ALCHEMY

photo of an ancient document showing some of the symbols commonly used by alchemists

Alchemical symbols

Understanding of the alchemists is hampered by their predilection for making their writings incomprehensible ( instant knowledge was not to be available to the uninitiated ) and the popular view that their quest was simply to isolate the Philosophers’ Stone and to use it to transform base metals into gold. There was in fact a genuine search for mental and spiritual advance

Using a world-view totally unlike that recognised today, the alchemists’ ideas of ‘spirit’ and ‘matter’ were intermingled – the ability to use ‘spirit’ in their experiments was the difficult part.

alchemical symbol for gold

To transform copper to gold: – copper could be heated with sulphur to reduce it to its ‘basic form’ (a black mass which is in fact copper sulphide) – its ‘metallic form’ being ousted by the treatment. The idea of introducing the ‘form of gold’ to this mass by manipulating and mixing suitable quantities of spirit stymied alchemists for over fifteen centuries.

Whilst this transmutation of metals was the mainstream concern of alchemy, there emerged in the sixteenth century a school that brought the techniques and philosophies of alchemy to bear on the preparation of medicines, the main figures involved being PARACELSUS and JOHANN VAN HELMONT.

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cartoon of ALCHEMISTS AT WORK

ALCHEMISTS AT WORK

THE EIGHTEENTH CENTURY

COMBUSTION and PHLOGISTON

Noticing that burning a candle in an upturned container, the open end of which is submerged in water, causes the water to rise into the container, Philon of Byzantium inferred correctly that some of the air in the container had been used up in the combustion. However, he proposed that this is because this portion of the air had been converted into ‘fire particles’, which were smaller than ‘air particles’.

In 1700 the German physician Georg Ernst Stahl (1660-1734) invoked ‘phlogiston’ to explain what happens when things burn. He suggested that a burning substance was losing an undetectable elementary principle analogous to the ‘sulfur’ of J’BIR IHBIN AYAM, which he re-named ‘phlogiston’. This could explain why a log (rich in phlogiston) could seem to be heavier than its ashes (deficient in phlogiston). The air that is required for burning served to transport the phlogiston away.

The English chemist JOSEPH PRIESTLY (1733-1804), although a supporter of the phlogiston theory, ironically contributed to its downfall. He heated mercury in air to form red mercuric oxide and then applied concentrated heat to the oxide and noticed that it decomposed again to form mercury whilst giving off a strange gas in which things burnt brightly and vigorously. He concluded that this gas must be ‘phlogiston poor’.

Priestly combined this result with the work of the Scottish physician Daniel Rutherford (1749-1819), who had found that keeping a mouse in an enclosed airtight space resulted in its death (by suffocation) and that nothing could be burnt in the enclosed atmosphere; he formed the idea that the trapped air was so rich in phlogiston that it could accept no more. Rutherford called this ‘phlogisticated air’ and so Priestly called his own gas ‘dephlogisticated air’.

In 1774 Priestley visited the French chemist ANTOINE LAVOISIER (1743-1794).
Lavoisier repeated Priestly’s experiments with careful measurements.
Reasoning that air is made up of a combination of two gases – one that will support combustion and life, another that will not; what was important about Lavoisier’s experiments was not the observation – others had reached a similar conclusion – but the interpretation.

Lavoisier called Priestley’s ‘dephlogisticated air’, ‘oxygene’, meaning ‘acidifying principle’, believing at the time that the active principle was present in all acids (it is not). He called the remaining, ‘phlogisticated’, portion of normal air, ‘azote’, meaning ‘without life’

Oxygen is the mirror image of phlogiston. In burning and rusting (the two processes being essentially the same) a substance picks up one of the gases from the air. Oxygen is consumed, there is no expulsion of ‘phlogiston’.

Lavoisier had been left with almost pure nitrogen, which makes up about four fifths of the air we breath. We now know azote as nitrogen. Rutherford’s ‘mephitic air’ was carbon dioxide.

CALORIC

Like phlogiston, caloric was a weightless fluid, rather like elemental fire, a quality that could be transmitted from one substance to another, so that the first warmed the second up.

It was believed that all substances contained caloric and that when a kettle was being heated over a fire, the fuel gave up its caloric to the flame, which passed it into the metal, which passed it on to the water. Similarly, two pieces of wood rubbed together would give heat because abrasion was releasing caloric trapped within.

What is being transmitted is heat energy. It was the crucial distinction between the physical and the chemical nature of substances that confused the Ancients and led to their minimal elemental schemes.

