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Thermodynamics

THERMODYNAMICS

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 energythe energy that an object has due to its positionand 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 exampleone involving mechanical energy in a gravitational fieldwhen 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 energyat least in relation to the system of height between the cliff and the bottomhas 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 systemthat 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 groundonly this time at the bottom of the canyonit 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 Stateswhere British measures typically still prevailis 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°Cbut 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 4.185which 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 compartmentthe area where food and other perishables are storedand 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 refrigeranta 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 energyno matter how "hot" it may be in ordinary termsno 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 gasdue to the loose attractions between its moleculesis 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, electronsfreed from the atoms of which they are normally a partare 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 gasesanything that tends to flow. Instead of simply moving heat, as in conduction, convection involves the movement of heated materialthat 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 convectiona 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 moisturethat is, perspiration.

RADIATION.

If the Sun is hothot enough to severely burn the skin of a person who spends too much time exposed to its raysthen 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 partsparticularly the infrared and ultraviolet bandsare 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 heatas for example, in the case of firelightthat 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 Kelvinwho 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 inputthe 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 entropythe 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 thermodynamicsstated as the conservation of energy lawis 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 itand 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 entirelyor 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 · 1010 K, or 0.00000000028K. This means that a fragment equal to only 28 parts in 100 billion separated this temperature from absolute zerobut 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).

KEY TERMS

ABSOLUTE ZERO:

The temperature, defined as 0K on the Kelvin scale, at which the motion of molecules in a solid virtually ceases. The third law of thermodynamics establishes the impossibility of actually reaching absolute zero.

BTU (BRITISH THERMAL UNIT):

A measure of energy or heat in the Britishsystem, often used in reference to the capacity of an air conditioner. A Btu is equal to 778 foot-pounds, or 1,054 joules.

CALORIE:

A measure of heat or energy in the SI or metric system, equal to the heat that must be added to or removed from 1 gram of water to change its temperature by 33.8°F (1°C). The dietary Calorie (capital C) with which most people are familiar is the same as the kilocalorie.

CONDUCTION:

The transfer of heat by successive molecular collisions. Conduction is the principal means of heat transfer in solids, particularly metals.

CONSERVATION OF ENERGY:

A law of physics which holds that within a system isolated from all other 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 is the same as the conservation of energy.

CONSERVE:

In physics, "to conserve" something means "to result in no net loss of" that particular component. It is possible that within a given system, the component may change form or position, but as long as the net value of the component remains the same, it has been conserved.

CONVECTION:

The transfer of heat through the motion of hot fluid from oneplace to another. In physics, a "fluid" can be either a gas or a liquid, and convection is the principal means of heat transfer, for instance, in air and water.

ENERGY:

The ability to accomplishwork.

ENTROPY:

The tendency of natural systems toward breakdown, and specifically, the tendency for the energy in a system to be dissipated. Entropy is closely related to the second law of thermodynamics.

FIRST LAW OF THERMODYNAMICS:

A law which states the amount of energy in a system remains constant, and therefore it is impossible to perform work that results in an energy output greater than the energy input. This is the same as the conservation of energy.

FOOT-POUND:

The principal unit of energyand thus of heatin the British or English system. The metric or SI unit is the joule. A foot-pound (ft · lb) is equal to 1.356 J.

HEAT:

Internal thermal energy that flows from one body of matter to another. Heat is transferred by three methods conduction, convection, and radiation.

HEAT CAPACITY:

The amount of heat that must be added to, or removed from, a unit of mass of a given substance to change its temperature by 33.8°F (1°C). Heat capacity is sometimes called specific heat capacity or specific heat. A kilocalorie is the heat capacity of 1 gram of water.

HEAT ENGINE:

A machine that absorbs heat at a high temperature, performs mechanical work, and as a result gives off heat at a lower temperature.

KINETIC ENERGY:

The energy that an object possesses by virtue of its motion.

JOULE:

The principal unit of energyand thus of heatin the SI or metric system, corresponding to 1 newton-meter (N · m). A joule (J) is equal to 0.7376 foot-pounds.

KELVIN SCALE:

Established by William Thomson, Lord Kelvin (1824-1907), the Kelvin scale measures temperature in relation to absolute zero, or 0K.(Units in the Kelvin system, known as Kelvins, do not include the word or symbol for degree.) The Kelvin and Celsius scales are directly related; hence Celsius temperatures can be converted to Kelvins by adding273.15.

