# MAX PLANCK (1856-1947)

1900 – Germany

‘Energy is not a continuous quantity but it is quantised; it flows in discrete packets or quanta. When particles emit energy they do so only in quanta’

According to Quantum theory, the energy (E) of one quantum (photon) is given by E = hf where f is the frequency of radiation and h is Planck’s constant.
Its value is 6.63 × 10-34 joules per second.

h is a tiny number, close to zero, but it is has a finite value. This implies energy is released in discrete chunks, a revolutionary notion.

MAX PLANCK

By the late 1800s the science of thermodynamics was developing to the point that people were beginning to understand the nature of energy.
The traditional view was that energy was released in a continuous stream and that any amount of energy could be indefinitely divided into smaller and smaller ‘lumps’. Planck’s work on the laws of thermodynamics and black body radiation led him to abandon this classical notion of the dynamic principles of energy and formulate the quantum theory, which assumes that energy changes take place in distinct packages, or quanta, that cannot be subdivided. This successfully accounted for certain phenomena that Newtonian theory could not explain.

The basic laws of thermodynamics recognised that energy could not be created or destroyed, but was always conserved. The second law was drawn from an understanding that heat would not pass from a colder body to a hotter body.
The study of thermodynamics was based on the assumption that matter was ultimately composed of particles. LUDWIG BOLTZMAN had proposed an explanation of thermodynamics, saying the energy contained in a system is the collective result of the movements of many tiny particles rattling around. He believed the second law was only valid in a statistical sense; it only worked if you added up all the bits of energy in all the little particles.
Among his detractors was Max Karl Ernst Ludwig Planck.

Planck began his work on the second law of thermodynamics and the concept of entropy. He investigated how materials transform between solid, liquid and gaseous states. In doing so he found explanations for the laws governing the differing freezing and boiling points of various substances.
He also looked at the conduction of electricity through liquid solutions (electrolysis).

In the mid 1890s Planck turned his attention to the question of how heated substances radiate energy. Physicists were aware that all bodies radiate heat at all frequencies – although maximum radiation is emitted only at a certain frequency, which depends on the temperature of the body. The hotter the body, the higher the frequency for maximum radiation. (Frequency is the rate per second of a wave of any form of radiation).

Planck had been considering formulae for the radiation released by a body at high temperature. Using ideas developed by ROBERT KIRCHHOFF, he knew it should be expressible as a combination of wavelength frequency and temperature. For a theoretical ‘black body’, physicists could not predict expressions that were in line with the behaviour of hot bodies at high frequencies and were in agreement with other equations showing their nature at low frequencies. Thus no law could be found which fitted all frequencies and obeyed the laws of classical physics simultaneously.
Plank resolved to find a theoretical formula that would work mathematically, even if it did not reflect known physical laws. His first attempts were partially successful, but did not take into account any notion of particles or quanta of energy, as he was certain of the continuous nature of energy. In an ‘act of despair’ he renounced classical physics and embraced quanta.

The final straw had been a concept developed by John Rayleigh and James Jeans that became known as the ‘ultraviolet catastrophe’ theory. They had developed a formula that predicted values for radiation distribution and worked at low frequencies, but not at high frequencies. It was at odds with Planck’s formula, which worked for high frequencies but broke down at low frequencies. In June 1900 Rayleigh had pointed out that classical mechanics, when applied to the oscillators of a black-body, leads to an energy distribution that increases in proportion to the square of the frequency. This conflicted with all known data.

Planck’s answer was to introduce what he called ‘energy elements’ or quanta and to express the energy emitted as a straightforward multiplication of frequency by a constant, which became known as ‘Planck’s constant’ (6.6256 × 10-34 Jsec-1). This only works with whole number multiples which means for the formula to have any practical use one must accept the radical theory that energy is only released in distinct, non-divisible chunks, known as ‘quanta’, or for a single chunk of energy, a ‘quantum’. This completely contradicts classical physics, which assumed that energy is emitted in a continuous stream. The individual quanta of energy were so small that when emitted at the everyday large levels observed, it appears that energy could seem to be flowing in a continuous stream.
Thus classical physics was cast into doubt and quantum theory was born.

Planck announced his theory on December 14 1900 in his paper ‘On the Theory of the Law of Energy Distribution in the Continuous Spectrum’. Planck said ‘energy is made up of a completely determinate number of finite equal parts, and for this purpose I use the constant of nature h = 6.55 × 10-27(erg sec).’

When ALBERT EINSTEIN was able to explain the ‘photoelectric’ effect in 1905, suggesting that light is emitted in quanta called ‘photons’, by applying Planck’s theory – and likewise NIELS BOHR in his explanation of atomic theory in 1913 – the abstract idea was shown to explain physical phenomena.

Planck was awarded the Nobel Prize for Physics in 1918.

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HEAT

QUANTUM MECHANICS

# 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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MECHANICS

# JOSEF STEFAN (1835- 93) LUDWIG BOLTZMANN (1844-1906)

1879 – Austria

## STEFAN-BOLTZMANN CONSTANT

‘The total energy radiated from a blackbody is proportional to the fourth power of the temperature of the body’

JOSEPH STEFAN

(A blackbody is a hypothetical body that absorbs all the radiation falling on it)

Stefan discovered the law experimentally, but Boltzmann discovered it theoretically soon after.

LUDWIG BOLTZMANN

## BOLTZMANN CONSTANT

‘Heat at the molecular level’

Shortly after JAMES CLERK MAXWELL’s analysis of molecular motion, Ludwig Boltzmann gave a statistical interpretation of CLAUSIUS’s notion of entropy.

Boltzmann’s formula for entropy is

S = k logW

S  is entropy, k  is now known as Boltzmann’s constant and  W  is a measure of the number of states available to the system whose entropy is being measured.

The notion that heat flows from hot to cold could be phrased in terms of molecular motions. Molecules in a container collide with one another and the faster ones slow down while the slower ones speed up. Thus the hotter part becomes cooler and the colder part becomes hotter – thermal equilibrium is reached.

The Boltzmann constant is a physical constant relating energy at the individual particle level with temperature. It is the gas constant R  divided by the Avogadro constant NA :

k = R/NA

It has the same dimension (energy divided by temperature) as entropy.

(In rolling a dice, a seven may be obtained by throwing a six and a one, a five and a two or a four and a three, while three needs only a two and a one. Seven has greater ‘entropy’ – more states.)

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HEAT