J’BIR IHBIN AYAM (722-804)

Around two thousand texts are attributed to this name; the founder of a Shi’ite sect. They were written over a hundred and fifty year period either side of the year 1000.

‘Sulfur and Mercury hypothesis’ (the idea that the glisten of mercury and the yellow of sulphur may somehow be combined in the form of gold).

An Alchemical theory: Accepting the Aristotelian ‘fundamental qualities’ of hot, cold, dry and moist, all metals are composed of two principles. Under the ground two fumes – one dry and smoky (sulfur), one wet and vaporous (mercury) – arising from the centre of the Earth, condense and combine to form metals.

This is said to explain the similarity of all metals; different metals contain different proportions of these two substances. In base metals the combination is impure, in silver and gold they co-exist in a higher state of purity.

The idea underpins the theory of transmutation, as all metals are composed of the same substances in differing proportions, and became the cornerstone of all chemical theory for the next eight hundred years.

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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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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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PARACELSUS (1493-1541)

Europe – early sixteenth century

‘Added salt to the mercury/sulfur diad, making a trinity to match the holy trinity’

picture of philippus aureolus theophrastus_paracelsus

PARACELSUS

Elaborating his writings with occult mystery, Theophrastus von Hohenheim renamed himself Paracelsus and helped to reform medicine by making it chemical.
Many of his ideas were erroneous and his writings were deliberately obscure; he insisted that the ‘doctrine of signatures’ could reveal efficacious drugs for different organs. Proclaiming that specific therapies could counter a particular disease was a radically different approach to the Aristotelian attempts to rebalance an individual’s internal humors.

Paracelsus extended the ‘fundamental qualities’ of the four Aristotelian elements by adding a third ‘hydrostatic principle’ to the diad of J’BIR IHBIN AYAM – saying the material manifestation of the ancient elements ( ‘…everything that lies in the four elements’ ) may be reduced to mercury, sulfur and salt.

The first distillate of an organic substance would be the thin, volatile ‘mercury’, which acted in favour of youth and life while next came the ‘sulfur’, acting in favour of growth and increase. Finally, the dry mass left behind was the ‘salt’. The concept of these three principles was considered a slight advance upon that of the four elements.

These are not the same things as we recognize today, nor elements in their own right; the first two were components of metals, salt was a principle common to all living things.

The Royal physicians of Elizabeth I of England and Henry IV of France assimilated and adapted Paracelsus’s ideas and although his theories lost credibility, his chemical remedies entered mainstream medicine.

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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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ROBERT BOYLE (1627- 91)

1662 – England

‘The volume of a given mass of a gas at constant temperature is inversely proportional to its pressure’

If you double the pressure of a gas, you halve its volume. In equation form: pV = constant; or p1V1 = p2V2 where the subscripts 1 & 2 refer to the values of pressure and volume at any two readings during the experiment.

Born at Lismore Castle, Ireland, Boyle was a son of the first Earl of Cork. After four years at Eton College, Boyle took up studies in Geneva in 1638. In 1654 he moved to Oxford where in 1656, with the philosopher John Locke and the architect Christopher Wren, he formed the experimental Philosophy Club and met ROBERT HOOKE, who became his assistant and with whom he began making the discoveries for which he became famous.

Robert Boyle. New Experiments Physico-Mechanical. Oxford: Thomas Robinson, 1662

New Experiments Physico-Mechanical 1662

In 1659, with Hooke, Boyle made an efficient vacuum pump, which he used to experiment on respiration and combustion, and showed that air is necessary for life as well as for burning. They placed a burning candle in a jar and then pumped the air out. The candle died. Glowing coal ceased to give off light, but would start glowing again if air was let in while the coal was still hot. In addition they placed a bell in the jar and again removed the air. Now they could not hear it ringing and so they found that sound cannot travel through a vacuum.

Boyle proved Galileo’s proposal that all matter falls at equal speed in a vacuum.

