DANIEL BERNOULLI (1700- 82) JAMES CLERK MAXWELL (1831- 79)

1738 – Switzerland
1859 – England

‘Gases are composed of molecules which are in constant random motion and their properties depend upon this motion’

The volume of a gas is simply the space through which molecules are free to move. Collisions of the molecules with each other and the walls of a container are perfectly elastic, resulting in no decrease in kinetic energy. The average kinetic energy of a gas increases with an increase in temperature and decreases with a decrease in temperature. The theory has been extended to provide a model for two states of matter – liquids and solids.

Bernoulli had a great advantage over DEMOCRITUS. He knew that free atoms were more than simply tiny grains flying though space; they were tiny grains flying through space and obeying NEWTON’s Laws of Motion.
Bernoulli proposed a ‘bombardment theory’, which stated that a gas consisted of tiny particles in rapid, random motion like a swarm of angry bees. He realized that in the case of such a gas visualized as a host of tiny grains in perpetual frenzied motion, the atoms hammering relentlessly on the walls of any containing vessel would produce a force by bombarding the container. The effect of each individual impact would of course be vanishingly small. The effect of billions upon billions of atoms, hammering away incessantly, however, would be to push the walls back. A gas made of atoms would exert a jittery force that we would detect as a ‘pressure’.

Heating a gas would make its particles move faster.
The pressure of a gas such as steam was easy to measure using a piston in a hollow container. This was essentially a moveable wall. To deduce how the pressure of a gas would be affected by different conditions, Bernoulli first made some simplifying assumptions. He assumed the atoms were very small compared to the gulf between them. This allowed Bernoulli to ignore any force – whether of attraction or repulsion – that existed between them, as being unlikely to be ‘long range’. (This is an ‘ideal’ or ‘perfect’ gas. The behaviour of a real gas may differ from the ideal, for example at very high pressure). With the motion of each atom unaffected by its fellows, Newton’s laws dictated that it should fly at a constant speed in a straight line. The exception was when it slammed into a piston or the walls of the container. Bernoulli assumed that in such a collision a gas atom bounced off the walls of the surface without losing any speed, in the process imparting a miniscule force to the wall.

What would happen if the volume of the gas were reduced by applying an outside force to the piston? If the gas were reduced to half its original volume, the atoms would now have to fly only half as far between collisions, in any given time they would collide with the piston twice as many times and would exert twice the pressure. Similarly, if the gas were compressed to a third of its volume, its pressure would triple. This had been observed by ROBERT BOYLE in 1660 and named Boyle’s Law.

What would happen to the pressure of gas in a closed cylinder if the gas were heated while its volume remained unchanged? Exploiting the insight that the temperature of a gas was a measure of how fast on average its atoms were flying about, that when a gas was heated, its atoms speeded up, he deduced that as the atoms would be moving faster they would collide with the piston more often and create a greater force. Consequently the pressure of the gas would rise. This was observed by the French scientist JACQUES ALEXANDRE CESARE CHARLES in 1787, and christened Charles’ law.

After 120 years MAXWELL polished Bernoulli’s ideas into a rigorous mathematical theory. In Germany, LUDWIG  BOLTZMANN championed the atomic hypothesis, but was refuted by the Austrian ERNST MACH, who was convinced that science should not concern itself with any feature of the world that could not be observed directly with the senses.

BERNOULLI’S PRINCIPLE

At a narrow constriction in a pipe or tube, the speed of a gas or liquid is increased, but its pressure is decreased, according to Bernoulli’s principle. This effect is named the Venturi effect (and a pipe or tube with a narrow constriction the Venturi tube) after the Italian G.B. Venturi (1746-1822) who first observed it in constrictions in water channels. An atomiser works on the same principle.

‘As the velocity of a liquid or gas increases, its pressure decreases; and when the velocity decreases, its pressure increases’

 

The principle is expressed as a complex equation, but it can be summed up simply as the faster the flow the lower the pressure.

An aircraft wing’s curved upper surface is longer than the lower one, which ensures that air has to travel further and so faster over the top than it does below the wing. Hence the air pressure underneath is greater than on top of the wing, causing an upward force, called lift.

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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.

He 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.

The Skeptical Chymist

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 insistence on experimental analysis as the arbiter of elemental status 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 the 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.

“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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