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Laws of thermodynamics



 
 
The laws of thermodynamics, in principle, describe the specifics for the transport of heat
Heat

In physics and thermodynamics, heat is any transfer of energy from one body or thermodynamic system to another due to a difference in temperature....
 and work
Work (thermodynamics)

In thermodynamics, work is the quantity of energy transferred from one system to another without an accompanying transfer of entropy. It is a generalization of the concept of mechanical work in mechanics....
 in thermodynamic processes
Thermodynamic processes

A thermodynamic process may be defined as the energetic evolution of a thermodynamic system proceeding from an initial state to a final state. Paths through the space of thermodynamic variables are often specified by holding certain thermodynamic variables constant....
. Since their inception, however, these law
Physical law

A physical law or scientific law is a scientific generalization based on empiricism observations of physical behavior . Laws of nature are observable....
s have become some of the most important in all of physics
Physics

Physics is the natural science which examines basic concepts such as energy, force, and spacetime and all that derives from these, such as mass, charge, matter and its Motion ....
 and other branches of science
Science

In its broadest sense, science refers to any systematic knowledge or practice. In its more usual restricted sense, science refers to a system of acquiring knowledge based on scientific method, as well as to the organized body of knowledge gained through such research....
 connected to thermodynamics
Thermodynamics

In physics, thermodynamics is the study of the conversion of heat energy into different forms of energy ; different energy conversions into heat energy; and its relation to macroscopic variables such as temperature, pressure, and volume....
.

There are generally considered to be four laws:

Over the last 80 years or so, occasionally, various writers have suggested additional Laws, but none of them have been widely accepted.

two systems are put in contact with each other, there will be a net exchange of energy
Energy

In physics, energy is a scalar physical quantity that describes the amount of Work_ that can be performed by a force. Energy is an attribute of objects and systems that is subject to a conservation law....
 between them unless or until they are in thermal equilibrium, that is, they are at the same temperature.






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The laws of thermodynamics, in principle, describe the specifics for the transport of heat
Heat

In physics and thermodynamics, heat is any transfer of energy from one body or thermodynamic system to another due to a difference in temperature....
 and work
Work (thermodynamics)

In thermodynamics, work is the quantity of energy transferred from one system to another without an accompanying transfer of entropy. It is a generalization of the concept of mechanical work in mechanics....
 in thermodynamic processes
Thermodynamic processes

A thermodynamic process may be defined as the energetic evolution of a thermodynamic system proceeding from an initial state to a final state. Paths through the space of thermodynamic variables are often specified by holding certain thermodynamic variables constant....
. Since their inception, however, these law
Physical law

A physical law or scientific law is a scientific generalization based on empiricism observations of physical behavior . Laws of nature are observable....
s have become some of the most important in all of physics
Physics

Physics is the natural science which examines basic concepts such as energy, force, and spacetime and all that derives from these, such as mass, charge, matter and its Motion ....
 and other branches of science
Science

In its broadest sense, science refers to any systematic knowledge or practice. In its more usual restricted sense, science refers to a system of acquiring knowledge based on scientific method, as well as to the organized body of knowledge gained through such research....
 connected to thermodynamics
Thermodynamics

In physics, thermodynamics is the study of the conversion of heat energy into different forms of energy ; different energy conversions into heat energy; and its relation to macroscopic variables such as temperature, pressure, and volume....
.

There are generally considered to be four laws:
  • The zeroth law of thermodynamics
    Zeroth law of thermodynamics

    In physics and physical chemistry, the zeroth law of thermodynamics is a generalization about the thermal equilibrium between bodies, or thermodynamic systems, in contact....
    , which underlies the definition of temperature.
  • The first law of thermodynamics
    First law of thermodynamics

    In thermodynamics, the first law of thermodynamics is an expression of the more universal physical law of the conservation of energy. Succinctly, the first law of thermodynamics states:...
    , which mandates conservation of energy
    Conservation of energy

    The law of conservation of energy states that the total amount of energy in an isolated system remains constant. A consequence of this law is that energy cannot be created or destroyed....
    , and states in particular that heat
    Heat

    In physics and thermodynamics, heat is any transfer of energy from one body or thermodynamic system to another due to a difference in temperature....
     is a form of energy.
  • The second law of thermodynamics
    Second law of thermodynamics

    The second law of thermodynamics is an expression of the universal law of increasing entropy, stating that the entropy of an isolated system which is not in Thermodynamic equilibrium will tend to increase over time, approaching a maximum value at equilibrium....
    , which states that the entropy
    Entropy

    In many branches of science, entropy is a measure of the disorder of a system. The concept of entropy is particularly notable as it is applied across physics, information theory and mathematics....
     of the universe always increases, or (equivalently) that perpetual motion machines are impossible.
  • The third law of thermodynamics
    Third law of thermodynamics

    The third law of thermodynamics is a statistical law of nature regarding entropy and the impossibility of reaching absolute zero of temperature....
    , which concerns the entropy of an object at absolute zero
    Absolute zero

    Absolute zero is a temperature marked by a 0 entropy configuration. It is the coldest temperature theoretically possible, and cannot be reached, by artificial or natural means....
     temperature, and implies that it is impossible to cool a system all the way to exactly absolute zero.


Over the last 80 years or so, occasionally, various writers have suggested additional Laws, but none of them have been widely accepted.

