- (used with a sing. verb) Physics that deals with the relationships and conversions between heat and other forms of energy.
- (used with a pl. verb) Thermodynamic phenomena and processes.
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Results for thermodynamics
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Concept
Thermodynamics is the study of the relationships between heat, work, and energy. Though rooted in physics, it has a clear application to chemistry, biology, and other sciences: in a sense, physical life itself can be described as a continual thermodynamic cycle of transformations between heat and energy. But these transformations are never perfectly efficient, as the second law of thermodynamics shows. Nor is it possible to get "something for nothing," as the first law of thermodynamics demonstrates: the work output of a system can never be greater than the net energy input. These laws disappointed hopeful industrialists of the early nineteenth century, many of whom believed it might be possible to create a perpetual motion machine. Yet the laws of thermodynamics did make possible such highly useful creations as the internal combustion engine and the refrigerator.
How It Works
Historical Context
Machines were, by definition, the focal point of the Industrial Revolution, which began in England during the late eighteenth and early nineteenth centuries. One of the central preoccupations of both scientists and industrialists thus became the efficiency of those machines: the ratio of output to input. The more output that could be produced with a given input, the greater the production, and the greater the economic advantage to the industrialists and (presumably) society as a whole.
At that time, scientists and captains of industry still believed in the possibility of a perpetual motion machine: a device that, upon receiving an initial input of energy, would continue to operate indefinitely without further input. As it emerged that work could be converted into heat, a form of energy, it began to seem possible that heat could be converted directly back into work, thus making possible the operation of a perfectly reversible perpetual motion machine. Unfortunately, the laws of thermodynamics dashed all those dreams.
Snow's Explanation
Some texts identify two laws of thermodynamics, while others add a third. For these laws, which will be discussed in detail below, British writer and scientist C. P. Snow (1905-1980) offered a witty, nontechnical explanation. In a 1959 lecture published as The Two Cultures and the Scientific Revolution, Snow compared the effort to transform heat into energy, and energy back into heat again, as a sort of game.
The first law of thermodynamics, in Snow's version, teaches that the game is impossible to win. Because energy is conserved, and thus, its quantities throughout the universe are always the same, one cannot get "something for nothing" by extracting more energy than one put into a machine.
The second law, as Snow explained it, offers an even more gloomy prognosis: not only is it impossible to win in the game of energy-work exchanges, one cannot so much as break even. Though energy is conserved, that does not mean the energy is conserved within the machine where it is used: mechanical systems tend toward increasing disorder, and therefore, it is impossible for the machine even to return to the original level of energy.
The third law, discovered in 1905, seems to offer a possibility of escape from the conditions imposed in the second law: at the temperature of absolute zero, this tendency toward breakdown drops to a level of zero as well. But the third law only proves that absolute zero cannot be attained: hence, Snow's third observation, that it is impossible to step outside the boundaries of this unwinnable heat-energy transformation game.
Work and Energy
Work and energy, discussed at length elsewhere in this volume, are closely related. Work is the exertion of force over a given distance to displace or move an object. It is thus the product of force and distance exerted in the same direction. Energy is the ability to accomplish work.
There are many manifestations of energy, including one of principal concern in the present context: thermal or heat energy. Other manifestations include electromagnetic (sometimes divided into electrical and magnetic), sound, chemical, and nuclear energy. All these, however, can be described in terms of mechanical energy, which is the sum of potential energy—the energy that an object has due to its position—and kinetic energy, or the energy an object possesses by virtue of its motion.
Mechanical Energy
Kinetic energy relates to heat more clearly than does potential energy, discussed below; however, it is hard to discuss the one without the other. To use a simple example—one involving mechanical energy in a gravitational field—when a stone is held over the edge of a cliff, it has potential energy. Its potential energy is equal to its weight (mass times the acceleration due to gravity) multiplied by its height above the bottom of the canyon below. Once it is dropped, it acquires kinetic energy, which is the same as one-half its mass multiplied by the square of its velocity.
Just before it hits bottom, the stone's kinetic energy will be at a maximum, and its potential energy will be at a minimum. At no point can the value of its kinetic energy exceed the value of the potential energy it possessed before it fell: the mechanical energy, or the sum of kinetic and potential energy, will always be the same, though the relative values of kinetic and potential energy may change.
Conservation of Energy
What mechanical energy does the stone possess after it comes to rest at the bottom of the canyon? In terms of the system of the stone dropping from the cliffside to the bottom, none. Or, to put it another way, the stone has just as much mechanical energy as it did at the very beginning. Before it was picked up and held over the side of the cliff, thus giving it potential energy, it was presumably sitting on the ground away from the edge of the cliff. Therefore, it lacked potential energy, inasmuch as it could not be "dropped" from the ground.
If the stone's mechanical energy—at least in relation to the system of height between the cliff and the bottom—has dropped to zero, where did it go? A number of places. When it hit, the stone transferred energy to the ground, manifested as heat. It also made a sound when it landed, and this also used up some of its energy. The stone itself lost energy, but the total energy in the universe was unaffected: the energy simply left the stone and went to other places. This is an example of the conservation of energy, which is closely tied to the first law of thermodynamics.
But does the stone possess any energy at the bottom of the canyon? Absolutely. For one thing, its mass gives it an energy, known as mass or rest energy, that dwarfs the mechanical energy in the system of the stone dropping off the cliff. (Mass energy is the other major form of energy, aside from kinetic and potential, but at speeds well below that of light, it is released in quantities that are virtually negligible.) The stone may have electromagnetic potential energy as well; and of course, if someone picks it up again, it will have gravitational potential energy. Most important to the present discussion, however, is its internal kinetic energy, the result of vibration among the molecules inside the stone.
