Thermodynamic work is one of the principal kinds of process by which a thermodynamic system can interact with and transfer energy to its surroundings. This results in externally measurable macroscopic forces on the system's surroundings, which can cause mechanical work, for example to lift a weight,Kittel, C. Kroemer, H. (1980). Thermal Physics, second edition, W.H. Freeman, San Francisco, North, G.R., Erukhimova, T.L. (2009). Atmospheric Thermodynamics. Elementary Physics and Chemistry, Cambridge University Press, Cambridge (UK), . or cause changes in external electromagnetic quantities.Guggenheim, E.A. (1985). Thermodynamics. An Advanced Treatment for Chemists and Physicists, seventh edition, North Holland, Amsterdam, .Jackson, J.D. (1975). Classical Electrodynamics, second edition, John Wiley and Sons, New York, .Konopinski, E.J. (1981). Electromagnetic Fields and Relativistic Particles, McGraw-Hill, New York, . Also, the surroundings can perform thermodynamic work on a thermodynamic system, which is measured by an opposite sign.
For thermodynamic work, appropriately chosen externally measured quantities are exactly matched by values of or contributions to changes in macroscopic internal state variables of the system, which always occur in conjugate pairs, for example pressure and volume or magnetic flux density and magnetization.
In the International System of Units (SI), work is measured in joules (symbol J). The rate at which work is performed is power, measured in joules per second, and denoted with the unit watt (W).
History 1824 - Carnot Work, i.e. "weight lifted through a height", was originally defined in 1824 by Sadi Carnot in his famous paper Reflections on the Motive Power of Fire, where he used the term motive power for work. Specifically, according to Carnot: We use here motive power to express the useful effect that a motor is capable of producing. This effect can always be likened to the elevation of a weight to a certain height. It has, as we know, as a measure, the product of the weight multiplied by the height to which it is raised.
1845 - Joule
In 1845, the English physicist James Joule wrote a paper On the mechanical equivalent of heat for the British Association meeting in Cambridge.Joule, J.P. (1845) "On the Mechanical Equivalent of Heat", Brit. Assoc. Rep., trans. Chemical Sect, p.31, which was read before the British Association at Cambridge, June In this paper, he reported his best-known experiment, in which the mechanical power released through the action of a "weight falling through a height" was used to turn a paddle-wheel in an insulated barrel of water.
In this experiment, the motion of the paddle wheel, through agitation and friction, heated the body of water, so as to increase its temperature. Both the temperature change of the water and the height of the fall of the weight were recorded. Using these values, Joule was able to determine the mechanical equivalent of heat. Joule estimated a mechanical equivalent of heat to be 819 ft•lbf/Btu (4.41 J/cal). The modern day definitions of heat, work, temperature, and energy all have connection to this experiment. In this arrangement of apparatus, it never happens that the process runs in reverse, with the water driving the paddles so as to raise the weight, not even slightly. Mechanical work was done by the apparatus of falling weight, pulley, and paddles, which lay in the surroundings of the water. Their motion scarcely affected the volume of the water. A quantity of mechanical work, measured as force × distance in the surroundings, that does not change the volume of the water, is said to be isochoric. Such work reaches the system only as friction, through microscopic modes, and is irreversible. It does not count as thermodynamic work. The energy supplied by the fall of the weight passed into the water as irreversible heat.
1850-1865 - Clausius The idealized notions of reversible work and heat are developed in scientific articles by Rudolf Clausius from 1850 - 1865. The reversible heat, defined by Clausius, is not based on calorimetry, an irreversible technique.
Overview Conservation of energy A fundamental guiding principle of thermodynamics is the conservation of energy. The total energy of a system is the sum of its internal energy, of its potential energy as a whole system in an external force field, such as gravity, and of its kinetic energy as a whole system in motion. Thermodynamics has special concern with transfers of energy, from a body of matter, such as, for example a cylinder of steam, to the surroundings of the body, by mechanisms through which the body exerts macroscopic forces on its surroundings so as to lift a weight there; such mechanisms are the ones that are said to mediate thermodynamic work.
Besides transfer of energy as work, thermodynamics admits transfer of energy as heat. For a process in a closed (no transfer of matter) thermodynamic system, the first law of thermodynamics relates changes in the internal energy (or other cardinal energy function, depending on the conditions of the transfer) of the system to those two modes of energy transfer, as work, and as heat. Adiabatic work is done without matter transfer and without heat transfer. In principle, in thermodynamics, for a process in a closed system, the quantity of heat transferred is defined by the amount of adiabatic work that would be needed to effect the change in the system that is occasioned by the heat transfer. In experimental practice, heat transfer is often estimated calorimetrically, through change of temperature of a known quantity of calorimetric material substance.