He established a direct relationship between air pressure and volumes of gas. By using mercury to trap some air in the short end of a ‘J’ shaped test tube, Boyle was able to observe the effect of increased pressure on its volume by adding more mercury. He found that by doubling the mass of mercury (in effect doubling the pressure), the volume of the air in the end halved; if he tripled it, the volume of air reduced to a third. His law concluded that as long as the mass and temperature of the gas is constant, then the pressure and volume are inversely proportional.

Boyle appealed for chemistry to free itself from its subservience to either medicine or alchemy and is responsible for the establishment of chemistry as a distinct scientific subject. His work promoted an area of thought which influenced the later breakthroughs of ANTOINE LAVOISIER (1743-93) and JOSEPH PRIESTLY (1733-1804) in the development of theories related to chemical elements.

Boyle extended the existing natural philosophy to include chemistry – until this time chemistry had no recognised theories.

The idea that events are component parts of regular and predictable processes precludes the action of magic.
Boyle sought to refute ARISTOTLE and to confirm his atomistic or ‘corpuscular’ theories by experimentation.

In 1661 he published his most famous work, ‘The Skeptical Chymist’, in which he rejected Aristotle’s four elements – earth, water, fire and air – and proposed that an element is a material substance consisting at root of ‘primitive and simple, or perfectly unmingled bodies’, that it can be identified only by experiment and can combine with other elements to form an infinite number of compounds.

The book takes the form of a dialogue between four characters. Boyle represents himself in the form of Carneades, a person who does not fit into any of the existing camps, as he disagrees with alchemists and sees chemists as lazy hobbyists. Another character, Themistius, argues for Aristotle’s four elements; while Philoponus takes the place of the alchemist, Eleutherius stands in as an interested bystander.

In the conclusion he attacks chemists.

page from one of Boyle's publications“I think I may presume that what I have hitherto Discursed will induce you to think, that Chymists have been much more happy finding Experiments than the Causes of them; or in assigning the Principles by which they may be best explain’d”
He pushes the point further: “me thinks the Chymists, in the searches after truth, are not unlike the Navigators of Solomon’s Tarshish Fleet, who brought home Gold and Silver and Ivory, but Apeas and Peacocks too; For so the Writings of several (for I say not, all) of your Hermetick Philosophers present us, together with divers Substantial and noble Experiments, Theories, which either like Peacock’s feathers made a great show, but are neither solid nor useful, or else like Apes, if they have some appearance of being rational, are blemished with some absurdity or other, that when they are Attentively consider’d, makes them appear Ridiculous”

The critical message from the book was that matter consisted of atoms and clusters of atoms. These atoms moved about, and every phenomenon was the result of the collisions of the particles.

He was a founder member of The Royal Society in 1663. Unlike the Accademia del Cimento the Royal Society thrived.

Like FRANCIS BACON he experimented relentlessly, accepting nothing to be true unless he had firm empirical grounds from which to draw his conclusions. He created flame tests in the detection of metals and tests for identifying acidity and alkalinity.

It was his insistence on publishing chemical theories supported by accurate experimental evidence – including details of apparatus and methods used, as well as failed experiments – which had the most impact upon modern chemistry.

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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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HENRY CAVENDISH (1731-1810)

1766 – England

‘Three Papers Containing Experiments On Factitious Airs’

(gases made from reactions between liquids and solids)

1798 – Density of the earth
Using a torsion balance and the application of NEWTON’s theory of gravity, Cavendish concluded that the earth’s density was 5.5 times that of water.

Born of the English aristocracy and inheritor of a huge sum of money half way through his life, Cavendish is remembered for his work in chemistry.
He demonstrated that hydrogen (inflammable air) and carbon dioxide (fixed air) were gases distinct from ‘atmospheric air’. His claim to the discovery that water was not a distinct element – a view held since the time of ARISTOTLE – but a compound made from two parts hydrogen to one part oxygen, became confused with similar observations made by ANTOINE LAVOISIER.