Heat and Temperature
Thermal energy, or the energy of heat, is really a form of kinetic energy between particles at the atomic or molecular level: the greater the movement of these particles, the greater the thermal energy. Heat itself is internal thermal energy that flows from one body of matter to another. It is not the same as the energy contained in a system—that is, the internal thermal energy of the system. Rather than being "energy-in-residence," heat is "energy-in-transit."
This may be a little hard to comprehend, but it can be explained in terms of the stone-and-cliff kinetic energy illustration used above. Just as a system can have no kinetic energy unless something is moving within it, heat exists only when energy is being transferred. In the above illustration of mechanical energy, when the stone was sitting on the ground at the top of the cliff, it was analogous to a particle of internal energy in body A. When, at the end, it was again on the ground—only this time at the bottom of the canyon—it was the same as a particle of internal energy that has transferred to body B. In between, however, as it was falling from one to the other, it was equivalent to a unit of heat.
Temperature
In everyday life, people think they know what temperature is: a measure of heat and cold. This is wrong for two reasons: first, as discussed below, there is no such thing as "cold"—only an absence of heat. So, then, is temperature a measure of heat? Wrong again.
Imagine two objects, one of mass M and the other with a mass twice as great, or 2 M. Both have a certain temperature, and the question is, how much heat will be required to raise their temperature by equal amounts? The answer is that the object of mass 2 M requires twice as much heat to raise its temperature the same amount. Therefore, temperature cannot possibly be a measure of heat.
What temperature does indicate is the direction of internal energy flow between bodies, and the average molecular kinetic energy in transit between those bodies. More simply, though a bit less precisely, it can be defined as a measure of heat differences. (As for the means by which a thermometer indicates temperature, that is beyond the parameters of the subject at hand; it is discussed elsewhere in this volume, in the context of thermal expansion.)
Measuring Temperature and Heat
Temperature, of course, can be measured either by the Fahrenheit or Centigrade scales familiar in everyday life. Another temperature scale of relevance to the present discussion is the Kelvin scale, established by William Thomson, Lord Kelvin (1824-1907).
Drawing on the discovery made by French physicist and chemist J. A. C. Charles (1746-1823), that gas at 0°C (32°F) regularly contracts by about 1/273 of its volume for every Celsius degree drop in temperature, Thomson derived the value of absolute zero (discussed below) as −273.15°C (−459.67°F). The Kelvin and Celsius scales are thus directly related: Celsius temperatures can be converted to Kelvins (for which neither the word nor the symbol for "degree" are used) by adding 273.15.
Measuring Heat and Heat Capacity
Heat, on the other hand, is measured not by degrees (discussed along with the thermometer in the context of thermal expansion), but by the same units as work. Since energy is the ability to perform work, heat or work units are also units of energy. The principal unit of energy in the SI or metric system is the joule (J), equal to 1 newton-meter (N · m), and the primary unit in the British or English system is the foot-pound (ft · lb). One foot-pound is equal to 1.356 J, and 1 joule is equal to 0.7376 ft · lb.
Two other units are frequently used for heat as well. In the British system, there is the Btu, or British thermal unit, equal to 778 ft · lb. or 1,054 J. Btus are often used in reference, for instance, to the capacity of an air conditioner. An SI unit that is also used in the United States—where British measures typically still prevail—is the kilocalorie. This is equal to the heat that must be added to or removed from 1 kilogram of water to change its temperature by 1°C. As its name suggests, a kilocalorie is 1,000 calories. A calorie is the heat required to change the temperature in 1 gram of water by 1°C—but the dietary Calorie (capital C), with which most people are familiar is the same as the kilocalorie.
A kilocalorie is identical to the heat capacity for one kilogram of water. Heat capacity (sometimes called specific heat capacity or specific heat) is the amount of heat that must be added to, or removed from, a unit of mass for a given substance to change its temperature by 1°C. this is measured in units of J/kg · °C (joules per kilogram-degree Centigrade), though for the sake of convenience it is typically rendered in terms of kilojoules (1,000 joules): kJ/kg · °c. Expressed thus, the specific heat of water 4.185—which is fitting, since a kilocalorie is equal to 4.185 kJ. Water is unique in many aspects, with regard to specific heat, in that it requires far more heat to raise the temperature of water than that of mercury or iron.
Real-Life Applications
Hot and "cold"
Earlier, it was stated that there is no such thing as "cold"—a statement hard to believe for someone who happens to be in Buffalo, New York, or International Falls, Minnesota, during a February blizzard. Certainly, cold is real as a sensory experience, but in physical terms, cold is not a "thing"—it is simply the absence of heat.
People will say, for instance, that they put an ice cube in a cup of coffee to cool it, but in terms of physics, this description is backward: what actually happens is that heat flows from the coffee to the ice, thus raising its temperature. The resulting temperature is somewhere between that of the ice cube and the coffee, but one cannot obtain the value simply by averaging the two temperatures at the beginning of the transfer.
For one thing, the volume of the water in the ice cube is presumably less than that of the water in the coffee, not to mention the fact that their differing chemical properties may have some minor effect on the interaction. Most important, however, is the fact that the coffee did not simply merge with the ice: in transferring heat to the ice cube, the molecules in the coffee expended some of their internal kinetic energy, losing further heat in the process.