Energy can also be transferred to or from a system through transfer of matter. The possibility of such transfer defines the system as an open system, as opposed to a closed system. By definition, such transfer is neither as work nor as heat.
Changes in the potential energy of a body as a whole with respect to forces in its surroundings, and in the kinetic energy of the body moving as a whole with respect to its surroundings, are by definition excluded from the body's cardinal energy (examples are internal energy and enthalpy).
Nearly reversible transfer of energy by work in the surroundings In the surroundings of a thermodynamic system, external to it, all the various mechanical and non-mechanical macroscopic forms of work can be converted into each other with no limitation in principle due to the laws of thermodynamics, so that the energy conversion efficiency can approach 100% in some cases; such conversion is required to be frictionless, and consequently adiabatic.F.C.Andrews Thermodynamics: Principles and Applications (Wiley-Interscience 1971), , p.17-18. In particular, in principle, all macroscopic forms of work can be converted into the mechanical work of lifting a weight, which was the original form of thermodynamic work considered by Carnot and Joule (see History section above). Some authors have considered this equivalence to the lifting of a weight as a defining characteristic of work.Silbey, R.J., Alberty, R.A., Bawendi, M.G. (2005). Physical Chemistry, 4th edition, Wiley, Hoboken NJ., , p.31K.Denbigh The Principles of Chemical Equilibrium (Cambridge University Press 1st ed. 1955, reprinted 1964), p.14.J.Kestin A Course in Thermodynamics (Blaisdell Publishing 1966), p.121.M.A.Saad Thermodynamics for Engineers (Prentice-Hall 1966) p.45-46. For example, with the apparatus of Joule's experiment in which, through pulleys, a weight descending in the surroundings drives the stirring of a thermodynamic system, the descent of the weight can be diverted by a re-arrangement of pulleys, so that it lifts another weight in the surroundings, instead of stirring the thermodynamic system.
Such conversion may be idealized as nearly frictionless, though it occurs relatively quickly. It usually comes about through devices that are not simple thermodynamic systems (a simple thermodynamic system is a homogeneous body of material substances). For example, the descent of the weight in Joule's stirring experiment reduces the weight's total energy. It is described as loss of gravitational potential energy by the weight, due to change of its macroscopic position in the gravity field, in contrast to, for example, loss of the weight's internal energy due to changes in its entropy, volume, and chemical composition. Though it occurs relatively rapidly, because the energy remains nearly fully available as work in one way or another, such diversion of work in the surroundings may be idealized as nearly reversible, or nearly perfectly efficient.
In contrast, the conversion of heat into work in a heat engine can never exceed the Carnot efficiency, as a consequence of the second law of thermodynamics. Such energy conversion, through work done relatively rapidly, in a practical heat engine, by a thermodynamic system on its surroundings, cannot be idealized, not even nearly, as reversible.
Thermodynamic work done by a thermodynamic system on its surroundings is defined so as to comply with this principle. Historically, thermodynamics was about how a thermodynamic system could do work on its surroundings.
Work done by and on a simple thermodynamic system Thermodynamic work and ordinary mechanical work are to be distinguished. Thermodynamic work is defined by the changes of the thermodynamic system's own internal state variables, such as volume, electric polarization, and magnetization, but excluding temperature and entropy.Adkins, C.J. (1968/1983). Equilibrium Thermodynamics, (1st edition 1968), third edition 1983, Cambridge University Press, Cambridge UK, , pp. 39–42.Callen, H. B. (1960/1985), Thermodynamics and an Introduction to Thermostatistics, (first edition 1960), second edition 1985, John Wiley & Sons, New York, , pp. 82, 479–483.Jackson, J.D. (1999), Classical Electromagnetism, third edition, John Wiley & Sons, Hoboken NJ, , pp. 165–169, 212–215. Ordinary mechanical work includes work done by compression, as well as shaft work, stirring, and rubbing; but shaft work, stirring, and rubbing are not thermodynamic work in so far as they do not change the volume of the system, though they change the temperature or entropy of the system. Work without change of volume is known as isochoric work, for example when friction acts on the surface or in the interior of the system.
In a process of transfer of energy from or to a thermodynamic system, the change of internal energy of the system is defined in theory by the amount of adiabatic work that would have been necessary to reach the final from the initial state, such adiabatic work being measurable only through the externally measurable mechanical or deformation variables of the system, that provide full information about the forces exerted by the surroundings on the system during the process. In the case of some of Joule's measurements, the process was so arranged that some heating that occurred outside the system (in the substance of the paddles) by the frictional process also led to heat transfer from the paddles into the system during the process, so that the quantity of work done by the surrounds on the system could be calculated as shaft work, an external mechanical variable.Buchdahl, H.A. (1966). The Concepts of Classical Thermodynamics, Cambridge University Press, London, p. 40.Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York, , pp. 35–36.