KILOCALORIE:

A measure of heat or energy in the SI or metric system, equal to the heat that must be added to or removed from 1 kilogram of water to change its temperature by 33.8°F (1°C). As its name suggests, a kilocalorie is 1,000 calories. The dietary Calorie (capital C) with which most people are familiar is the same as the kilocalorie.

MECHANICAL ENERGY:

The sum of potential energy and kinetic energy in a given system.

POTENTIAL ENERGY:

The energy that an object possesses due to its position.

RADIATION:

The transfer of heat by means of electromagnetic waves, which require no physical medium (e.g., water or air) for the transfer. Earth receives the Sun's heat by means of radiation.

SECOND LAW OF THERMODYNAMICS:

A law of thermodynamics which states that 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, and therefore it is impossible to build a perfectly efficient engine. This is a result of th efact that the natural flow of heat is always from a high-temperature reservoir to alow-temperature reservoira fact expressed in the concept of entropy. The second law is sometimes referred to as "the law of entropy."

SYSTEM:

In physics, the term "system" usually refers to any set of physical interactions isolated from the rest of the universe. Anything outside of the system, including all factors and forces irrelevant to a discussion of that system, is known as the environment.

TEMPERATURE:

The direction of internal energy flow between bodies when heat is being transferred. Temperature measures the average molecular kinetic energy in transit between those bodies.

THERMAL ENERGY:

Heat energy, a form of kinetic energy produced by the movement of atomic or molecular particles. The greater the movement of the separticles, the greater the thermal energy.

THERMODYNAMICS:

The study of the relationships between heat, work, and energy.

THIRD LAW OF THERMODYNAMICS:

A law of thermodynamics which states that at the temperature of absolute zero, entropy also approaches zero. Zero entropy would contradict the second law of thermodynamics, meaning that absolute zero is therefore impossible to reach.

WORK:

The exertion of force over a given distance to displace or move an object. Work is thus the product of force and distance exerted in the same direction.

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thermodynamics

thermodynamics, branch of science concerned with the nature of heat and its conversion to mechanical, electric, and chemical energy. Historically, it grew out of efforts to construct more efficient heat engines—devices for extracting useful work from expanding hot gases.

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).

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Thermodynamics

Thermodynamics


Thermodynamics is the science of heat and temperature and, in particular, of the laws governing the conversion of thermal energy into mechanical, electrical, or other forms of energy. It is a central branch of science that has important applications in chemistry, physics, biology, and engineering. Thermodynamics is a logical discipline that organizes the information obtained from experiments performed on systems and enables us to draw conclusions, without further experimentation, about other properties of the system. It allows us to predict whether a reaction will proceed and what the maximum yield might be.

Thermodynamics is a macroscopic science that deals with such properties as pressure, temperature, and volume. Unlike quantum mechanics , thermodynamics is not based on a specific model, and therefore it is unaffected by our changing concepts of atoms and molecules. By the same token, equations derived from thermodynamics do not provide us with molecular interpretations of complex phenomena. Furthermore, thermodynamics tells us nothing about the rate of a process except its likelihood.

Applications of thermodynamics are based on three fundamental laws that deal with energy and entropy changes. The laws of thermodynamics cannot be derived; their validity is based on the fact that they predict changes that are consistent with experimental observations.

The first law of thermodynamics is based on the law of conservation of energy, which states that energy can neither be created nor destroyed; therefore, the total energy of the universe is constant. It is convenient for scientists to divide the universe into two parts: the system (the part of the universe that is under studyfor example, a beaker of solution) and the surroundings (the rest of the universe). For any process, then, the change in the energy of the universe is zero. Chemists are usually interested only in what happens to the system. Consequently, for a given process the first law can be expressed as

ΔU = q + w          (1)

where ΔU is the change in the internal energy of the system, q is the heat exchange between the system and the surroundings, and w is the work done by the system or performed on the system by the surroundings. The first law is useful in studying the energetics of physical processes, such as the melting or boiling of a substance, and chemical reactionsfor example, combustion . The heat change occurring as part of a process is measured with a calorimeter. For a constant-volume process, the heat change is equated to the change in the internal energy ΔU of the system; for a constant-pressure process, which is more common, the heat change is equated to the change in the enthalpy ΔH of the system. Enthalpy H is a thermodynamic function closely related to the internal energy of the system, and is defined as

H = U + PV          (2)

where P and V are the pressure and volume of the system, respectively.