Full length drawing of Henry Cavendish  &copy:

CAVENDISH

1871 – England

Almost all his discoveries remained unpublished until the late nineteenth century when his notes were found and JAMES CLERK MAXWELL dedicated himself to publishing Cavendish’s work, a task he completed in 1879.
By then many potential breakthroughs, significant at the time, had been surpassed by history.

In 1871 the endowment of the Cavendish Laboratory was made to Cambridge University by Cavendish’s legatees.

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JOSEPH PRIESTLEY (1733-1804)

1774 – England

portrait of JOSEPH PRIESTLY (1733-1804) ©

JOSEPH PRIESTLY

‘Priestly stumbled upon oxygen in 1774 while heating mercury oxide and discovered that it greatly enhanced the burning of a candle’s flame’

Priestly did not realise the true impact of his findings and it was left to ANTOINE LAVOISIER whom he told of his findings in 1775 to establish the central place oxygen has in the fields of chemistry and biology.

Priestly named the gas ‘dephlogisticated air’, in keeping with the accepted theory that all flammable substances contained the elusive substance ‘phlogiston‘ which was central to the combustion process and was released (and lost) during it.

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JACQUES-ALEXANDRE-CESARE CHARLES (1746-1823)

1787 – France

‘The volume of a given mass of gas at constant pressure is directly proportional to its absolute temperature’

Portrait of Jacques_Charles ©

JACQUES CHARLES

In other words, if you double the temperature of a gas, you double its volume. In equation form:  V/T = constant, or  V1/T1 = V2/T2,  where  V1 is the volume of the gas at a temperature  T1 (in kelvin) and  V2 the new volume at a new temperature  T2.

This principle is now known as Charles’ Law (although sometimes named after GAY-LUSSAC because of his popularisation of it fifteen years later – Gay Lussac’s experimental proof was more accurate than Charles’).
It completed the two ‘gas laws’.

A fixed amount of any gas expands equally at the same increments in temperature, as long as it is at constant pressure.

Likewise for a decline in temperature, all gases reduce in volume at a common rate, to the point at about minus 273degrees C, where they would theoretically converge to zero volume. It is for this reason that the kelvin temperature scale later fixed its zero degree value at this point.

CHARLES’ Law and BOYLE‘s Law may be expressed as a single equation, pV/T = constant. If we also include AVOGADRO‘s law, the relationship becomes pV/nT = constant, where n is the number of molecules or number of moles.

The constant in this equation is called the gas constant and is shown by R
The equation – known as the ideal gas equation – is usually written as pV = nRT

Strictly, it applies to ideal gases only. An ideal gas obeys all the assumptions of the kinetic theory of gases. There are no ideal gases in nature, but under certain conditions all real gases approach ideal behaviour.

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Related sites
poster describing the combined gas laws

Combined Gas Laws

ANTOINE LAVOISIER (1743- 94)

1789 – France

‘In a chemical reaction, the total mass of the reacting substances is equal to the total mass of the products formed’

Mass is neither created nor destroyed in a chemical change.

Lavoisier’s Table of Elements

Lavoisier’s Table of Elements

Antoine Lavoisier made the first list of the elements, established the idea of conservation of mass and discovered the true nature of burning and the role of oxygen. Lavoisier continued the work of ROBERT BOYLE. He radically reformed the concept of chemistry and killed off the ARISTOTLEIAN concepts of elemental matter. Lavoisier realised that every substance can exist in three phases – solid, liquid and gas – and proved that water and air are not elements, as had been believed for centuries, but chemical compounds. He thus helped to provide a foundation for DALTON’s atomic theory. He opened the way to the idea that air not only had mass but may be a mixture of gases.

Lavoisier was instrumental in disproving the phlogiston theory, a widely held view that when substances burn they give off ‘phlogiston’, a weightless substance. The phlogiston debate owed much to ALCHEMY and said that anything burnable contained a special ‘active’ substance called phlogiston that dissolved into the air when it burned. Therefore, anything that burned must become lighter because it loses phlogiston. This had become the scientific orthodoxy.

