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.

JAMES PRESCOTT JOULE

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).

Manchester Museum of Science & Industry

TIMELINE

HEAT

LUIGI GALVANI (1737- 98) ALESSANDRO VOLTA (1745-1827)

1791 & 1799 – Italy

‘Galvani: An electric current is produced when an animal tissue comes into contact with two different metals.

Volta: An electric current is not dependent on an animal tissue and can be produced by chemicals’

Galvani was wrong and Volta was right.

Galvani had found that by touching a dead frog’s legs with two different metal implements, the muscles in the frog’s legs would twitch. Galvani wrongly concluded it was the animal tissue that was storing the electricity, releasing it when touched by the metals. He felt he had discovered the very force of life – ‘animal electricity’ – that animated flesh and bone.

GALVANI

Soon dozens of scientists were trying to bring corpses back to life by electrifying them. Volta was not convinced the animal muscle was the important factor in the production of the current.

He repeated Galvani’s experiments and concluded, controversially at the time, the different metals were the important factor.

A bitter dispute arose as to whose interpretation was correct. Volta began putting together different combinations of metals to see if they produced any current; later he produced a wet battery of fluid and metals. Volta’s method of producing electric current involved using discs of silver and zinc dipped in a bowl of salt solution. He reasoned that a much larger charge could be produced by stacking several discs separated by cards soaked in salt water – by attaching copper wires to each end of the ‘pile’ he successfully obtained a steady current.

The ‘voltaic pile’ was the first battery in history (1800). Napoleon Bonaparte, who at the time controlled the territory in which Volta lived, was so impressed he made him a Count and awarded him the Legion d’Honour.

VOLTA

Volt, the SI unit of electric potential, honours Volta.

Although Galvani’s theory on ‘animal electricity’ was not of any major importance, he has also achieved nominal immortality; like ‘volt’, the words ‘galvanic’ (sudden and dramatic), ‘galvanised’ (iron or steel coated with zinc) and ‘galvanometer’ (an instrument for detecting small currents) have become part of everyday language.

A volt is defined as the potential difference between two points on a conductor carrying one ampere current when the power dissipated between the points is one watt.

ANDRE MARIE AMPERE (1775-1836)

1827 – France

‘Two current-carrying wires attract each other if their currents are in the same direction, but repel each other if their currents are opposite.
The force of attraction or repulsion (magnetic force) is directly proportional to the product of the strengths of the currents and inversely proportional to the square of the distance between them’

ANDRE AMPERE

Another addition to the succession of ‘inverse-square’ laws begun with NEWTON’s law of universal gravitation.
Ampere had noted that two magnets could affect each other and wondered, given the similarities between electricity and magnetism, what effect two currents would have upon each other. Beginning with electricity run in two parallel wires, he observed that if the currents ran in the same direction, the wires were attracted to each other and if they ran in opposite directions they were repelled.

He experimented with other shapes of wires and generalised that the magnetic effect produced by passing a current in an electric wire is the result of the circular motion of that current. The effect is increased when the wire is coiled. When a bar of soft iron is placed in the coil it becomes a magnet. This is the solenoid, used in devices where mechanical motion is required.

Ampere exploited OERSTED’s work, devising a galvanometer which measured electric current flow via the degree of deflection upon its magnetic needle.

He attempted to interpret all his results mathematically in a bid to find an encompassing explanation for what later became referred to as electromagnetism (Ampere had at that time christened it electrodynamics), resulting in his 1827 definition.

Ampere’s name is commemorated in the SI unit of electric current, the ampere.

TIMELINE

ELECTRICITY

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.

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.

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 NUMBER

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.

TIMELINE

CHEMISTRY