The first law of thermodynamics deals only with energy changes and cannot predict the direction of a process. It asks, for example: Under a given set of conditions of pressure, temperature, and concentration, will a specific reaction occur? To answer the question we need a new thermodynamic function called entropy S. To define entropy, we need to use a quantum mechanical concept. The entropy of a system is related to the distribution of energy among the available molecular energy levels at a given temperature. The greater the number of energy levels that have significant occupation, the greater the entropy.

The second law of thermodynamics states that the entropy of the universe increases in a spontaneous process and remains unchanged in an equilibrium process. The mathematical statement of the second law of thermodynamics is given by

ΔS univ = ΔS sys + ΔS surr 0          (3)

where the subscripts denote the universe, the system, and the surroundings, respectively. The greater than portion of the "greater than or equal to" sign corresponds to a spontaneous process, and the equal portion corresponds to a system at equilibrium. Because processes in the real world are spontaneous, the entropy of the universe therefore constantly increases with time.

As is not the case with energy and enthalpy , it is possible to determine the absolute value of entropy of a system. To measure the entropy of a substance at room temperature, it is necessary to add up entropy from the absolute zero up to 25°C (77°F). However, the absolute zero is unattainable in practice. This dilemma is resolved by applying the third law of thermodynamics, which states that the entropy of a pure, perfect crystalline substance is zero at the absolute zero of temperature. The increase in entropy from the lowest reachable temperature upward can then be determined from heat capacity measurements and enthalpy changes due to phase transitions.

Because it is inconvenient to use the change in entropy of the universe to determine the direction of a reaction, an additional thermodynamic function, called the Gibbs free energy (G ), is introduced to help chemists to focus only on the system. The Gibbs free energy of a system is defined as G = H TS, where T is the absolute temperature. At constant temperature and pressure, ΔG is negative for a spontaneous process, is positive for an unfavorable process, and equals zero for a system at equilibrium. The change in Gibbs free energy can be related to the changes in enthalpy and entropy of a reaction, and also to the equilibrium constant of the reaction, according to the equation ΔG ° = RT ln K, where ΔG ° is the change in Gibbs free energy under standard-state conditions (1 bar), R is the gas constant, and K is the equilibrium constant.

Many chemical reactions can be classified as either kinetically controlled or thermodynamically controlled. In a kinetically controlled process the products are thermodynamically more stable than the reactants, hence the reaction is favorable. However, the rate of reaction is often very slow due to a high activation energy barrier. The conversion of the less stable allotropic form of carbon, diamond, to the more stable graphite is an example: The process can take millions of years to complete. In a thermodynamically controlled reaction the reactants may have a number of kinetically accessible routes to follow to form different products, but what is eventually formed is governed by relative thermodynamic stability. In protein folding, for example, a denatured protein may have many possibilities of intermediate conformation; however, the conformation it finally assumes, which corresponds to the physiologically functioning protein, is the most stable state thermodynamically.

see also Chemistry and Energy; Energy; Heat; Kinetics; Physical Chemistry; Temperature.

Raymond Chang

Bibliography

Bent, Henry A. (1965). The Second Law: An Introduction to Classical and Statistical Thermodynamics. New York: Oxford University Press.

Berry, R. Stephen (1991). Understanding Energy: Energy, Entropy, and Thermodynamics for Everyman. River Edge, NJ: World Scientific.

Smith, E. Brian (1990). Basic Chemical Thermodynamics, 4th edition. New York: Oxford University Press.

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Thermodynamics

Thermodynamics

Thermodynamics is the science that deals with work and heatand the transformation of one into the other. It is a macroscopic theory, dealing with matter in bulk, disregarding the molecular nature of materials. The corresponding microscopic theory, based on the fact that materials are made up of a vast number of particles, is called statistical mechanics.

Historical background

The origins of thermodynamics can be traced to the late eighteenth century. English-American physicist Benjamin Thomson, Count Rumford (17531814), became intrigued by the physical changes accompanying the boring of cannons. (Boring is the process of making a holein this case the barrel of the cannonwith a twisting movement.) He found that the work (or mechanical energy) involved in the boring process was converted to heat as a result of friction, causing the temperature of the cannon to rise.

Some of the fundamental relationships involved in thermodynamics were later developed by English physicist James Joule (18181889), who showed that work can be converted to heat without limit. Other researchers found, however, that the opposite is not truethat is, that there are limiting factors that operate in the conversion of heat to work. The research of French physicist Sadi Carnot (17961832), British physicist William Thomson, Lord Kelvin (18241907), and German physicist Rudolf Clausius (18221888), among others, has led to an understanding of these limitations.

