EPICURUS (341 – 270 BCE)

Third Century BCE

“Epicurus’s philosophy combines a physics based on an atomistic materialism with a rational hedonistic ethics that emphasizes moderation of desires and cultivation of friendships.”

Summarized by the Roman author Lucretius, who wrote ‘On the Nature of the Universe’ in 55 BCE – “The light and heat of the Sun; these are composed of minute atoms which, when they are shoved off, lose no time in shooting right across the interspace of air in the direction imparted by the shove”. This may be considered as accurate for the time, when most people thought that sight was associated with something reaching out from the eye (EMPEDOCLES) .

Plato wrote of a marriage between the inner light and the outer light.

Euclid worried about the speed with which sight worked. He pointed out that if you close your eyes, then open them again, even the distant stars reappear immediately in your sight, although the influence of sight has had to travel all the way from your eyes to the stars and back again before you could see them.

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ALCHEMY

photo of an ancient document showing some of the symbols commonly used by alchemists

Alchemical symbols

Understanding of the alchemists is hampered by their predilection for making their writings incomprehensible ( instant knowledge was not to be available to the uninitiated ) and the popular view that their quest was simply to isolate the Philosophers’ Stone and to use it to transform base metals into gold. There was in fact a genuine search for mental and spiritual advance

Using a world-view totally unlike that recognised today, the alchemists’ ideas of ‘spirit’ and ‘matter’ were intermingled – the ability to use ‘spirit’ in their experiments was the difficult part.

alchemical symbol for gold

To transform copper to gold: – copper could be heated with sulphur to reduce it to its ‘basic form’ (a black mass which is in fact copper sulphide) – its ‘metallic form’ being ousted by the treatment. The idea of introducing the ‘form of gold’ to this mass by manipulating and mixing suitable quantities of spirit stymied alchemists for over fifteen centuries.

Whilst this transmutation of metals was the mainstream concern of alchemy, there emerged in the sixteenth century a school that brought the techniques and philosophies of alchemy to bear on the preparation of medicines, the main figures involved being PARACELSUS and JOHANN VAN HELMONT.

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cartoon of ALCHEMISTS AT WORK

ALCHEMISTS AT WORK

THE EIGHTEENTH CENTURY

COMBUSTION and PHLOGISTON

Noticing that burning a candle in an upturned container, the open end of which is submerged in water, causes the water to rise into the container, Philon of Byzantium inferred correctly that some of the air in the container had been used up in the combustion. However, he proposed that this is because this portion of the air had been converted into ‘fire particles’, which were smaller than ‘air particles’.

In 1700 the German physician Georg Ernst Stahl (1660-1734) invoked ‘phlogiston’ to explain what happens when things burn. He suggested that a burning substance was losing an undetectable elementary principle analogous to the ‘sulfur’ of J’BIR IHBIN AYAM, which he re-named ‘phlogiston’. This could explain why a log (rich in phlogiston) could seem to be heavier than its ashes (deficient in phlogiston). The air that is required for burning served to transport the phlogiston away.

The English chemist JOSEPH PRIESTLY (1733-1804), although a supporter of the phlogiston theory, ironically contributed to its downfall. He heated mercury in air to form red mercuric oxide and then applied concentrated heat to the oxide and noticed that it decomposed again to form mercury whilst giving off a strange gas in which things burnt brightly and vigorously. He concluded that this gas must be ‘phlogiston poor’.

Priestly combined this result with the work of the Scottish physician Daniel Rutherford (1749-1819), who had found that keeping a mouse in an enclosed airtight space resulted in its death (by suffocation) and that nothing could be burnt in the enclosed atmosphere; he formed the idea that the trapped air was so rich in phlogiston that it could accept no more. Rutherford called this ‘phlogisticated air’ and so Priestly called his own gas ‘dephlogisticated air’.

In 1774 Priestley visited the French chemist ANTOINE LAVOISIER (1743-1794).
Lavoisier repeated Priestly’s experiments with careful measurements.
Reasoning that air is made up of a combination of two gases – one that will support combustion and life, another that will not; what was important about Lavoisier’s experiments was not the observation – others had reached a similar conclusion – but the interpretation.

Lavoisier called Priestley’s ‘dephlogisticated air’, ‘oxygene’, meaning ‘acidifying principle’, believing at the time that the active principle was present in all acids (it is not). He called the remaining, ‘phlogisticated’, portion of normal air, ‘azote’, meaning ‘without life’

Oxygen is the mirror image of phlogiston. In burning and rusting (the two processes being essentially the same) a substance picks up one of the gases from the air. Oxygen is consumed, there is no expulsion of ‘phlogiston’.

