Thermodynamics

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Annotated color version of the original 1824 Carnot heat engine showing the hot body (boiler), working
body (system, steam), and cold body (water), the letters labeled according to the stopping points in
Carnot cycle.

Thermodynamics

Carnot heat engine 2.svg

The classical Carnot heat engine

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Thermodynamics is the branch of physics that deals with heat and temperature, and their relation to
energy, work, radiation, and properties of matter. The behavior of these quantities is governed by the
four laws of thermodynamics which convey a quantitative description using measurable macroscopic
physical quantities, but may be explained in terms of microscopic constituents by statistical mechanics.
Thermodynamics applies to a wide variety of topics in science and engineering, especially physical
chemistry, chemical engineering and mechanical engineering, but also in fields as complex as
meteorology.

Historically, thermodynamics developed out of a desire to increase the efficiency of early steam engines,
particularly through the work of French physicist Nicolas Léonard Sadi Carnot (1824) who believed that
engine efficiency was the key that could help France win the Napoleonic Wars.[1] Scots-Irish physicist
Lord Kelvin was the first to formulate a concise definition of thermodynamics in 1854[2] which stated,
"Thermo-dynamics is the subject of the relation of heat to forces acting between contiguous parts of
bodies, and the relation of heat to electrical agency."

The initial application of thermodynamics to mechanical heat engines was extended early on to the
study of chemical compounds and chemical reactions. Chemical thermodynamics studies the nature of
the role of entropy in the process of chemical reactions and has provided the bulk of expansion and
knowledge of the field.[3][4][5][6][7][8][9][10][11] Other formulations of thermodynamics emerged.
Statistical thermodynamics, or statistical mechanics, concerns itself with statistical predictions of the
collective motion of particles from their microscopic behavior. In 1909, Constantin Carathéodory
presented a purely mathematical approach in an axiomatic formulation, a description often referred to
as geometrical thermodynamics.

Heat is energy can be converted from one form to another, or transferred from one object to another.
For example, a stove burner converts electrical energy to heat and conducts that energy through the pot
to the water. This increases the kinetic energy of the water molecules, causing them to move faster and
faster. At a certain temperature (the boiling point), the atoms have gained enough energy to break free
of the molecular bonds of the liquid and escape as vapor.

(Image: © Carolyn Franks | Shutterstock )

Thermodynamics is the branch of physics that deals with the relationships between heat and other
forms of energy. In particular, it describes how thermal energy is converted to and from other forms of
energy and how it affects matter.

Thermal energy is the energy a substance or system has due to its temperature, i.e., the energy of
moving or vibrating molecules, according to the Energy Education website of the Texas Education
Agency. Thermodynamics involves measuring this energy, which can be "exceedingly complicated,"
according to David McKee, a professor of physics at Missouri Southern State University. "The systems
that we study in thermodynamics … consist of very large numbers of atoms or molecules interacting in
complicated ways. But, if these systems meet the right criteria, which we call equilibrium, they can be
described with a very small number of measurements or numbers. Often this is idealized as the mass of
the system, the pressure of the system, and the volume of the system, or some other equivalent set of
numbers. Three numbers describe 1026 or 1030 nominal independent variables."

Heat

Thermodynamics, then, is concerned with several properties of matter; foremost among these is heat.
Heat is energy transferred between substances or systems due to a temperature difference between
them, according to Energy Education. As a form of energy, heat is conserved, i.e., it cannot be created or
destroyed. It can, however, be transferred from one place to another. Heat can also be converted to and
from other forms of energy. For example, a steam turbine can convert heat to kinetic energy to run a
generator that converts kinetic energy to electrical energy. A light bulb can convert this electrical energy
to electromagnetic radiation (light), which, when absorbed by a surface, is converted back into heat.

Temperature

The amount of heat transferred by a substance depends on the speed and number of atoms or
molecules in motion, according to Energy Education. The faster the atoms or molecules move, the
higher the temperature, and the more atoms or molecules that are in motion, the greater the quantity
of heat they transfer.

emperature is "a measure of the average kinetic energy of the particles in a sample of matter, expressed
in terms of units or degrees designated on a standard scale," according to the American Heritage
Dictionary. The most commonly used temperature scale is Celsius, which is based on the freezing and
boiling points of water, assigning respective values of 0 degrees C and 100 degrees C. The Fahrenheit
scale is also based on the freezing and boiling points of water which have assigned values of 32 F and
212 F, respectively.