The laws of thermodynamics

The most basic facts about thermodynamics can be summarized in two general laws. The first law of thermodynamics is actually nothing other than the law of conservation of energy: energy can neither be created nor destroyed. It can be converted from one form to another, but the total amount of energy in a system always remains constant.

For example, consider the simple example of heating a beaker of water with a gas flame. One can measure the amount of heat energy given off by the flame. One also can measure the increase in the heat energy of the water in the beaker, the beaker itself, and any air surrounding the beaker. Under ideal circumstances, the total amount of energy produced by the flame is equal to the total amount of energy gained by the water, the beaker, and the air.

The first law of thermodynamics is sometimes stated in a somewhat different form because of the kinds of systems to which it is applied. Another statement is that the internal energy of a system is equal to the amount of work done on the system plus any heat added to the system. In this definition, the term work is used to describe all forms of energy other than heat.

The first law can be thought of as a quantitative law (involving measurement of some quantity or amount): the amount of energy lost by one system is equal to the amount of energy gained by a second system. The second law, in contrast, can be thought of as a qualitative law (involving quality or kind): the second law says that all natural processes occur in such a way as to result in an increase in entropy.

To understand this law, it is first necessary to explain the concept of entropy. Entropy means disorder. Consider the dissolving of a sugar cube in water. The sugar cube itself represents a highly ordered state in which every sugar particle is arranged in an exact position within the sugar crystal. The entropy of a sugar cube is low because there is little disorder.

Words to Know

Energy: The capacity for doing work.

Entropy: The amount of disorder in a system.

First law of thermodynamics: The internal energy of a system is increased by the amount of work done on the system and the heat flow to the system (Conservation of Energy).

Heat: A form of energy produced by the motion of molecules that make up a substance.

Second law of thermodynamics: All natural processes proceed in a direction that leads to an increase in entropy.

Submicroscopic level of phenomena: Phenomena that cannot be observed directly by any of the five human senses, aided or unaided.

Work: Transfer of energy by a force acting to move matter.

But consider what happens when the sugar cube is dissolved in water. The cube breaks apart, and sugar molecules are dispersed completely throughout the water. There is no longer any order among the sugar molecules at all. The entropy of the system has increased because the sugar molecules have become completely disorganized.

The second law of thermodynamics simply says that any time some change takes place in nature, there will be more entropymore disorganizationthan there was to begin with. As a practical example, consider the process by which electricity is generated in most instances in the United States today. Coal or oil is burned in a large furnace, heating water and changing it to steam. The steam then is used to run turbines and generators that manufacture electricity. The first law of thermodynamics says that all of the energy stored in coal and oil must ultimately be converted to some other form: electricity or heat, for example. But the second law says that some of the energy from coal and oil will end up as "waste" heat, heat that performs no useful function. It is energy that simply escapes into the surrounding environment and is distributed throughout the universe.

The second law is sometimes described as the "death of the universe" law because it means that over very long periods of time, all forms of energy will be evenly distributed throughout the universe. The waste energy produced by countless numbers of natural processes will add up over the millennia until that is the only form in which energy will remain in our universe.

[See also Gases, properties of; Heat; Temperature ]

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thermodynamics

thermodynamics Branch of physics that studies heat and how it is transformed to and from other forms of energy. The original laws of thermodynamics were conceived by observing large-scale properties of systems and with no understanding of the underlying atomic structure. The kinetic theory of gases developed in the mid-19th century. In general, the temperature of a body is a measure of its internal energy. The three existing laws are now calculated using statistics and quantum mechanics. The first law of thermodynamics, basically a restatement of the conservation law of energy, is that the change in a system's internal energy is equal to the heat that flows into the system plus the work done on the system. The two main forms of change are adiabatic (without heat entering or leaving a system) and isothermal (at constant temperature). The second law says that if a system is left alone, its entropy tends to increase. This rules out the possibility of perpetual motion. The third law states that a system at absolute zero would effectively have an entropy of zero. See also Carnot cycle; Clausius; Kelvin

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thermodynamics

ther·mo·dy·nam·ics / ˌ[unvoicedth]ərmōdīˈnamiks/ • pl. n. [treated as sing.] the branch of physical science that deals with the relations between heat and other forms of energy (such as mechanical, electrical, or chemical energy), and, by extension, of the relationships and interconvertibility of all forms of energy. DERIVATIVES: ther·mo·dy·nam·ic adj. ther·mo·dy·nam·i·cal / -ikəl/ adj. ther·mo·dy·nam·i·cal·ly / -ik(ə)lē/ adv. ther·mo·dy·nam·i·cist / -ˌdīˈnamisist/ n.

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