Lavoisier had been left with almost pure nitrogen, which makes up about four fifths of the air we breath. We now know azote as nitrogen. Rutherford’s ‘mephitic air’ was carbon dioxide.

CALORIC

Like phlogiston, caloric was a weightless fluid, rather like elemental fire, a quality that could be transmitted from one substance to another, so that the first warmed the second up.

It was believed that all substances contained caloric and that when a kettle was being heated over a fire, the fuel gave up its caloric to the flame, which passed it into the metal, which passed it on to the water. Similarly, two pieces of wood rubbed together would give heat because abrasion was releasing caloric trapped within.

What is being transmitted is heat energy. It was the crucial distinction between the physical and the chemical nature of substances that confused the Ancients and led to their minimal elemental schemes.

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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.

Boyle 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.

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 work 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 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.

page from one of Boyle's publications“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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THOMAS NEWCOMEN (1663-1729)

1712 – England

‘Uses the property of condensing steam to create a partial vacuüm in a cylinder and therefore pull a piston. The system was highly inefficient but was used to pump water from mines’

Today, the credit for the steam engine is usually given to James Watt, while the name Thomas Newcomen remains shrouded in obscurity.

The design of his low-pressure steam engine involved heating water underneath a large piston that was encased in a cylinder.

Steam that was released as a result of the heating forced the piston upwards. A jet of water was then released from a tank above the piston. The sudden cooling of the steam made it condense, creating a partial vacuüm which atmospheric pressure then pushed down on, forcing the piston downwards again. The piston was attached to a two-headed lever, the other side of which was attached to a pump in the mineshaft. As it moved up and down, the lever moved likewise and a pumping motion was created in the shaft, which could be used to eject floodwater.

The first engine could remove about 120 gallons per minute, completing about twelve strokes in that time, and had the equivalent of about 5.5 horsepower. Even though the engine was still not particularly powerful, was hugely inefficient to run, and burnt huge amounts of coal, it would work reliably 24-hours a day.

The steam engine originally developed by Newcomen for work in the mines was quickly developed by engineers like JAMES WATT and RICHARD TREVITHICK (1771-1833) into the steam locomotive.

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JOSEPH BLACK (1728- 99)

1757 – Edinburgh

‘Different quantities of heat are required to bring equal weights of different materials to the same temperature’

This definition relates to the concept of specific heat.

Through meticulous experimentation and measurement of results he discovered the concept of ‘latent heat’, the ability of matter to absorb heat without necessarily changing in temperature.
True in the transformation of ice into water at 0degrees C, the same principle applies in the process of transforming water to steam and indeed, all solids to liquids and all liquids to gases.
Through this work Black made the important distinction between heat and temperature.

JAMES WATT benefited from these discoveries during his development of the condensing steam engine.

‘Fixed Air’

Black’s insistence on the importance of quantitative experiments was a step towards setting the standard for modern chemistry.

Black found that heating or treating carbonate salts with acid resulted in the release of a gas that, he reasoned, must have been ‘fixed’ in the solids. He outlined the cycle of chemical changes from limestone (calcium carbonate) to quicklime (calcium oxide) and ‘fixed air’ (carbon dioxide) when heated; quicklime mixed with water to become slaked lime (calcium hydroxide); which when combined with ‘fixed air’ becomes limestone again (turning the solution cloudy).

Although JAN BAPTISTA VAN HELMONT had identified the existence of separate, distinct gases in air over a century before, Black is still often credited with the discovery of carbon dioxide (fixed air) – despite that van Helmont had clearly been aware of its existence.

Black was able to prove that carbon dioxide is made by respiration, through fermentation and in the burning of charcoal, but that the gas would not allow a candle to burn in it nor sustain animal life.

Black’s student Daniel Rutherford (1749 – 1819) called the gas ‘mephitic air’ after the mephitis of legend, a noxious emanation said to cause pestilence, for animals died in an atmosphere of the new gas. Rutherford’s ‘air’ is not, however, the same as Lavoisier’s mephitic air, which is nitrogen (azote).

Observing the effect that removing carbon dioxide from limestone made the latter more alkaline, Black deduced that carbon dioxide is an acidic gas.