By carefully weighing substances before and after burning, Lavoisier showed that combustion was a chemical reaction in which a fuel combined with oxygen.

He burned a piece of tin inside a sealed container and showed that it became heavier after burning, while the air became lighter.
While the overall weight of the vessel remained the same during Lavoisier’s experiments – for example when burning tin, phosphorus or sulphur in a sealed container – the solids being heated could in fact gain mass. There was no change in total mass as substances were simply changing places.
It became apparent that rather than losing something (phlogiston) to the air, the tin was taking something from it. The explanation was that the weight gain was caused by combination of the solid with the air trapped in the container.

Full length picture of LAVOISIER

LAVOISIER

After meeting JOSEPH PRIESTLY in Paris, Lavoisier realised that Priestley’s ‘dephlogisticated air’ was not only the gas from the atmosphere that was combining with the matter but, moreover, it was actually essential for combustion. He renamed it ‘oxygen’ (‘acid producer’ in Greek) from the mistaken belief that the element was evident in the make up of all acids. He also noted the existence of the other main component of air, the inert gas nitrogen that he named ‘azote’.

Lavoisier’s wife Marie-Anne Pierrette assisted him in much of his experimental work and illustrated his book, Traite Elementaire de Chimie (Elementary Treatise on Chemistry). The text defined a chemical element, saying that it was any substance that could not be analysed further. With this definition he compiled a list of the then known elements, which founded the naming process for chemical compounds. Lavoisier’s list contained 23 ‘elements’. Many turned out not to be elements at all, but the list included sulphur, mercury, iron and zinc, silver and gold. Lavoisier’s name is still used in the title of the modern chemical naming system.
It took John Dalton to connect the concept of elements with the concept of atoms. Dalton noticed that when elements combined to make a compound, they always did so in fixed proportions.

During the French revolution, Lavoisier was guillotined.

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LUIGI GALVANI (1737- 98) ALESSANDRO VOLTA (1745-1827)

1791 & 1799 – Italy

‘Galvani: An electric current is produced when an animal tissue comes into contact with two different metals.

Volta: An electric current is not dependent on an animal tissue and can be produced by chemicals’

Galvani was wrong and Volta was right.

Galvani had found that by touching a dead frog’s legs with two different metal implements, the muscles in the frog’s legs would twitch. Galvani wrongly concluded it was the animal tissue that was storing the electricity, releasing it when touched by the metals. He felt he had discovered the very force of life – ‘animal electricity’ – that animated flesh and bone.

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GALVANI

Soon dozens of scientists were trying to bring corpses back to life by electrifying them. Volta was not convinced the animal muscle was the important factor in the production of the current.

He repeated Galvani’s experiments and concluded, controversially at the time, the different metals were the important factor.

A bitter dispute arose as to whose interpretation was correct. Volta began putting together different combinations of metals to see if they produced any current; later he produced a wet battery of fluid and metals.
Volta’s method of producing electric current involved using discs of silver and zinc dipped in a bowl of salt solution. He reasoned that a much larger charge could be produced by stacking several discs separated by cards soaked in salt water – by attaching copper wires to each end of the ‘pile’ he successfully obtained a steady current.

The ‘voltaic pile’ was the first battery in history (1800). Napoleon Bonaparte, who at the time controlled the territory in which Volta lived, was so impressed he made him a Count and awarded him the Legion d’Honour.

portrait of ALESSANDRO VOLTA ©

VOLTA

Volt, the SI unit of electric potential, honours Volta.

Although Galvani’s theory on ‘animal electricity’ was not of any major importance, he has also achieved nominal immortality; like ‘volt’, the words ‘galvanic’ (sudden and dramatic), ‘galvanised’ (iron or steel coated with zinc) and ‘galvanometer’ (an instrument for detecting small currents) have become part of everyday language.

A volt is defined as the potential difference between two points on a conductor carrying one ampere current when the power dissipated between the points is one watt.

