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

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

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.

 

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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JAMES CLERK MAXWELL (1831- 79)

1864 Scotland

‘Four equations that express mathematically the way electric or magnetic fields behave’

The Scottish physicist examined Faraday’s ideas concerning the link between electricity and magnetism interpreted in terms of fields of force and saw that they were alternative expressions of the same phenomena. Maxwell took the experimental discoveries of Faraday in the field of electromagnetism and provided his unified mathematical explanation, which outlined the relationship between magnetic and electric fields. He then proved this by producing intersecting magnetic and electric waves from a straightforward oscillating electric current.

In 1831 – following the demonstration by HANS CHRISTIAN OERSTED that passing an electric current through a wire produced a magnetic field around the wire, thereby causing a nearby compass needle to be deflected from north – MICHAEL FARADAY had shown that when a wire moves within the field of a magnet, it causes an electric current to flow along the wire.
This is known as electromagnetic induction.

In 1864 Maxwell published his ‘Dynamical Theory of the Electric Field’, which offered a unifying, mathematical explanation for electromagnetism.

In 1873 he published ‘Treatise on Electricity and Magnetism’.

The equations are complex, but in general terms they describe:

  • a general relationship between electric field and electric charge
  • a general relationship between magnetic field and magnetic poles
  • how a changing magnetic field produces electric current
  • how an electric current or a changing electric field produces a magnetic field

The equations predict the existence of electromagnetic waves, which travel at the speed of light and consist of electric and magnetic fields vibrating in harmony in directions at right angles to each other. The equations also show that light is related to electricity and magnetism.

Maxwell worked out that the speed of these waves would be similar to the speed of light and concluded, as Faraday had hinted, that normal visible light was a form of electromagnetic radiation. He argued that infrared and ultraviolet light were also forms of electromagnetic radiation, and predicted the existence of other types of wave – outside the ranges known at that time – which would be similarly explainable.

Verification came with the discovery of radio waves in 1888 by HEINRICH RUDOLPH HERTZ. Further confirmation of Maxwell’s theory followed with the discovery of X-rays in 1895.

photo portrait of JAMES CLERK MAXWELL ©

JAMES CLERK MAXWELL

Maxwell undertook important work in thermodynamics. Building on the idea proposed by JAMES JOULE, that heat is a consequence of the movement of molecules in a gas, Maxwell suggested that the speed of these particles would vary greatly due to their collisions with other molecules.

In 1855 as an undergraduate at Cambridge, Maxwell had shown that the rings of Saturn could not be either liquid or solid. Their stability meant that they were made up of many small particles interacting with one another.

In 1859 Maxwell applied this statistical reasoning to the general analysis of molecules in a gas. He produced a statistical model based on the probable distribution of molecules at any given moment, now known as the Maxwell-Boltzmann kinetic theory of gases.
He asked what sort of motion you would expect the molecules to have as they moved around inside their container, colliding with one another and the walls. A reasonably sized vessel, under normal pressure and temperature, contains billions and billions of molecules. Maxwell said the speed of any single molecule is always changing because it is colliding all the time with other molecules. Thus the meaningful quantities are molecular average speed and the distribution about the average. Considering a vessel containing several different types of gas, Maxwell realized there is a sharp peak in the plot of the number of molecules versus their speeds. That is, most of the molecules have speeds within a small range of some particular value. The average value of the speed varies from one kind of molecule to another, but the average value of the kinetic energy, one half the molecular mass times the square of the speed, (1/2 mv2), is almost exactly the same for all molecules. Temperature is also the same for all gases in a vessel in thermal equilibrium. Assuming that temperature is a measure of the average kinetic energy of the molecules, then absolute zero is absolute rest for all molecules.

The Joule-Thomson effect, in which a gas under high pressure cools its surroundings by escaping through a nozzle into a lower pressure environment, is caused by the expanding gas doing work and losing energy, thereby lowering its temperature and drawing heat from its immediate neighbourhood. By contrast, during expansion into an adjacent vacuüm, no energy is lost and temperature is unchanged.

The explanation that heat in gas is the movement of molecules dispensed with the idea of the CALORIC  fluid theory of heat.

The first law of thermodynamics states that the heat in a container is the sum of all the molecular kinetic energies.
Thermal energy is another way of describing motion energy, a summing of the very small mechanical kinetic energies of a very large number of molecules; energy neither appears nor disappears.
According to BOYLE’s, CHARLES’s and GAY-LUSSAC’s laws, molecules beating against the container walls cause pressure; the higher the temperature, the faster they move and the greater the pressure. This also explains Gay-Lussac’s experiment. Removing the divider separating half a container full of gas from the other, evacuated half allows the molecules to spread over the whole container, but their average speed does not change. The temperature remains the same because temperature is the average molecular kinetic energy, not the concentration of caloric fluid.

In 1871 Maxwell became the first Professor of Physics at the Cavendish Laboratory. He died at age 48.

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