Cooling Machines
Even cooling machines, such as refrigerators and air conditioners, actually use heat, simply reversing the usual process by which particles are heated. The refrigerator pulls heat from its inner compartment—the area where food and other perishables are stored—and transfers it to the region outside. This is why the back of a refrigerator is warm.
Inside the refrigerator is an evaporator, into which heat from the refrigerated compartment flows. The evaporator contains a refrigerant—a gas, such as ammonia or Freon 12, that readily liquifies. This gas is released into a pipe from the evaporator at a low pressure, and as a result, it evaporates, a process that cools it. The pipe takes the refrigerant to the compressor, which pumps it into the condenser at a high pressure. Located at the back of the refrigerator, the condenser is a long series of pipes in which pressure turns the gas into liquid. As it moves through the condenser, the gas heats, and this heat is released into the air around the refrigerator.
An air conditioner works in a similar manner. Hot air from the room flows into the evaporator, and a compressor circulates refrigerant from the evaporator to a condenser. Behind the evaporator is a fan, which draws in hot air from the room, and another fan pushes heat from the condenser to the outside. As with a refrigerator, the back of an air conditioner is hot because it is moving heat from the area to be cooled.
Thus, cooling machines do not defy the principles of heat discussed above; nor do they defy the laws of thermodynamics that will be discussed at the conclusion of this essay. In accordance with the second law, in order to move heat in the reverse of its usual direction, external energy is required. Thus, a refrigerator takes in energy from a electric power supply (that is, the outlet it is plugged into), and extracts heat. Nonetheless, it manages to do so efficiently, removing two or three times as much heat from its inner compartment as the amount of energy required to run the refrigerator.
Transfers of Heat
It is appropriate now to discuss how heat is transferred. One must remember, again, that in order for heat to be transferred from one point to another, there must be a difference of temperature between those two points. If an object or system has a uniform level of internal thermal energy—no matter how "hot" it may be in ordinary terms—no heat transfer is taking place.
Heat is transferred by one of three methods: conduction, which involves successive molecular collisions; convection, which requires the motion of hot fluid from one place to another; or radiation, which involves electromagnetic waves and requires no physical medium for the transfer.
Conduction
Conduction takes place best in solids and particularly in metals, whose molecules are packed in relatively close proximity. Thus, when one end of an iron rod is heated, eventually the other end will acquire heat due to conduction. Molecules of liquid or nonmetallic solids vary in their ability to conduct heat, but gas—due to the loose attractions between its molecules—is a poor conductor.
When conduction takes place, it is as though a long line of people are standing shoulder to shoulder, passing a secret down the line. In this case, however, the "secret" is kinetic thermal energy. And just as the original phrasing of the secret will almost inevitably become garbled by the time it gets to the tenth or hundredth person, some energy is lost in the transfer from molecule to molecule. Thus, if one end of the iron rod is sitting in a fire and one end is surrounded by air at room temperature, it is unlikely that the end in the air will ever get as hot as the end in the fire.
Incidentally, the qualities that make metallic solids good conductors of heat also make them good conductors of electricity. In the first instance, kinetic energy is being passed from molecule to molecule, whereas in an electrical field, electrons—freed from the atoms of which they are normally a part—are able to move along the line of molecules. Because plastic is much less conductive than metal, an electrician will use a screwdriver with a plastic handle. Similarly, a metal pan typically has a handle of wood or plastic.
Convection
There is a term, "convection oven," that is actually a redundancy: all ovens heat through convection, the principal means of transferring heat through a fluid. In physics, "fluid" refers both to liquids and gases—anything that tends to flow. Instead of simply moving heat, as in conduction, convection involves the movement of heated material—that is, fluid. When air is heated, it displaces cold (that is, unheated) air in its path, setting up a convection current.
Convection takes place naturally, as for instance when hot air rises from the land on a warm day. This heated air has a lower density than that of the less heated air in the atmosphere above it, and, therefore, is buoyant. As it rises, however, it loses energy and cools. This cooled air, now more dense than the air around it, sinks again, creating a repeating cycle.
The preceding example illustrates natural convection; the heat of an oven, on the other hand, is an example of forced convection—a situation in which some sort of pump or mechanism moves heated fluid. So, too, is the cooling work of a refrigerator, though the refrigerator moves heat in the opposite direction.
Forced convection can also take place within a natural system. The human heart is a pump, and blood carries excess heat generated by the body to the skin. The heat passes through the skin by means of conduction, and at the surface of the skin, it is removed from the body in a number of ways, primarily by the cooling evaporation of moisture—that is, perspiration.
Radiation
If the Sun is hot—hot enough to severely burn the skin of a person who spends too much time exposed to its rays—then why is it cold in the upper atmosphere? After all, the upper atmosphere is closer to the Sun. And why is it colder still in the empty space above the atmosphere, which is still closer to the Sun? The reason is that in outer space there is no medium for convection, and in the upper atmosphere, where the air molecules are very far apart, there is hardly any medium. How, then, does heat come to the Earth from the Sun? By radiation, which is radically different from conduction or convection. The other two involve ordinary thermal energy, but radiation involves electromagnetic energy.
A great deal of "stuff" travels through the electromagnetic spectrum, discussed in another essay in this book: radio waves, microwaves for television and radar, infrared light, visible light, x rays, gamma rays. Though the relatively narrow band of visible-light wavelengths is the only part of the spectrum of which people are aware in everyday life, other parts—particularly the infrared and ultraviolet bands—are involved in the heat one feels from the Sun. (Ultraviolet rays, in fact, cause sunburns.)