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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 MONTGOLFIER (1740-1810)

1783 – France

‘ Frenchmen Joseph-Michel Montgolfier and his brother Jacques-Etienne (1745-99) observed a simple natural phenomenon and realised the ‘unachievable’ ‘

Replica of the historic Montgolfier hot air balloon in flight. --- Image by © Skyscan/CORBIS ©

Replica of the historic Montgolfier hot air balloon in flight

Photograph of a statue depicting the MONTGOLFIER BROTHERS ©

MONTGOLFIER BROTHERS

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BENJAMIN THOMPSON (1753-1814) known as Count Rumford

1798 – England

‘Mechanical work can be converted into heat. Heat is the energy of motion of particles’

Heat is a form of energy associated with the random motion of atoms or molecules. Temperature is a measure of the hotness of an object.

In the eighteenth century, scientists imagined heat as a flow of a fluid substance called CALORIC. Each object contained a certain amount of caloric. If caloric flowed out, the object’s temperature decreased; if more caloric flowed into the object, its temperature increased.

Like PHLOGISTON, caloric was a weightless fluid, a quality that could be transmitted from one substance to another, so that the first warmed the second up. What is being transmitted is heat energy.

Working for the Elector of Bavaria, Rumford investigated the heat generated during the reaming out of the metal core when the bore of a cannon is formed. According to the caloric theory, the heat was released from the shards of metal during boring; Rumford noticed that if the tools were blunt and removed little or no metal, more heat was generated, rather than less.

Rumford postulated that the heat source had to be the work done in drilling the hole. Heat was not an indestructible caloric fluid, as LAVOISIER had argued, but something that could come and go. Mechanical energy could produce heat and heat could lead to mechanical energy.

One analogy he drew was to a bell; heat was like sound, with cold being similar to low notes and hot, to high ones. Temperature was therefore just the frequency of the bell. A hot object would emit ‘calorific rays’, whilst a cold one would emit ‘frigorific rays’ – an idea raised in Plutarch’s De Primo Frigido. Cold was an entity in itself, not simply the absence of heat.

Rumford thought there was no separate caloric fluid and that the heat content of an object was associated with motion or internal vibrations – motion which in the case of the cannon was bolstered by the friction of the tools. He had recognized the relationship between heat energy and the physicists’ concept of ‘work’ – the transfer of energy from a system into the surroundings, caused by the work done, results in a difference in temperature.
This transfer of energy measured as a temperature difference is called ‘heat’.

Half a century was to pass before in 1849, JAMES JOULE established the ‘mechanical equivalent of heat’ and JAMES CLERK MAXWELL launched the kinetic theory. According to Maxwell, the heat content of a body is equivalent to the sum of the individual energies of motion (kinetic energies) of its constituent atoms and molecules.

US born Rumford founded the Royal Institution in London and invented the calorimeter, a device measuring heat.

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NICOLAS SADI CARNOT (1796-1832)

1824 – France

‘The Carnot cycle is the most efficient cycle for operating a reversible heat engine’

It illustrates the principle that the efficiency of a heat engine depends on the temperature range through which it works.

The cycle has a four-stage reversible sequence:

adiabatic compression and isothermal expansion at high temperature; adiabatic expansion and isothermal compression at low temperature.

( ADIABATIC: – no heat flows into or out of a system; ISOTHERMAL: – at a constant temperature )

Carnot suggested that the puissance motrice (motive power, by which he meant work or energy) of a heat engine was derived from the fall of heat from a higher to a lower temperature.

Carnot was the first to grasp the principles that later became known as the second law of thermodynamics.

By the time of Carnot’s death it had become clear there was no such thing as a calorific fluid ; heat is a form of energy, one of many, and the sum of all forms of energy in an isolated system is conserved. This has come to be known as the first law of thermodynamics.

In the case of a steam engine, the heat taken in at the boiler is not equal to the heat removed at the condenser. The work done by the ideal engine is the difference between the two. The first modern experiment proving the first law of thermodynamics was performed by a student of John Dalton’s, JAMES JOULE.

 

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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 (1200 x 1600)

JAMES JOULE

The apparatus pictured was used by James Joule to demonstrate equivalence of mechanical work and heat. He calculated the work done by the pull of gravity on the weight. That pull turned the paddle wheels, which mixed the water in the insulated container. The water was warmed by the mixing, showing that heat = work

Calorimeter used by Joule in his 1876 determination of the mechanical equivalent of 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 -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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WILLIAM THOMSON (known as LORD KELVIN) (1824-1907)

1848 – Scotland

‘Molecular motion (or heat) approaches zero at temperatures approaching -273.15 degrees C’

Photo portrait of WILLIAM THOMSON (known as LORD KELVIN) ©

LORD KELVIN

This temperature is known as absolute zero. It is the theoretical lowest limit of temperature. Like the speed of light, absolute zero can be approached closely but cannot be reached; as to actually reach it an infinite amount of energy is required.