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JOSEPH LOUIS PROUST (1754-1826)

1799 – France

A MIXTURE VERSUS A COMPOUND. (Robert L. Wolke)

‘Chemical compounds contain elements in definite proportions by mass’

Proust’s law is now referred to as the law of constant composition or the law of definite proportions.

Claude Berthollet (1748-1822), then the recognised leader of science in France, rejected Proust’s law. Berthollet believed that the force of chemical affinity, like gravity, must be proportional to the masses of acting substances. He suggested that the composition of chemical compounds could vary widely. Proust showed that Berthollet’s experiments were not done on pure compounds, but rather on mixtures. Thus for the first time a clear distinction was made between mixtures and compounds.

When Dalton proposed his atomic theory, Proust’s law helped to confirm the hypothesis. According to Dalton, atoms would always combine in simple whole number ratios. For example, all water molecules are alike, consisting of two atoms of hydrogen and one atom of oxygen. Therefore, all water has the same composition.

Proust’s law has been confirmed by experiments. For example, water always contains 11.2 percent hydrogen and 88.8 percent oxygen.

In recent years chemists have discovered certain rare compounds in which elements do not combine in simple whole number ratios. These compounds are known as ‘berthollides’.
In contrast, compounds in which elements do combine in simple whole number ratios are sometimes referred to as ‘daltonides’.

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JOHN DALTON (1766-1844)

1801 England

‘The total pressure of a mixture of gases is the sum of the partial pressures exerted by each of the gases in the mixture’

Partial pressures of gases:
Dalton stated that the pressure of a mixture of gases is equal to the sum of the pressures of the gases in the mixture. On heating gases they expand and he realised that each gas acts independently of the other.

Each gas in a mixture of gases exerts a pressure, which is equal to the pressure it would exert if it were present alone in the container; this pressure is called partial pressure.

Dalton’s law of partial pressures contributed to the development of the kinetic theory of gases.

His meteorological observations confirmed the cause of rain to be a fall in temperature, not pressure and he discovered the ‘dew point’ and that the behaviour of water vapour is consistent with that of other gases.

He showed that a gas could dissolve in water or diffuse through solid objects.

Graph demonstrating the varying solubility of gases

The varying solubility of gases

Further to this, his experiments on determining the solubility of gases in water, which, unexpectedly for Dalton, showed that each gas differed in its solubility, led him to speculate that perhaps the gases were composed of different ‘atoms’, or indivisible particles, which each had different masses.
On further examination of his thesis, he realised that not only would it explain the different solubility of gases in water, but would also account for the ‘conservation of mass’ observed during chemical reactions – as well as the combinations into which elements apparently entered when forming compounds – because the atoms were simply ‘rearranging’ themselves and not being created or destroyed.

In his experiments, he observed that pure oxygen will not absorb as much water vapour as pure nitrogen – his conclusion was that oxygen atoms were bigger and heavier than nitrogen atoms.

‘ Why does not water admit its bulk of every kind of gas alike? …. I am nearly persuaded that the circumstance depends on the weight and number of the ultimate particles of the several gases ’

In a paper read to the Manchester Society on 21 October 1803, Dalton went further,

‘ An inquiry into the relative weight of the ultimate particles of bodies is a subject as far as I know, entirely new; I have lately been prosecuting this enquiry with remarkable success ’

Dalton described how he had arrived at different weights for the basic units of each elemental gas – in other words the weight of their atoms, or atomic weight.

Dalton had noticed that when elements combine to make a compound, they always did so in fixed proportions and went on to argue that the atoms of each element combined to make compounds in very simple ratios, and so the weight of each atom could be worked out by the weight of each element involved in a compound – the idea of the Law of Multiple Proportions.

When oxygen and hydrogen combined to make water, 8 grammes of oxygen was used for every 1 gramme of hydrogen. If oxygen consisted of large numbers of identical oxygen atoms and hydrogen large numbers of hydrogen atoms, all identical, and the formation of water from oxygen and hydrogen involved the two kinds of atoms colliding and sticking to make large numbers of particles of water (molecules) – then as water has an identity as distinctive as either hydrogen or oxygen, it followed that water molecules are all identical, made of a fixed number of oxygen atoms and a fixed number of hydrogen atoms.