Heat by means of radiation is not as "other-worldly" as it might seem: in fact, one does not have to point to the Sun for examples of it. Any time an object glows as a result of heat—as for example, in the case of firelight—that is an example of radiation. Some radiation is emitted in the form of visible light, but the heat component is in infrared rays. This also occurs in an incandescent light bulb. In an incandescent bulb, incidentally, much of the energy is lost to the heat of infrared rays, and the efficiency of a fluorescent bulb lies in the fact that it converts what would otherwise be heat into usable light.
The Laws of Thermodynamics
Having explored the behavior of heat, both at the molecular level and at levels more easily perceived by the senses, it is possible to discuss the laws of thermodynamics alluded to throughout this essay. These laws illustrate the relationships between heat and energy examined earlier, and show, for instance, why a refrigerator or air conditioner must have an external source of energy to move heat in a direction opposite to its normal flow.
The story of how these laws came to be discovered is a saga unto itself, involving the contributions of numerous men in various places over a period of more than a century. In 1791, Swiss physicist Pierre Prevost (1751-1839) put forth his theory of exchanges, stating correctly that all bodies radiate heat. Hence, as noted earlier, there is no such thing as "cold": when one holds snow in one's hand, cold does not flow from the snow into the hand; rather, heat flows from the hand to the snow.
Seven years later, an American-British physicist named Benjamin Thompson, Count Rumford (1753) was boring a cannon with a blunt drill when he noticed that this action generated a great deal of heat. This led him to question the prevailing wisdom, which maintained that heat was a fluid form of matter; instead, Thompson began to suspect that heat must arise from some form of motion.
Carnot's Engine
The next major contribution came from the French physicist and engineer Sadi Carnot (1796-1832). Though he published only one scientific work, Reflections on the Motive Power of Fire (1824), this treatise caused a great stir in the European scientific community. In it, Carnot made the first attempt at a scientific definition of work, describing it as "weight lifted through a height." Even more important was his proposal for a highly efficient steam engine.
A steam engine, like a modern-day internal combustion engine, is an example of a larger class of machine called heat engine. A heat engine absorbs heat at a high temperature, performs mechanical work, and, as a result, gives off heat a lower temperature. (The reason why that temperature must be lower is established in the second law of thermodynamics.)
For its era, the steam engine was what the computer is today: representing the cutting edge in technology, it was the central preoccupation of those interested in finding new ways to accomplish old tasks. Carnot, too, was fascinated by the steam engine, and was determined to help overcome its disgraceful inefficiency: in operation, a steam engine typically lost as much as 95% of its heat energy.
In his Reflections, Carnot proposed that the maximum efficiency of any heat engine was equal to (TH-TL)/TH, where TH is the highest operating temperature of the machine, and TL the lowest. In order to maximize this value, TL has to be absolute zero, which is impossible to reach, as was later illustrated by the third law of thermodynamics.
In attempting to devise a law for a perfectly efficient machine, Carnot inadvertently proved that such a machine is impossible. Yet his work influenced improvements in steam engine design, leading to levels of up to 80% efficiency. In addition, Carnot's studies influenced Kelvin—who actually coined the term "thermodynamics"—and others.
The First Law of Thermodynamics
During the 1840s, Julius Robert Mayer (1814-1878), a German physicist, published several papers in which he expounded the principles known today as the conservation of energy and the first law of thermodynamics. As discussed earlier, the conservation of energy shows that within a system isolated from all outside factors, the total amount of energy remains the same, though transformations of energy from one form to another take place.
The first law of thermodynamics states this fact in a somewhat different manner. As with the other laws, there is no definitive phrasing; instead, there are various versions, all of which say the same thing. One way to express the law is as follows: Because the amount of energy in a system remains constant, it is impossible to perform work that results in an energy output greater than the energy input. For a heat engine, this means that the work output of the engine, combined with its change in internal energy, is equal to its heat input. Most heat engines, however, operate in a cycle, so there is no net change in internal energy.
Earlier, it was stated that a refrigerator extracts two or three times as much heat from its inner compartment as the amount of energy required to run it. On the surface, this seems to contradict the first law: isn't the refrigerator putting out more energy than it received? But the heat it extracts is only part of the picture, and not the most important part from the perspective of the first law.
A regular heat engine, such as a steam or internal-combustion engine, pulls heat from a high-temperature reservoir to a low-temperature reservoir, and, in the process, work is accomplished. Thus, the hot steam from the high-temperature reservoir makes possible the accomplishment of work, and when the energy is extracted from the steam, it condenses in the low-temperature reservoir as relatively cool water.
A refrigerator, on the other hand, reverses this process, taking heat from a low-temperature reservoir (the evaporator inside the cooling compartment) and pumping it to a high-temperature reservoir outside the refrigerator. Instead of producing a work output, as a steam engine does, it requires a work input—the energy supplied via the wall outlet. Of course, a refrigerator does produce an "output," by cooling the food inside, but the work it performs in doing so is equal to the energy supplied for that purpose.
The Second Law of Thermodynamics
Just a few years after Mayer's exposition of the first law, another German physicist, Rudolph Julius Emanuel Clausius (1822-1888) published an early version of the second law of thermodynamics. In an 1850 paper, Clausius stated that "Heat cannot, of itself, pass from a colder to a hotter body." He refined this 15 years later, introducing the concept of entropy—the tendency of natural systems toward breakdown, and specifically, the tendency for the energy in a system to be dissipated.
The second law of thermodynamics begins from the fact that the natural flow of heat is always from a high-temperature reservoir to a low-temperature reservoir. As a result, no engine can be constructed that simply takes heat from a source and performs an equivalent amount of work: some of the heat will always be lost. In other words, it is impossible to build a perfectly efficient engine.