Scientists worldwide, however, use the Kelvin (K with no degree sign) scale, named after William
Thomson, 1st Baron Kelvin, because it works in calculations. This scale uses the same increment as the
Celsius scale, i.e., a temperature change of 1 C is equal to 1 K. However, the Kelvin scale starts at
absolute zero, the temperature at which there is a total absence of heat energy and all molecular
motion stops. A temperature of 0 K is equal to minus 459.67 F or minus 273.15 C.

Specific heat

The amount of heat required to increase the temperature of a certain mass of a substance by a certain
amount is called specific heat, or specific heat capacity, according to Wolfram Research. The
conventional unit for this is calories per gram per kelvin. The calorie is defined as the amount of heat
energy required to raise the temperature of 1 gram of water at 4 C by 1 degree.

The specific heat of a metal depends almost entirely on the number of atoms in the sample, not its
mass. For instance, a kilogram of aluminum can absorb about seven times more heat than a kilogram of
lead. However, lead atoms can absorb only about 8 percent more heat than an equal number of
aluminum atoms. A given mass of water, however, can absorb nearly five times as much heat as an
equal mass of aluminum. The specific heat of a gas is more complex and depends on whether it is
measured at constant pressure or constant volume.

Thermal conductivity

Thermal conductivity (k) is “the rate at which heat passes through a specified material, expressed as the
amount of heat that flows per unit time through a unit area with a temperature gradient of one degree
per unit distance,” according to the Oxford Dictionary. The unit for k is watts (W) per meter (m) per
kelvin (K). Values of k for metals such as copper and silver are relatively high at 401 and 428 W/m·K,
respectively. This property makes these materials useful for automobile radiators and cooling fins for
computer chips because they can carry away heat quickly and exchange it with the environment. The
highest value of k for any natural substance is diamond at 2,200 W/m·K.

Other materials are useful because they are extremely poor conductors of heat; this property is referred
to as thermal resistance, or R-value, which describes the rate at which heat is transmitted through the
material. These materials, such as rock wool, goose down and Styrofoam, are used for insulation in
exterior building walls, winter coats and thermal coffee mugs. R-value is given in units of square feet
times degrees Fahrenheit times hours per British thermal unit (ft2·°F·h/Btu) for a 1-inch-thick slab.

Newton's Law of Cooling

In 1701, Sir Isaac Newton first stated his Law of Cooling in a short article titled "Scala graduum Caloris"
("A Scale of the Degrees of Heat") in the Philosophical Transactions of the Royal Society. Newton's
statement of the law translates from the original Latin as, "the excess of the degrees of the heat ... were
in geometrical progression when the times are in an arithmetical progression." Worcester Polytechnic
Institute gives a more modern version of the law as "the rate of change of temperature is proportional
to the difference between the temperature of the object and that of the surrounding environment."
This results in an exponential decay in the temperature difference. For example, if a warm object is
placed in a cold bath, within a certain length of time, the difference in their temperatures will decrease
by half. Then in that same length of time, the remaining difference will again decrease by half. This
repeated halving of the temperature difference will continue at equal time intervals until it becomes too
small to measure.

Heat transfer

Heat can be transferred from one body to another or between a body and the environment by three
different means: conduction, convection and radiation. Conduction is the transfer of energy through a
solid material. Conduction between bodies occurs when they are in direct contact, and molecules
transfer their energy across the interface.

Convection is the transfer of heat to or from a fluid medium. Molecules in a gas or liquid in contact with
a solid body transmit or absorb heat to or from that body and then move away, allowing other
molecules to move into place and repeat the process. Efficiency can be improved by increasing the
surface area to be heated or cooled, as with a radiator, and by forcing the fluid to move over the
surface, as with a fan.