Dalton realised that hydrogen was the lightest gas, and so he assigned it an atomic weight of 1. Because of the weight of oxygen that combined with hydrogen in water, he first assigned oxygen an atomic weight of 8.

There was a basic flaw in Dalton’s method, because he did not realise that atoms of the same element can combine. He assumed that a compound of atoms, a molecule, had only one atom of each element. It was not until Italian scientist AMADEO AVOGADRO’s idea of using molecular proportions was introduced that he would be able to calculate atomic weights correctly.

In his book of 1808, ‘A New System of Chemical Philosophy’ he summarised his beliefs based on key principles: atoms of the same element are identical; distinct elements have distinct atoms; atoms are neither created nor destroyed; everything is made up of atoms; a chemical change is simply the reshuffling of atoms; and compounds are made up of atoms from the relevant elements. He published a table of known atoms and their weights, (although some of these were slightly wrong), based on hydrogen having a mass of one.

Nevertheless, the basic idea of Dalton’s atomic theory – that each element has its own unique sized atoms – has proved to be resoundingly correct.

If oxygen atoms all had a certain weight which is unique to oxygen and hydrogen atoms all had a certain weight that was unique to hydrogen, then a fixed number of oxygen atoms and a fixed number of hydrogen atoms combined to form a fixed weight of water molecules. Each water molecule must therefore contain the same weight of oxygen atoms relative to hydrogen atoms.

Here then is the reason for the ‘law of fixed proportions’. It is irrelevant how much water is involved – the same factors always hold – the oxygen atoms in a single water molecule weigh 8 times as much as the hydrogen atoms.

Dalton wrongly assumed that elements would combine in one-to-one ratios as a base principle, only converting into ‘multiple proportions’ (for example from carbon monoxide, CO, to carbon dioxide, CO2) under certain conditions. Each water molecule (H2O) actually contains two atoms of hydrogen and one atom of oxygen. An oxygen atom is actually 16 times as heavy as a hydrogen atom. This does not affect Dalton’s reasoning.

The law of fixed proportions holds because a compound consists of a large number of identical molecules, each made of a fixed number of atoms of each component element.

Although the debate over the validity of Dalton’s thesis continued for decades, the foundation for the study of modern atomic theory had been laid and with ongoing refinement was gradually accepted.

A_New_System_of_Chemical_Philosophy - DALTON's original outline

A_New_System_of_Chemical_Philosophy

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JOHN DALTON

1808 – Manchester, England

‘All matter is made up of atoms, which cannot be created, destroyed or divided. Atoms of one element are identical but different from those of other elements. All chemical change is the result of combination or separation of atoms’

Dalton struggled to accept the theory of GAY-LUSSAC because he believed, as a base case, that gases would seek to combine in a one atom to one atom ratio (hence he believed the formula of water to be HO not H2O). Anything else would contradict Dalton’s theory on the indivisibility of the atom, which he was not prepared to accept.

The reason for the confusion was that at the time the idea of the molecule was not understood.
Dalton believed that in nature all elementary gases consisted of indivisible atoms, which is true for example of the inert gases. The other gases, however, exist in their simplest form in combinations of atoms called molecules. In the case of hydrogen and oxygen, for example, their molecules are made up of two atoms, described as H2 and O2 respectively.

Gay-Lussac examined various substances in which two elements form more than one type of compound and concluded that if two elements A and B combine to form more than one compound, the different masses of A that combine with a fixed mass of B are in a simple whole number ratio. This is the law of multiple proportions.

AVOGADRO’s comprehension of molecules helped to reconcile Gay-Lussac’s ratios with Dalton’s theories on the atom.

Gay-Lussac’s ratio for water could be explained by two molecules of hydrogen (four ‘atoms’) combining with one molecule of oxygen (two ‘atoms’) to result in two molecules of water (2H2O).