Though its relation to the first law is obvious, inasmuch as it further defines the limitations of machine output, the second law of thermodynamics is not derived from the first. Elsewhere in this volume, the first law of thermodynamics—stated as the conservation of energy law—is discussed in depth, and, in that context, it is in fact necessary to explain how the behavior of machines in the real world does not contradict the conservation law.
Even though they mean the same thing, the first law of thermodynamics and the conservation of energy law are expressed in different ways. The first law of thermodynamics states that "the glass is half empty," whereas the conservation of energy law shows that "the glass is half full." The thermodynamics law emphasizes the bad news: that one can never get more energy out of a machine than the energy put into it. Thus, all hopes of a perpetual motion machine were dashed. The conservation of energy, on the other hand, stresses the good news: that energy is never lost.
In this context, the second law of thermodynamics delivers another dose of bad news: though it is true that energy is never lost, the energy available for work output will never be as great as the energy put into a system. A car engine, for instance, cannot transform all of its energy input into usable horsepower; some of the energy will be used up in the form of heat and sound. Though energy is conserved, usable energy is not.
Indeed, the concept of entropy goes far beyond machines as people normally understand them. Entropy explains why it is easier to break something than to build it—and why, for each person, the machine called the human body will inevitably break down and die, or cease to function, someday.
The Third Law of Thermodynamics
The subject of entropy leads directly to the third law of thermodynamics, formulated by German chemist Hermann Walter Nernst (1864-1941) in 1905. The third law states that at the temperature of absolute zero, entropy also approaches zero. From this statement, Nernst deduced that absolute zero is therefore impossible to reach.
All matter is in motion at the molecular level, which helps define the three major phases of matter found on Earth. At one extreme is a gas, whose molecules exert little attraction toward one another, and are therefore in constant motion at a high rate of speed. At the other end of the phase continuum (with liquids somewhere in the middle) are solids. Because they are close together, solid particles move very little, and instead of moving in relation to one another, they merely vibrate in place. But they do move.
Absolute zero, or 0K on the Kelvin scale of temperature, is the point at which all molecular motion stops entirely—or at least, it virtually stops. (In fact, absolute zero is defined as the temperature at which the motion of the average atom or molecule is zero.) As stated earlier, Carnot's engine achieves perfect efficiency if its lowest temperature is the same as absolute zero; but the second law of thermodynamics shows that a perfectly efficient machine is impossible. This means that absolute zero is an unreachable extreme, rather like matter exceeding the speed of light, also an impossibility.
This does not mean that scientists do not attempt to come as close as possible to absolute zero, and indeed they have come very close. In 1993, physicists at the Helsinki University of Technology Low Temperature Laboratory in Finland used a nuclear demagnetization device to achieve a temperature of 2.8 · 10−10 K, or 0.00000000028K. This means that a fragment equal to only 28 parts in 100 billion separated this temperature from absolute zero—but it was still above 0K. Such extreme low-temperature research has a number of applications, most notably with superconductors, materials that exhibit virtually no resistance to electrical current at very low temperatures.
Where to Learn More
Beiser, Arthur. Physics, 5th ed. Reading, MA: Addison-Wesley, 1991.
Brown, Warren. Alternative Sources of Energy. Introduction by Russell E. Train. New York: Chelsea House, 1994.
Encyclopedia of Thermodynamics (Web site). <http://therion.minpet.unibas.ch/minpet/groups/thermodict/> (April 12, 2001).
Entropy and the Second Law of Thermodynamics (Web site). <http://www.2ndlaw.com> (April 12, 2001).
Fleisher, Paul. Matter and Energy: Principles of Matter and Thermodynamics. Minneapolis, MN: Lerner Publications, 2002.
Macaulay, David. The New Way Things Work. Boston: Houghton Mifflin, 1998.
Moran, Jeffrey B. How Do We Know the Laws of Thermodynamics? New York: Rosen Publishing Group, 2001.
Santrey, Laurence. Heat. Illustrated by Lloyd Birmingham. Mahwah, N.J.: Troll Associates, 1985.
Suplee, Curt. Everyday Science Explained. Washington, D.C.: National Geographic Society, 1996.
"Temperature and Thermodynamics" PhysLINK.com (Web site). <http://www.physlink.com/ae_thermo.cfm> (April 12, 2001).
For more information on thermodynamics, visit Britannica.com.
The science of the transformation of heat and energy.
The Thermodynamic System and Its Environment
In thermodynamics, one usually considers both the thermodynamic system and its environment. The environment often contains one or more idealized heat reservoirs—heat sources with infinite heat capacity enabling them to give up or absorb heat without changing their temperature. (An ocean or other large body of water approximates a heat reservoir.) A typical thermodynamic system is a definite quantity of gas enclosed in a cylinder with a sliding piston that allows the volume to vary. In general, a thermodynamic system is defined by its temperature, volume, pressure, and chemical composition. A system is in equilibrium when these variables have the same value at all points.
A mathematical statement that links the variables to show their interdependence is called an equation of state; the gas laws are simple examples of such equations. Equations of state take on their simplest form when the Kelvin temperature scale is used; on this scale 0° corresponds to the lowest temperature theoretically possible.