The temperature scale based on absolute zero is the kelvin scale (kelvin, symbol K without the degree sign). One kelvin degree equals one celsius degree.

The energy of a body at absolute zero is called ‘zero-point energy’. The twentieth century model states that atomic particles can exist only at certain energy levels; the lowest energy level is called the ground state and all higher levels are called excited states. At absolute zero all particles are in the ground state.

Thomson, together with JOULE, discovered the effect whereby most gases fall in temperature on expansion due to work taking place to pull apart the molecules. He independently enunciated and publicised the second law of thermodynamics describing the one-way spontaneous flow of heat – from a hotter body to a colder one. The German RUDOLPH CLAUSIUS also arrived at the same conclusion during the same period.

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RUDOLPH CLAUSIUS (1822- 88)

1850 – Germany

‘Heat does not flow spontaneously from a colder to a hotter body’

’The second law of thermodynamics’. The law says that many processes in nature are irreversible, never going backwards. It defines the direction of time (time cannot go backwards).

In 1857 Clausius wrote a paper entitled ‘The Kind of Motion We Call Heat’, relating average molecular motion to thermal quantities. Two years later, JAMES CLERK MAXWELL took up the problem using a statistical approach.

Clausius tried to understand why mechanical energy is in some sense a ‘higher’ form of energy than heat, and why it isn’t possible to change heat into mechanical energy with 100% efficiency, although the opposite is true.

He managed to link the degree of order and disorder in a system to the reversibility of a process.

ca. 1850s-1888 --- Original caption: Portrait of German mathematical physicist Rudolph Clausius (1822-1888), one of the founders of thermodynamics. Undated photograph. --- Image by © Bettmann/CORBIS ©

RUDOLPH CLAUSIUS

In 1865, Clausius used the term entropy as a measure of the disorder or randomness of a system. The more random and disordered a system is, the greater the entropy. The entropy of an irreversible system must increase; therefore, the entropy of the universe is increasing. A force acts to minimize the disequilibrium of energy and to maximize entropy, an object rolling down a hill can come to a stop by friction, but the heat generated through that friction cannot be used to bring the object back to the top.

  • First Law – The energy of the universe is constant

  • Second Law – The entropy of the universe tends to a maximum (overall disorder always increases)

  • The third law of thermodynamics, enunciated by Hermann Nernst (Nernst’s theorem) dictates that it is impossible to cool an object to a temperature of absolute zero ( -273.15 degrees Celsius ). Absolute zero temperature is a state of complete order.

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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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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’

portrait drawing of JOSEPH STEFAN ©

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.

photo portrait of LUDWIG BOLTZMANN &copy:

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.

Coloured graphic depicting distribution of heat energy according to boltzman's model

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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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 x 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 KIRCHOFF, 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 x 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 x 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.

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GEORGE GAMOW (1904- 68)

1948 – USA

‘The universe began when a single point of infinitely dense and infinitely hot matter exploded spontaneously. The debris of this explosion began to fly away from the explosion point and is still flying and will keep on flying indefinitely. All the galaxies, stars and planets were formed from this debris’

Portrait photograph of George Gamow

GEORGE GAMOW

In 1927 the Belgian astronomer Georges Lemaitre (1894-1966) suggested that at some time in the remote past all the matter in the universe was concentrated at one point. The universe began when this ‘primeval atom’ exploded. This idea was further developed by Gamow, who predicted that leftover warmth from this explosion would still fill the universe. The name Big Bang was given to this theory by Fred Hoyle, who believed in the opposing steady-state theory. It was meant to be a put-down when Hoyle first used it scornfully on a radio talk show in 1950.

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EPICURUS (341 – 270 BCE)

Third Century BCE

Bust of EPICURUS

EPICURUS

Summarized by the Roman author Lucretius, who wrote ‘On the Nature of the Universe’ in 55 BCE – “The light and heat of the sun; these are composed of minute atoms which, when they are shoved off, lose no time in shooting right across the interspace of air in the direction imparted by the shove”. Accurate for the time, when most people thought that sight was associated with something reaching out from the eye ( EMPEDOCLES ).

Plato wrote of a marriage between the inner light and the outer light.

Euclid worried about the speed with which sight worked. He pointed out that if you close your eyes, then open them again, even the distant stars reappear immediately in your sight, although the influence of sight has had to travel all the way from your eyes to the stars and back again before you could see them.

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