Radiation is the emission of electromagnetic (EM) energy, particularly infrared photons that carry heat
energy. All matter emits and absorbs some EM radiation, the net amount of which determines whether
this causes a loss or gain in heat.

The Carnot cycle

In 1824, Nicolas Léonard Sadi Carnot proposed a model for a heat engine based on what has come to be
known as the Carnot cycle. The cycle exploits the relationships among pressure, volume and
temperature of gasses and how an input of energy can change form and do work outside the system.

Compressing a gas increases its temperature so it becomes hotter than its environment. Heat can then
be removed from the hot gas using a heat exchanger. Then, allowing it to expand causes it to cool. This
is the basic principle behind heat pumps used for heating, air conditioning and refrigeration.
Conversely, heating a gas increases its pressure, causing it to expand. The expansive pressure can then
be used to drive a piston, thus converting heat energy into kinetic energy. This is the basic principle
behind heat engines.

Entropy

All thermodynamic systems generate waste heat. This waste results in an increase in entropy, which for
a closed system is "a quantitative measure of the amount of thermal energy not available to do work,"
according to the American Heritage Dictionary. Entropy in any closed system always increases; it never
decreases. Additionally, moving parts produce waste heat due to friction, and radiative heat inevitably
leaks from the system.

This makes so-called perpetual motion machines impossible. Siabal Mitra, a professor of physics at
Missouri State University, explains, "You cannot build an engine that is 100 percent efficient, which
means you cannot build a perpetual motion machine. However, there are a lot of folks out there who
still don't believe it, and there are people who are still trying to build perpetual motion machines."

Entropy is also defined as "a measure of the disorder or randomness in a closed system," which also
inexorably increases. You can mix hot and cold water, but because a large cup of warm water is more
disordered than two smaller cups containing hot and cold water, you can never separate it back into hot
and cold without adding energy to the system. Put another way, you can’t unscramble an egg or remove
cream from your coffee. While some processes appear to be completely reversible, in practice, none
actually are. Entropy, therefore, provides us with an arrow of time: forward is the direction of increasing
entropy.

The four laws of thermodynamics

The fundamental principles of thermodynamics were originally expressed in three laws. Later, it was
determined that a more fundamental law had been neglected, apparently because it had seemed so
obvious that it did not need to be stated explicitly. To form a complete set of rules, scientists decided
this most fundamental law needed to be included. The problem, though, was that the first three laws
had already been established and were well known by their assigned numbers. When faced with the
prospect of renumbering the existing laws, which would cause considerable confusion, or placing the
pre-eminent law at the end of the list, which would make no logical sense, a British physicist, Ralph H.
Fowler, came up with an alternative that solved the dilemma: he called the new law the “Zeroth Law.” In
brief, these laws are:
The Zeroth Law states that if two bodies are in thermal equilibrium with some third body, then they are
also in equilibrium with each other. This establishes temperature as a fundamental and measurable
property of matter.

The First Law states that the total increase in the energy of a system is equal to the increase in thermal
energy plus the work done on the system. This states that heat is a form of energy and is therefore
subject to the principle of conservation.

The Second Law states that heat energy cannot be transferred from a body at a lower temperature to a
body at a higher temperature without the addition of energy. This is why it costs money to run an air
conditioner.

The Third Law states that the entropy of a pure crystal at absolute zero is zero. As explained above,
entropy is sometimes called "waste energy," i.e., energy that is unable to do work, and since there is no
heat energy whatsoever at absolute zero, there can be no waste energy. Entropy is also a measure of
the disorder in a system, and while a perfect crystal is by definition perfectly ordered, any positive value
of temperature means there is motion within the crystal, which causes disorder. For these reasons,
there can be no physical system with lower entropy, so entropy always has a positive value.

The science of thermodynamics has been developed over centuries, and its principles apply to nearly
every device ever invented. Its importance in modern technology cannot be overstated.

Additional resources

Some of the greatest minds in the history of science have contributed to the development of
thermodynamics. A list of notable pioneers in the field can be found at the University of Waterloo
website.

Energy Education is an interactive curriculum supplement for secondary-school science students.

Eric Weisstein's World of Science contains encyclopedias of astronomy, scientific biography, chemistry
and physics.