. Kirchhoff used the concept of the dispersion of
white light by a prism in the invention of the spectroscope, a device with a prism at its centre which split
the light from Bunsens flames into distinct bands of its constituent colours the elements spectral lines.
Kirchhoff and Bunsen realised these spectral lines were unique to each element, and, using this
technique they discovered two new elements, cesium and rubidium.
Paul Emile Lecoq de Boisbaudran discovers Gallium[edit]
In 1875 the Parisian chemist Paul Emile Lecoq de Boisbaudran used a spectroscope to discover a new
metallic element. It was a silvery-white, soft metal with an atomic weight of 68, which he
named gallium, after his native France. It also turned out to have a very low melting point, thus
matching all the expected properties of the element Mendeleev expected to fill the gap he had left after
zinc; indeed, this is exactly where the element was placed in the periodic table.
Even though Mendeleev had left the necessary gap for gallium as well as other elements, it was
becoming clear there was an entire group that was missing altogether.
Pierre Janssen and Norman Lockyer discover Helium[edit]
In 1868, the French astronomer Pierre Janssen travelled to India in time for the total solar eclipse that
occurred in August of that year. As well as his telescope, he also went equipped with a spectroscope, to
study the spectral lines of the light emitted from the sun. Normally, due to the intensity of sunlight many
weaker spectral lines are not visible next to the extreme brightness of the stronger lines. Janssen hoped
that he would observe more spectral lines during the eclipse when the suns light was less intense.
The eclipse allowed Janssen to observe a spectral line never seen before, which was not associated with
any known element. The same spectral line was confirmed by the English astronomer Norman Lockyer,
who thinking the element only existed in the sun, named it helium, after the Greek Sun God.
However, it wasnt long before another British scientist had discovered helium on Earth.
William Ramsay discovers the noble gases[edit]
By dissolving the radioactive ore cleveite in acid, William Ramsay was able to collect a gas trapped within
the rock, which had an atomic weight of 4, and the same spectral lines which Lockyer had observed:
helium. Prior to this, Ramsay had already isolated a new gas from the atmosphere; argon, with an atomic
weight of 40.

A problem now arose Mendeleev had not left any gaps which were suitable for either of these two new
elements, which led Ramsay to conclude an entire group was missing from the periodic table only two
of whose members were now known to exist, helium and argon.
Ramsey successfully discovered all the other stable elements in the group which he named neon (Greek
for new), krypton (Greek for hidden) and xenon (Greek for stranger). All the elements of this new group
had one overwhelming characteristic; their lack of reactivity. It was this particular characteristic that
brought to mind a name for the new group: the noble gases.
Mendeleev vindicated
Mendeleevs periodic table had brought order to all the elements, allowing him to make predictions that
future scientists tested and found to be true. By the time he died he was world-renowned in chemistry. His
periodic table was set in stone in St Petersburg and an element was eventually named after
him: mendelevium.
The periodic table does not however tell us why some elements are highly reactive, others completely
inert, why some are volatile, whilst others less so. It wasnt until the beginning of the 20th century that an
entirely different branch of science began to unravel the answers to these questions.
Niels Bohrs fixed shell model[edit]
In 1909, the physicist Ernest Rutherford proposed the structure of the atom was like that of a solar
system: mostly empty space with electrons floating around a dense nucleus.
Subsequently the Danish Physicist Niels Bohr introduced the idea that electrons occupied "fixed shells"
around the nucleus, which was further developed when it was suggested that each such shell could only
accommodate a fixed number of electrons: 2 in the first shell; 8 in the second shell; 18 in the third shell,
and so on, each shell holding an increasing number of electrons.
The chemical behaviour of all elements is explained by the number of electrons in their outer shells: to
increase the energetic stability of their electron configurations atoms have a tendency to gain or lose
electrons in such a way so as to achieve a full outer shell. Sodium, with 11 electrons one in its outermost occupied shell, will transfer an electron in the presence of fluorine to its outer-most occupied shell,
which contains seven electrons. The result is both sodium and fluorine now have a full outer shell, and
Sodium Fluoride is formed.
This theory explained why all elements react in the way they do and why some formed the compounds
they do, while others did not. It also explained why elements had the physical properties they did, which
in turn explained why the periodic table had the shape it did. However, there was one fundamental
question left unanswered: how many elements were there could there be an infinite number of elements
between Hydrogen and Uranium?

Henry Moseleys proton numbers[edit]

Early 20th century chemist Henry Moseley speculated that the answer to the number of elements lay in
the nucleus. By firing a radioactive source at copper, he was able to knock electrons from their atoms,
releasing a burst of energy in the form of an x-ray. When measured, the x-rays always had the same
energy, unique to copper. He discovered each element released x-rays of different energies. Moseleys
brilliance was to realise the x-ray energy is related to the number of protons inside the atom: the atomic
number.
Because this is the number of protons, the atomic number must be a whole number there cannot be
any fractional values. Moseley realised it was the atomic number, not the atomic weight that determines
the order of the elements. Whats more, because the atomic number increases in whole numbers from
one element to the next there can be no extra elements between Hydrogen (atomic number 1) and
Uranium (atomic number 92) there can only be 92 elements, there is no room for any more.
Moseley was just 26 when he completed this research. Aged 27 he was killed in action during the First
World War shot through the head by a sniper.