When the external conditions are altered, a thermodynamic system will respond by changing its state; the temperature, volume, pressure, and chemical composition will adjust to a new equilibrium. The most important kinds of changes are adiabatic and isothermal changes. An adiabatic change is one that occurs without any flow of heat. The system is thermally insulated from the environment, and the first law of thermodynamics requires that the work done by or on the system be equal to the loss or gain of the system's internal energy. An isothermal change occurs when the system is in contact with a heat reservoir, so that the system remains at the temperature of the reservoir. In the isothermal process, heat flows from the reservoir if the system is expanding and into the reservoir if the system is being compressed. For an ideal gas the internal energy depends only on the temperature; hence the internal energy remains constant during an isothermal change, and the heat absorbed from or by the reservoir is equal to the work done on or by the environment.
The First Law of Thermodynamics
Toward the middle of the 19th cent. heat was recognized as a form of energy associated with the motion of the molecules of a body (see kinetic-molecular theory of gases). Speaking more strictly, heat refers only to energy that is being transferred from one body to another. The total energy a body contains as a result of the positions and motions of its molecules is called its internal energy; in general, a body's temperature is a direct measure of its internal energy. All bodies can increase their internal energies by absorbing heat (see heat capacity). However, mechanical work done on a body can also increase its internal energy; e.g., the internal energy of a gas increases when the gas is compressed. Conversely, internal energy can be converted into mechanical energy; e.g., when a gas expands it does work on the external environment. In general, the change in a body's internal energy is equal to the heat absorbed from the environment minus the work done on the environment. This statement constitutes the first law of thermodynamics, which is a general form of the law of conservation of energy (see conservation laws).
The Second Law of Thermodynamics
A cyclic process is one that returns the system, but not the environment, to its original state. A closed cycle consisting of two isothermal and two adiabatic transformations is called a Carnot cycle after the French physicist Sadi Carnot, who first discussed the implications of such cycles. During the Carnot cycle occurring in the operation of a heat engine, a definite quantity of heat is absorbed from a reservoir at high temperature; part of this heat is converted into useful work, but the balance is expelled into a low-temperature reservoir and thus “wasted.” The greater the temperature difference between the two reservoirs, which in a steam engine are represented by the boiler and the condenser, the greater the fraction of absorbed heat that is converted into useful work. It is, however, theoretically impossible to convert all the heat extracted from the reservoir into useful work.
In general it is impossible to perform a transformation whose only final result is to convert into useful work heat extracted from a source that is at the same temperature throughout. This statement is Lord Kelvin's version of the second law of thermodynamics. Another version of this law, formulated by R. J. E. Clausius, states that a transformation is impossible whose only final result is to transfer heat from a body at a given temperature to a body at higher temperature; in other words, the spontaneous flow of heat from hot to cold bodies is reversible only with the expenditure of mechanical or other nonthermal energy. These two versions of the second law of thermodynamics can be shown to be entirely equivalent.
The second law is expressed mathematically in terms of the concept of entropy. When a body absorbs an amount of heat Q from a reservoir at temperature T, the body gains and the reservoir loses an amount of entropy S=Q/T. Thus, in a reversible adiabatic process (no heat change) there is no change in the total entropy. If an amount of heat Q flows from a hot to a cold body, the total entropy increases; because S=Q/T is larger for smaller values of T, the cold body gains more entropy than the hot body loses. The statement that heat never flows from a cold to a hot body can be generalized by saying that in no spontaneous process does the total entropy decrease.
In all real physical processes entropy increases; in ideal reversible processes entropy remains constant. Thus, in the Carnot cycle, which is reversible, there is no change in the total entropy. The engine itself experiences no net change in entropy because it is returned to its original state at the end of the cycle. The entropy gained by the low temperature reservoir is equal to the entropy lost by the high temperature reservoir. However, according to the formula S=Q/T, less heat need be expelled into the low temperature reservoir than is extracted from the high temperature reservoir for equal and opposite changes in entropy. In the Carnot cycle this difference in heat appears as useful mechanical work.
The Third Law of Thermodynamics
A postulate related to but independent of the second law is that it is impossible to cool a body to absolute zero by any finite process. Although one can approach absolute zero as closely as one desires, one cannot actually reach this limit. The third law of thermodynamics, formulated by Walter Nernst and also known as the Nernst heat theorem, states that if one could reach absolute zero, all bodies would have the same entropy. In other words, a body at absolute zero could exist in only one possible state, which would possess a definite energy, called the zero-point energy. This state is defined as having zero entropy.
Bibliography
See E. Fermi, Thermodynamics (1937); F. W. Sears, Thermodynamics, the Kinetic Theory of Gases, and Statistical Mechanics (2d ed. 1953); M. W. Zemansky, Heat and Thermodynamics (5th ed. 1968).
The branch of physics devoted to the study of heat and related phenomena. The behavior of heat is governed by the three laws of thermodynamics: (1) The total energy of an isolated system cannot change; this is the law of conservation of energy. (2) Heat will not flow from a cold to a hot object spontaneously (see entropy). (3) It is impossible, in a finite number of operations, to produce a temperature of absolute zero.
The branch of science dealing with heat and energy, their interconversion, and problems related thereto.
The study of heat and its transformation to mechanical and other forms of energy.
Thermodynamics (from the Greek θερμη, therme, meaning "heat" and δυναμις, dynamis, meaning "power") is a branch of physics that studies the effects of changes in temperature, pressure, and volume on physical systems at the macroscopic scale by analyzing the collective motion of their particles using statistics.[1][2] Roughly, heat means "energy in transit" and dynamics relates to "movement"; thus, in essence thermodynamics studies the movement of energy and how energy instills movement. Historically, thermodynamics developed out of need to increase the efficiency of early steam engines.[3]
The starting point for most thermodynamic considerations are the laws of thermodynamics, which postulate that energy can be exchanged between physical systems as heat or work.[4] They also postulate the existence of a quantity named entropy, which can be defined for any system.[5] In thermodynamics, interactions between large ensembles of objects are studied and categorized. Central to this are the concepts of system and surroundings. A system is composed of particles, whose average motions define its properties, which in turn are related to one another through equations of state. Properties can be combined to express internal energy and thermodynamic potentials, which are useful for determining conditions for equilibrium and spontaneous processes.