2H2 + O2 ↔ 2H2O

When Dalton had considered water, he could not understand how one atom of hydrogen could divide itself (thereby undermining his indivisibility of the atom theory) to form two particles of water. The answer proposed by Avogadro was that oxygen existed in molecules of two and therefore the atom did not divide itself at all.

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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.

Drawing of AVOGADRO ©

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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JOSEF VON FRAUNHOFER (1787-1826)

1823 – Germany

‘The spectroscope’

A significant improvement on the apparatus used by Newton. Sunlight, instead of passing through a pinhole before striking a prism, is passed through a long thin slit in a metal plate. This creates a long ribbon-like spectrum, which may be scanned from end to end with a microscope.

image of the visible portion of the electromagnetic spectrum showing a series of dark fraunhofer lines

Cutting across the ribbon of rainbow colours are thin black lines. The lines are present even when a diffraction grating is used instead of a prism, proving that the lines are not produced by the material of a prism, but are inherent in sunlight.

An equivalent way of describing colours is as light waves of different sizes.
The wavelength of light is fantastically small, on average about a thousandth of a millimeter, with the wavelength of red light being about twice as long as that of blue light.

Fraunhofer’s black lines correspond to missing wavelengths of light.

By 1823 Fraunhofer had measured the positions of 574 spectral lines, labeling the most prominent ones with the letters of the alphabet. The lines labeled with the letters ‘H’ and ‘K’ correspond to light at a wavelength of 0.3968 thousandths of a millimeter and 0.3933 thousandths of a millimeter, respectively. The lines are present in the spectrum of light from stars, usually in different combinations.

Fraunhofer died early at the age of 39 and it was left to the German GUSTAV KIRCHOFF to make the breakthrough that explained their significance.

Astronomers today know the wavelengths of more than 25,000 ‘Fraunhofer lines’.

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THOMAS GRAHAM (1805- 69)

1833 – UK

‘Under the same conditions, the rate of diffusion of a gas is inversely proportional to the square root of its density’

For example, hydrogen diffuses four times as fast as oxygen under the same conditions of temperature and pressure.

Gases have no fixed volume; they expand to fill the entire volume of their container. This spreading of gas particles is called diffusion. The lightest gases diffuse most rapidly.

Graham is referred to as the father of colloid chemistry. In 1854 he invented the process of dialysis, which is based on the principle that some material will diffuse across a semi-permeable membrane and some material will not.

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JANS JACOB BERZELIUS (1779-1848)

1840 – Sweden

‘An element can exist in two or more forms with different properties’

The various forms are known as allotropes. Graphite, diamond and buckyballs are three crystalline allotropes of carbon.

Berzelius contributed more than just allotropes to chemistry. When DALTON revived the idea of the atom as the unit of matter, he used circular symbols to represent atoms. Berzelius discarded Dalton’s cumbersome system and in its place introduced a rational system of chemical shorthand.

He declared ‘I shall take as the chemical sign the initial letter of the Latin name of each element. If the first two letters be common to two elements I shall use both the initial letter and the first letter they have not in common’.

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EDWARD FRANKLAND (1825- 99)

1852 – England

‘The capacity of a given element to combine with other elements to form compounds is determined by the number of chemical bonds that element can form with other elements’

This ‘combining power’ is now termed valency or valence.

Photo portrait of EDWARD FRANKLAND ©

EDWARD FRANKLAND

Valency is the number of electrons an atom of an element must lose or gain, either completely or by sharing, in order to form a compound. This leaves the atom with the stable electronic configuration of a noble gas (that is a completely full outer shell).
For example, in H2O, hydrogen has a valency of +1 (H+) and Oxygen -2 (O-2). Two hydrogen atoms lose one electron each; one oxygen atom gains these two electrons.

