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.

GUSTAV KIRCHHOFF (1824- 87)

1845 – Germany

‘First law (Junction law): At any junction point in an electrical circuit, the sum of all currents entering the junction must equal the sum of all currents leaving the junction’

‘Second law (Loop law): For any closed loop in an electrical circuit, the sum of the voltages must add up to zero’

In equation form the first law is I = I1 + I2 + I3 + I4 +…. where I is the total current and I1, I2, I3 etc. are the separate currents.

Second law is V = V1 + V2 + V3 + … where V is the total voltage and V1, V2, V3 etc. are the separate voltages.

photo portrait of GUSTAV KIRCHHOFF ©

GUSTAV KIRCHHOFF

These laws are an extension of OHM‘s law and are used for calculating current and voltage in a network of circuits. Kirchhoff formulated these laws when he was a student at the University of Konisburg.

Kirchhoff also showed that objects that are good emitters of heat are also good absorbers. This is Kirchhoff’s law of radiation.

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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 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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JACQUES-ALEXANDRE-CESARE CHARLES (1746-1823)

1787 – France

‘The volume of a given mass of gas at constant pressure is directly proportional to its absolute temperature’

In other words, if you double the temperature of a gas, you double its volume. In equation form:  V/T = constant, or  V1/T1 = V2/T2,  where  V1 is the volume of the gas at a temperature  T1 (in kelvin) and  V2 the new volume at a new temperature  T2.

This principle is now known as Charles’ Law (although sometimes named after GAY-LUSSAC because of his popularisation of it fifteen years later – Gay Lussac’s experimental proof was more accurate than Charles’).
It completed the two ‘gas laws’.

A fixed amount of any gas expands equally at the same increments in temperature, as long as it is at constant pressure.

Likewise for a decline in temperature, all gases reduce in volume at a common rate, to the point at about -273degrees C, where they would theoretically converge to zero volume. It is for this reason that the kelvin temperature scale later fixed its zero degree value at this point.

CHARLES’ Law and BOYLE‘s Law may be expressed as a single equation, pV/T = constant. If we also include AVOGADRO‘s law, the relationship becomes pV/nT = constant, where n is the number of molecules or number of moles.

The constant in this equation is called the gas constant and is shown by R
The equation – known as the ideal gas equation – is usually written as pV = nRT

Strictly, it applies to ideal gases only. An ideal gas obeys all the assumptions of the kinetic theory of gases. There are no ideal gases in nature, but under certain conditions all real gases approach ideal behaviour.

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Poster describing the combined Gas Laws

Combined Gas Laws