With these tools, thermodynamics describes how systems respond to changes in their surroundings. This can be applied to a wide variety of topics in science and engineering, such as engines, phase transitions, chemical reactions, transport phenomena, and even black holes. The results of thermodynamics are essential for other fields of physics and for chemistry, chemical engineering, aerospace engineering, mechanical engineering, cell biology, biomedical engineering, and materials science to name a few.[6][7]
A brief history of thermodynamics begins with Otto von Guericke who in 1650 built and designed the world's first vacuum pump and created the world's first ever vacuum (known as the Magdeburg hemispheres). He was driven to make a vacuum in order to disprove Aristotle's long-held supposition that 'nature abhors a vacuum'. Shortly thereafter, Irish physicist and chemist Robert Boyle had learned of Guericke's designs and in 1656, in coordination with English scientist Robert Hooke, built an air pump.[8] Using this pump, Boyle and Hooke noticed the pressure-temperature-volume correlation. In time, Boyle's Law was formulated, which states that pressure and volume are inversely proportional. Then, in 1679, based on these concepts, an associate of Boyle's named Denis Papin built a bone digester, which was a closed vessel with a tightly fitting lid that confined steam until a high pressure was generated.
Later designs implemented a steam release valve that kept the machine from exploding. By watching the valve rhythmically move up and down, Papin conceived of the idea of a piston and a cylinder engine. He did not, however, follow through with his design. Nevertheless, in 1697, based on Papin's designs, engineer Thomas Savery built the first engine. Although these early engines were crude and inefficient, they attracted the attention of the leading scientists of the time. One such scientist was Sadi Carnot, the "father of thermodynamics", who in 1824 published Reflections on the Motive Power of Fire, a discourse on heat, power, and engine efficiency. The paper outlined the basic energetic relations between the Carnot engine, the Carnot cycle, and Motive power. This marks the start of thermodynamics as a modern science.[1]
The term thermodynamics was coined by James Joule in 1858 to designate the science of relations between heat and power.[1] By 1849, "thermo-dynamics", as a functional term, was used in William Thomson's paper An Account of Carnot's Theory of the Motive Power of Heat.[9] The first thermodynamic textbook was written in 1859 by William Rankine, originally trained as a physicist and a civil and mechanical engineering professor at the University of Glasgow.[10]
Classical thermodynamics is the original early 1800s variation of thermodynamics concerned with thermodynamic states, and properties as energy, work, and heat, and with the laws of thermodynamics, all lacking an atomic interpretation. In precursory form, classical thermodynamics derives from chemist Robert Boyle’s 1662 postulate that the pressure P of a given quantity of gas varies inversely as its volume V at constant temperature; i.e. in equation form: PV = k, a constant. From here, a semblance of a thermo-science began to develop with the construction of the first successful atmospheric steam engines in England by Thomas Savery in 1697 and Thomas Newcomen in 1712. The first and second laws of thermodynamics emerged simultaneously in the 1850s, primarily out of the works of William Rankine, Rudolf Clausius, and William Thomson (Lord Kelvin).[11]
With the development of atomic and molecular theories in the late 19th century, thermodynamics was given a molecular interpretation. This field is called statistical thermodynamics, which can be thought of as a bridge between macroscopic and microscopic properties of systems.[12] Essentially, statistical thermodynamics is an approach to thermodynamics situated upon statistical mechanics, which focuses on the derivation of macroscopic results from first principles. It can be opposed to its historical predecessor phenomenological thermodynamics, which gives scientific descriptions of phenomena with avoidance of microscopic details. The statistical approach is to derive all macroscopic properties (temperature, volume, pressure, energy, entropy, etc.) from the properties of moving constituent particles and the interactions between them (including quantum phenomena). It was found to be very successful and thus is commonly used.
Chemical thermodynamics is the study of the interrelation of heat with chemical reactions or with a physical change of state within the confines of the laws of thermodynamics. During the years 1873-76 the American mathematical physicist Josiah Willard Gibbs published a series of three papers, the most famous being On the Equilibrium of Heterogeneous Substances, in which he showed how thermodynamic processes could be graphically analyzed, by studying the energy, entropy, volume, temperature and pressure of the thermodynamic system, in such a manner to determine if a process would occur spontaneously.[13] During the early 20th century, chemists such as Gilbert N. Lewis, Merle Randall, and E. A. Guggenheim began to apply the mathematical methods of Gibbs to the analysis of chemical processes.[14]
An important concept in thermodynamics is the “system”. Everything in the universe except the system is known as surroundings. A system is the region of the universe under study. A system is separated from the remainder of the universe by a boundary which may be imaginary or not, but which by convention delimits a finite volume. The possible exchanges of work, heat, or matter between the system and the surroundings take place across this boundary. Boundaries are of four types: fixed, moveable, real, and imaginary.