Every atom has a fixed number of bonds that it can form, and to be stable all of these must be employed. If a hydrogen atom bonds to another hydrogen atom, then the bonds on each atom will be fully used in forming H2, a molecule of hydrogen. The same can occur between two atoms of oxygen.
Alternatively, the two bonds on oxygen could be occupied by the bonds on two hydrogen atoms, forming water, H2O.
Frankland understood that only molecules in which atoms had all of their bonds occupied were stable. Most elements have a fixed valency, although some have more than one. The numerical values of valences represent the charge on the ion.

Lone pair shapes

Lone pair shapes

The concept of valence was further developed by FRIEDRICH AUGUST KEKULE who decided that the valence of carbon must be four which allowed carbon to form into chains of atoms or link into closed, six-atom rings. In the simplest such molecule, three of each carbon’s bonds are used to keep the ring together and the remaining bond on each carbon binds to a hydrogen atom. The resulting molecule of benzene contains six atoms of carbon and six atoms of hydrogen.

(image source)

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ROBERT BUNSEN (1811- 99) GUSTAV KIRCHHOFF (1824- 87)

1860 – Germany

‘Each chemical element, when heated to incandescence, produces its own characteristic lines in the spectrum of light’

For example, sodium produces two bright yellow lines.
Bunsen developed the Bunsen burner in 1855.
In the flame test the Bunsen burner’s non-luminous flame does not interfere with the coloured flame given off by the sample.

bunsen_burner_flame_types1398x1026

Kirchhoff was a professor of physics at Heidelberg. Bunsen and Kirchhoff together developed the first spectroscope, a device used to produce and observe a spectrum. They used their spectroscope to discover two new elements, caesium (1860) and rubidium (1861).

In 1860 Kirchhoff made the discovery that when heated to incandescence, each element produces its own characteristic lines in the spectrum.

This means that each element emits light of a certain wavelength – sodium’s spectrum has two yellow lines (wavelengths about 588 and 589 nanometres). The Sun’s spectrum contains a number of dark lines, some of which correspond to these wavelengths.

The Swedish scientist ANDERS ANGSTROM had, four years earlier, found that a gas always absorbs light at the same wavelength that it emits light. If the gas is hotter than the light source, then more light is emitted by the gas than absorbed, creating a bright line in the spectrum of the light source. If the gas is cooler than the light source the opposite happens; more light is absorbed by the gas than is emitted, creating a dark line.
The dark solar D lines told Kirchhoff that sodium is present in the relatively cool outer atmosphere of the Sun. This could be tested in the laboratory by burning a piece of chalk in a hot oxygen-hydrogen torch. The intensely bright limelight that is produced may be passed through a cooler sodium flame and the light emerging examined through a spectroscope. Crossing the spectrum of the artificial light occur black lines at the same wavelength that a sodium flame emits light. This solved the mystery of the FRAUNHOFER LINES.

Scientists now had a means to determine the presence of elements in stars. By comparing the dark lines in the spectra of light from the stars with the bright lines produced by substances in the laboratory, Kirchhoff had been able to identify the elements that made up a celestial body millions of miles away in space.

Portrait of GUSTAV KIRCHHOFF

GUSTAV KIRCHHOFF

In England the astronomer William Huggins recorded the spectra of hundreds of stars and showed the unmistakable fingerprints of familiar elements that are found on the Earth’s surface. The stars are made of exactly the same kind of atoms as the Earth.

In 1868 Norman Lockyer described a spectral line in the yellow region very close to the wavelength of the two ‘D’ spectral lines of sodium. After repeated attempts to discover a substance that produced the same line on Earth, it appeared that the line did not correspond to any hitherto known element. Lockyer gave the element the name ‘helium’, the gas later to be found associated with radioactive decay in ores containing uranium.


    

Helium had not previously been found on Earth because it is both inert and lighter than air, ironic because after hydrogen, helium is the second most common element in the universe.

In 1904 RUTHERFORD would declare that the presence of helium in the Sun was evidence that sunlight was a product of radioactive processes. The absence of any FRAUNHOFER lines in sunlight that corresponded to radium dealt a blow to this hypothesis. Was there another way of releasing atomic energy than radioactivity?

 

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