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.

photo portrait of MAX PLANCK ©

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).’

photo portrait of MAX PLANCK ©

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.

picture of the Nobel medal - link to nobelprize.org
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JAMES CLERK MAXWELL (1831- 79)

1864 Scotland

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.

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

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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JAMES PRESCOTT JOULE (1818- 89)

1843 – England

‘A given amount of work produces a specific amount of heat’

4.18 joules of work is equivalent to one calorie of heat.

In 1798 COUNT RUMFORD suggested that mechanical work could be converted into heat. This idea was pursued by Joule who conducted thousands of experiments to determine how much heat could be obtained from a given amount of work.

Even in the nineteenth century, scientists did not fully understand the properties of heat. The common belief held that it was some form of transient fluid – retained and released by matter – called CALORIC. Gradually, the idea that it was another form of energy, expressed as the movement of molecules gained ground.
Heat is now regarded as a mode of transfer of energy – the transfer of energy by virtue of a temperature difference. Heat is the name of a process, not that of an entity.

Joule began his experiments by examining the relationship between electric current and resistance in the wire through which it passed, in terms of the amount of heat given off. This led to the formulation of Joule’s ideas in the 1840s, which mathematically determined the link.

Joule is remembered for his description of the conversion of electrical energy into heat; which states that the heat (Q) produced when an electric current (I) flows through a resistance (R) for a time (t) is given by Q=I2Rt

Its importance was that it undermined the concept of ‘caloric’ as it effectively determined that one form of energy was transforming itself into another – electrical energy to heat energy. Joule proved that heat could be produced from many different types of energy, including mechanical energy.

john collier portrait of james prescott joule

JAMES PRESCOTT JOULE

Joule's apparatus to show equivalence of work and heat

Joule’s apparatus to show equivalence of work and heat

Joule was the son of a brewer and all his experiments on the mechanical equivalent of heat depended upon his ability to measure extremely slight increases in temperature, using the sensitive thermometers available to him at the brewery. He formulated a value for the work required to produce a unit of heat. Performing an improved version of Count Rumford’s experiment, he used weights on a pulley to turn a paddle wheel immersed in water. The friction between the water and the paddle wheel caused the temperature of the water to rise slightly. The amount of work could be measured from the weights and the distance they fell, the heat produced could be measured by the rise in temperature.

Joule went on to study the role of heat and movement in gases and subsequently with WILLIAM THOMSON, who later became Lord Kelvin, described what became known as the ‘Joule-Thomson effect’ (1852-9). This demonstrated how most gases lose temperature on expansion due to work being done in pulling the molecules apart.

Thomson thought, as CARNOT had, that heat IN equals heat OUT during a steam engine’s cycle. Joule convinced him he was wrong.

The essential correctness of Carnot’s insight is that the work performed in a cycle divided by heat input depends only on the temperature of the source and that of the sink.

Synthesising Joule’s results with Carnot’s ideas, it became clear that a generic steam engine’s efficiency – work output divided by heat input – differed from one (100%) by an amount that could be expressed either as heat OUT at the sink divided by heat IN at the source, or alternatively as temperature of the sink divided by temperature of the source. Carnot’s insight that the efficiency of the engine depends on the temperature difference was correct. Temperature has to be measured using the right scale. The correct one had been hinted at by DALTON and GAY-LUSSAC’s experiments, in which true zero was minus 273degrees Celsius.

A perfect cyclical heat engine with a source at 100degrees Celsius and a sink at 7degrees has an efficiency of 1 – 280/373. The only way for the efficiency to equal 100% – for the machine to be a perfect transformer of heat into mechanical energy – is for the sink to be at absolute zero temperature.

Joule’s work helped in determining the first law of thermodynamics; the principle of the conservation of energy. This was a natural extension of his work on the ability of energy to transform from one type to another.

Joule contended that the natural world has a fixed amount of energy which is never added to nor destroyed, but which just changes form.

The SI unit of work and energy is named the joule (J).

link to James Joule - Manchester Museum of Science & Industry

Manchester Museum of Science & Industry

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Energy House research leads to new skills for industry | University of Salford Manchester

Energy House research leads to new skills for industry | University of Salford Manchester.

JAMES WATT (1736-1819)

1765 – Glasgow, Lanarkshire, UK

‘Steam engine’

Watt’s steam engine was the driving force behind the industrial revolution and his development of the rotary engine in 1781 brought mechanisation to several industries such as weaving, spinning and transportation.

Portrait of JAMES WATT who developed the steam engine ©

JAMES WATT

Although THOMAS NEWCOMEN had developed the steam engine before Watt was even born, Newcomen’s machines had been confined to the world of mining.

In 1764, when Watt was asked to repair a scale model of Newcomen’s engine he noted its huge inefficiency. The heating and cooling of the cylinder with every stroke wasted huge amounts of fuel; and wasted time in bringing the cylinder back up to steam producing temperature, which limited the frequency of strokes. He realised that the key to improved efficiency lay in condensing the steam in a separate container – thereby allowing the cylinder and piston to remain always hot. Watt continued to improve his steam engine and developed a way to make it work with a circular, rotary motion. Another of his improvements was the production of steam under pressure, thus increasing the temperature gap between source and sink and raising the efficiency in a manner later described by SADI CARNOT and elucidated by JAMES JOULE.

Richard_Arkwright_by_Mather_Brown_1790

RICHARD ARKWRIGHT

RICHARD ARKWRIGHT was the first to realise the engine could be used to spin cotton, and later in weaving. Flour and paper mills were other early adopters, and in 1788 steam power was used to paddle marine transportation. In the same year, Watt developed the ‘centrifugal governor’ to regulate the speed of the engine and to keep it constant.

diagram of the Watt 10hp engine

Watt 10hp engine

Watt was the first to coin the term ‘horsepower’, which he used when comparing how many horses it would require to provide the same pull as one of his machines. In 1882 the British Association named the ‘watt’ unit of power in his honour.

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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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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 NUMBERAvogadro'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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