KARL WILHELM SCHEELE (1742- 86)

1772 – France

Portrait of CARL WILHELM SCHEELE ©

CARL WILHELM SCHEELE

Scheele discovers oxygen two years before Joseph Priestly, but does not publish his findings until 1777.

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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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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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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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JOSEPH LOUIS GAY-LUSSAC (1778-1850)

1808 – France

‘Volumes of gases which combine or which are produced in chemical reactions are always in the ratio of small whole numbers’

One volume of nitrogen and three volumes of hydrogen produce two volumes of ammonia. These volumes are in the whole number ratio of 1:3:2

N2 + 3H2 ↔ 2NH3

Along with his compatriot Louis Thenard, Gay-Lussac proved LAVOISIER’s assumption, that all acids had to contain oxygen, to be wrong.

portrait of GAY-LUSSAC ©

GAY-LUSSAC

Gay-Lussac re-examined JACQUES CHARLES’ unpublished and little known work describing the effect that the volume of a gas at constant pressure is directly proportional to temperature and ensured that Charles received due credit for his discovery.

Alongside JOHN DALTON, Gay-Lussac concluded that once pressure was kept fixed, near zero degrees Celsius all gases increased in volume by 1/273 the original value for every degree Celsius rise in temperature. At 10degrees, the volume would become 283/273 of its original value and at – 10degrees it would be 263/273 of that same original value. He extended this relation by showing that when volume was kept fixed, gas would increase or decrease the pressure exerted on the outside of the gas container by the same 1/273 factor when temperature was shifted by a degree Celsius. This did not depend upon the gas being studied and hinted at a deep connection shared by all gases. If the volume of a gas at fixed pressure decreased by 1/273 for every 1degree drop, it would reach zero volume at -273degrees Celsius. The same was true for pressure at fixed volume. That had to be the end of the scale, the lowest possible temperature one could reach. Absolute zero.

In an 1807 gas-experiment, Gay-Lussac took a large container with a removable divider down the middle and filled half with gas and made the other half a vacuüm. When the divider was suddenly removed, the gas quickly filled the whole container. According to caloric theory, temperature was a measure of the concentration of caloric fluid and removal of the divider should have led to a drop in temperature because the fluid was spread out over a greater volume without any loss of caloric fluid. (The same amount of fluid in a larger container means lower concentration).
Evidence linking heat to mechanical energy accumulated. Expenditure of the latter seemed to lead to the former.

Gay-Lussac was an experimentalist and his law was based on extensive experiments. The explanation of why gases combine in this way came from AVOGADRO.

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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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