First Law of Thermodynamics

The first law of thermodynamics is a version of the law of conservation of energy, adapted for thermodynamic systems. The law of conservation of energy states that the total energy of an isolated system is constant; energy can be transformed from one form to another, but cannot be created or destroyed. The first law is often formulated by stating that the change in the internal energy of a closed system is equal to the amount of heat supplied to the system, minus the amount of work done by the system on its surroundings. Equivalently, perpetual motion machines of the first kind are impossible.

Investigations into the nature of heat and work and their relationship began with the invention of the first engines used to extract water from mines. Improvements to such engines so as to increase their efficiency and power output came first from mechanics that worked with such machines but only slowly advanced the art. Deeper investigations that placed those on a mathematical and physics basis came later.

The first law of thermodynamics was developed empirically over about half a century. The first full statements of the law came in 1850 from Rudolf Clausius and from William Rankine; Rankine's statement is less distinct relative to Clausius'. A main aspect of the struggle was to deal with the previously proposed caloric theory of heat.

In 1840, Germain Hess stated a conservation law for the so-called 'heat of reaction' for chemical reactions. His law was later recognized as a consequence of the first law of thermodynamics, but Hess's statement was not explicitly concerned with the relation between energy exchanges by heat and work.

According to Truesdell (1980), Julius Robert von Mayer in 1841 made a statement that meant that "in a process at constant pressure, the heat used to produce expansion is universally interconvertible with work", but this is not a general statement of the first law.

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