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JOHANN VAN HELMONT (1579-1644)

1621 – Brussels, Belgium

Portrait of  JOHANN VAN HELMONT

JOHANN VAN HELMONT

‘There are gases other than air’

Van Helmont coined the term ‘gas’.

He hypothesised that the proof that matter is made entirely of water was provided by his experiment of growing a tree-shoot in a weighed quantity of soil and finding that the weight of the tree increased by over a thousand fold whilst that of the soil decreased only slightly. He failed to consider the contribution of the air.

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JOSEPH BLACK (1728- 99)

1757 – Edinburgh

‘Different quantities of heat are required to bring equal weights of different materials to the same temperature’

This definition relates to the concept of specific heat.

Through meticulous experimentation and measurement of results he discovered the concept of ‘latent heat’, the ability of matter to absorb heat without necessarily changing in temperature.
True in the transformation of ice into water at 0degrees C, the same principle applies in the process of transforming water to steam and indeed, all solids to liquids and all liquids to gases.
Through this work Black made the important distinction between heat and temperature.

JAMES WATT benefited from these discoveries during his development of the condensing steam engine.

‘Fixed Air’

Black’s insistence on the importance of quantitative experiments was a step towards setting the standard for modern chemistry.

Black found that heating or treating carbonate salts with acid resulted in the release of a gas that, he reasoned, must have been ‘fixed’ in the solids. He outlined the cycle of chemical changes from limestone (calcium carbonate) to quicklime (calcium oxide) and ‘fixed air’ (carbon dioxide) when heated; quicklime mixed with water to become slaked lime (calcium hydroxide); which when combined with ‘fixed air’ becomes limestone again (turning the solution cloudy).

Although JAN BAPTISTA VAN HELMONT had identified the existence of separate, distinct gases in air over a century before, Black is still often credited with the discovery of carbon dioxide (fixed air) – despite that van Helmont had clearly been aware of its existence.

Black was able to prove that carbon dioxide is made by respiration, through fermentation and in the burning of charcoal, but that the gas would not allow a candle to burn in it nor sustain animal life.

Black’s student Daniel Rutherford (1749 – 1819) called the gas ‘mephitic air’ after the mephitis of legend, a noxious emanation said to cause pestilence, for animals died in an atmosphere of the new gas. Rutherford’s ‘air’ is not, however, the same as Lavoisier’s mephitic air, which is nitrogen (azote).

Observing the effect that removing carbon dioxide from limestone made the latter more alkaline, Black deduced that carbon dioxide is an acidic gas.

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AMEDEO AVOGADRO (1776-1856)

1811 – Italy

‘Equal volumes of all gases at the same temperature and pressure contain the same number of molecules’

In 1811, when Avogadro proposed his HYPOTHESIS, very little was known about atoms and molecules. Avogadro claimed that the same volume of any gas under identical conditions would always contain the same number of fundamental particles, or molecules. A litre of hydrogen would contain exactly the same number of molecules as a litre of oxygen or a litre of carbon dioxide.

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In 1814 ANDRE AMPERE was credited with discovering that if a gas consisted of a single element, its atoms could clump in pairs. The molecules of oxygen consisted of pairs of oxygen atoms, and the molecules of chlorine, pairs of chlorine atoms.
Diatomic gases possess a total of six degrees of simple freedom per molecule that are related to atomic motion.

This provides a way of comparing the weights of different molecules. It was only necessary to weigh equal volumes of different gases and compare them. This would be exactly the same as comparing the weights of the individual molecules of each gas.

Avogadro realised that GAY-LUSSAC‘s law provided a way of proving that an atom and a molecule are not the same. He suggested that the particles (molecules) of which nitrogen gas is composed consist of two atoms, thus the molecule of nitrogen is N2. When one volume (one molecule) of nitrogen combines with three volumes (three molecules) of hydrogen, two volumes (two molecules) of ammonia, NH3, are produced.

N2 + 3H2 ↔ 2NH3

However, the idea of a molecule consisting of two or more atoms bound together was not understood at that time.

Avogadro’s law was forgotten until 1860 when the Italian chemist STANISLAO CANNIZZARO (1826-1910) explained the necessity of distinguishing between atoms and molecules.

Avogadro’s constant
From Avogadro’s law it can be deduced that the same number of molecules of all gases at the same temperature and pressure should have the same volume. This number has been determined experimentally: it’s value is 6.022 1367(36) × 1023AVOGADRO’S NUMBER

Avogadro's_number_in_e_notation

That at the same temperature and pressure, equal volumes of all gases have the same number of molecules allows a simple calculation for the combining ratios of all gases – by measuring their percentages by volume in any compound. This in turn facilitates simple calculation of the relative atomic masses of the elements of which it is composed.

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