Basically, the “boundary” is simply an imaginary dotted line drawn around the volume of a something in which there is going to be a change in the internal energy of that something. Anything that passes across the boundary that effects a change in the internal energy of that something needs to be accounted for in the energy balance equation. That “something” can be the volumetric region surrounding a single atom resonating energy, such as Max Planck defined in 1900; it can be a body of steam or air in a steam engine, such as Sadi Carnot defined in 1824; it can be the body of a tropical cyclone, such as Kerry Emanuel theorized in 1986 in the field of atmospheric thermodynamics; it could also be just one nuclide (i.e. a system of quarks) as some are theorizing presently in quantum thermodynamics.
For an engine, a fixed boundary means the piston is locked at its position; as such, a constant volume process occurs. In that same engine, a moveable boundary allows the piston to move in and out. For closed systems, boundaries are real while for open system boundaries are often imaginary. There are five dominant classes of systems:
As time passes in an isolated system, internal differences in the system tend to even out and pressures and temperatures tend to equalize, as do density differences. A system in which all equalizing processes have gone practically to completion, is considered to be in a state of thermodynamic equilibrium.
In thermodynamic equilibrium, a system's properties are, by definition, unchanging in time. Systems in equilibrium are much simpler and easier to understand than systems which are not in equilibrium. Often, when analysing a thermodynamic process, it can be assumed that each intermediate state in the process is at equilibrium. This will also considerably simplify the situation. Thermodynamic processes which develop so slowly as to allow each intermediate step to be an equilibrium state are said to be reversible processes.
The central concept of thermodynamics is that of energy, the ability to do work. As stipulated by the first law, the total energy of the system and its surroundings is conserved. It may be transferred into a body by heating, compression, or addition of matter, and extracted from a body either by cooling, expansion, or extraction of matter. For comparison, in mechanics, energy transfer results from a force which causes displacement, the product of the two being the amount of energy transferred. In a similar way, thermodynamic systems can be thought of as transferring energy as the result of a generalized force causing a generalized displacement, with the product of the two being the amount of energy transferred. These thermodynamic force-displacement pairs are known as conjugate variables. The most common conjugate thermodynamic variables are pressure-volume (mechanical parameters), temperature-entropy (thermal parameters), and chemical potential-particle number (material parameters)..
There are two types of thermodynamic instruments, the meter and the reservoir. A thermodynamic meter is any device which measures any parameter of a thermodynamic system. In some cases, the thermodynamic parameter is actually defined in terms of an idealized measuring instrument. For example, the zeroth law states that if two bodies are in thermal equilibrium with a third body, they are also in thermal equilibrium with each other. This principle, as noted by James Maxwell in 1872, asserts that it is possible to measure temperature. An idealized thermometer is a sample of an ideal gas at constant pressure. From the ideal gas law PV=nRT, the volume of such a sample can be used as an indicator of temperature; in this manner it defines temperature. Although pressure is defined mechanically, a pressure-measuring device, called a barometer may also be constructed from a sample of an ideal gas held at a constant temperature. A calorimeter is a device which is used to measure and define the internal energy of a system.
A thermodynamic reservoir is a system which is so large that it does not appreciably alter its state parameters when brought into contact with the test system. It is used to impose a particular value of a state parameter upon the system. For example, a pressure reservoir is a system at a particular pressure, which imposes that pressure upon any test system that it is mechanically connected to. The earth's atmosphere is often used as a pressure reservoir.
It is important that these two types of instruments are distinct. A meter does not perform its task accurately if it behaves like a reservoir of the state variable it is trying to measure. If, for example, a thermometer, were to act as a temperature reservoir it would alter the temperature of the system being measured, and the reading would be incorrect. Ideal meters have no effect on the state variables of the system they are measuring.
When a system is at equilibrium under a given set of conditions, it is said to be in a definite state. The state of the system can be described by a number of intensive variables and extensive variables. The properties of the system can be described by an equation of state which specifies the relationship between these variables. State may be thought of as the instantaneous quantitative description of a system with a set number of variables held constant.
A thermodynamic process may be defined as the energetic evolution of a thermodynamic system proceeding from an initial state to a final state. Typically, each thermodynamic process is distinguished from other processes, in energetic character, according to what parameters, as temperature, pressure, or volume, etc., are held fixed. Furthermore, it is useful to group these processes into pairs, in which each variable held constant is one member of a conjugate pair. The seven most common thermodynamic processes are shown below:
In thermodynamics, there are four laws of very general validity, and as such they do not depend on the details of the interactions or the systems being studied. Hence, they can be applied to systems about which one knows nothing other than the balance of energy and matter transfer. Examples of this include Einstein's prediction of spontaneous emission around the turn of the 20th century and current research into the thermodynamics of black holes.
The four laws are:
As can be derived from the energy balance equation on a thermodynamic system there exist energetic quantities called thermodynamic potentials, being the quantitative measure of the stored energy in the system. The five most well known potentials are:
| Internal energy | ![]() |
| Helmholtz free energy | ![]() |
| Enthalpy | ![]() |
| Gibbs free energy | ![]() |
| Grand potential | ![]() |
Potentials are used to measure energy changes in systems as they evolve from an initial state to a final state. The potential used depends on the constraints of the system, such as constant temperature or pressure. Internal energy is the internal energy of the system, enthalpy is the internal energy of the system plus the energy related to pressure-volume work, and Helmholtz and Gibbs energy are the energies available in a system to do useful work when the temperature and volume or the pressure and temperature are fixed, respectively.
| “ | Thermodynamics is a funny subject. The first time you go through it, you don't understand it at all. The second time you go through it, you think you understand it, except for one or two small points. The third time you go through it, you know you don't understand it, but by that time you are so used to it, it doesn't bother you any more. | ” |