Zeroth law


When two systems are put in contact with each other, there will be a net exchange of energy
Energy

In physics, energy is a scalar physical quantity that describes the amount of Work_ that can be performed by a force. Energy is an attribute of objects and systems that is subject to a conservation law....
 between them unless or until they are in thermal equilibrium, that is, they are at the same temperature. While this is a fundamental concept of thermodynamics, the need to state it explicitly as a law was not perceived until the first third of the 20th century, long after the first three laws were already widely in use, hence the zero numbering. The Zeroth Law asserts that thermal equilibrium, viewed as a binary relation
Binary relation

In mathematics, a binary relation is an arbitrary association of elements within a set or with elements of another set.An example is the "divides" relation between the set of prime numbers P and the set of integers Z, in which every prime p is associated with every integer z that is a divisibility of p, and no othe...
, is an equivalence relation
Equivalence relation

In mathematics, an equivalence relation is, loosely, a binary relation on a Set that specifies how to split up the set into subsets such that every element of the larger set is in exactly one of the subsets....
.

First law



The First Law states that energy cannot be created or destroyed; rather, the amount of energy lost in a steady state process cannot be greater than the amount of energy gained. This is the statement of conservation of energy
Conservation of energy

The law of conservation of energy states that the total amount of energy in an isolated system remains constant. A consequence of this law is that energy cannot be created or destroyed....
 for a thermodynamic system
Thermodynamic system

In thermodynamics, a thermodynamic system, originally called a working substance, is defined as that part of the universe that is under consideration....
. It refers to the two ways that a closed system
Closed system

A closed system is a system in the state of being isolated from its surrounding. It is often used to refer to a theoretical system where perfect closure is an assumption, however in practice no system can be completely closed; there are only varying degrees of closure....
 transfers energy to and from its surroundings - by the process of heating (or cooling) and the process of mechanical work. The rate of gain or loss in the stored energy of a system is determined by the rates of these two processes. In open systems, the flow of matter is another energy transfer mechanism, and extra terms must be included in the expression of the first law.

The First Law clarifies the nature of energy. It is a stored quantity which is independent of any particular process path, i.e., it is independent of the system history. If a system undergoes a thermodynamic cycle
Thermodynamic cycle

A thermodynamic cycle is a series of thermodynamic processes transferring heat and work, while varying pressure, temperature, and other state variables, eventually returning a system to its initial state....
, whether it becomes warmer, cooler, larger, or smaller, then it will have the same amount of energy each time it returns to a particular state. Mathematically speaking, energy is a state function
State function

In thermodynamics, a state function, state quantity, or a function of state, is a physical quantity of a system that depends only on the current Thermodynamic state, not on the way in which the system got to that state....
 and infinitesimal changes in the energy are exact differential
Exact differential

In mathematics, a differential dQ is said to be exact, as contrasted with an inexact differential, if the differentiable function Q exists....
s.

All laws of thermodynamics but the First are statistical and simply describe the tendencies of macroscopic systems. For microscopic systems with few particles, the variations in the parameters become larger than the parameters themselves, and the assumptions of thermodynamics become meaningless. The First Law, i.e. the law of conservation, has become the most secure of all basic laws of science. At present, it is unquestioned.

Fundamental Thermodynamic Relation

The first law can be expressed as the Fundamental Thermodynamic Relation:

Here, E is internal energy
Internal energy

In thermodynamics, the internal energy of a thermodynamic system, or a physical body with well-defined dimension, denoted by U, or sometimes E, is the total of the kinetic energy due to the motion of molecules and the potential energy associated with the vibrational and electricity energy of atoms within molecules or crysta...
, T is temperature
Temperature

In physics, temperature is a physical property of a Physical system that underlies the common notions of hot and cold; something that feels hotter generally has the greater temperature....
, S is entropy
Entropy

In many branches of science, entropy is a measure of the disorder of a system. The concept of entropy is particularly notable as it is applied across physics, information theory and mathematics....
, p is pressure
Pressure

Pressure is the force per unit area applied to an object in a direction surface normal to the surface. Gauge pressure is the pressure relative to the local atmospheric or ambient pressure....
, and V is volume
Volume

The volume of any solid, liquid, plasma, vacuum or theoretical object is how much three-dimensional space it occupies, often quantified numerically....
. This is a statement of conservation of energy: The net change in internal energy (dE) equals the heat energy that flows in (TdS), minus the energy that flows out via the system performing work (pdV).

Second law


In a simple manner, the second law states that "energy systems have a tendency to increase their entropy" rather than decrease it. This can also be stated as "heat can spontaneously flow from a higher-temperature region to a lower-temperature region, but not the other way around." (Heat can flow from cold to hot, but not spontaneously—for example, a refrigerator requires electricity.)

A way of looking at the second law for non-scientists is to look at entropy as a measure of disorder. So, for example, a broken cup has less order than an intact one. Likewise, solid crystals, the most organized form of matter, have very low entropy values; and gas
Gas

In physics, a gas is a state of matter, consisting of a collection of particles without a definite shape or volume that are in more or less random motion....
es, which are highly disorganized, have high entropy values.

The entropy
Entropy

In many branches of science, entropy is a measure of the disorder of a system. The concept of entropy is particularly notable as it is applied across physics, information theory and mathematics....
 of a thermally isolated macroscopic system never decreases. However, a microscopic system may exhibit fluctuations of entropy opposite to that dictated by the Second Law (see Maxwell's demon
Maxwell's demon

Maxwell's demon was an 1867 thought experiment by the Scotland physicist James Clerk Maxwell, meant to raise questions about the possibility of violating the second law of thermodynamics....
 and Fluctuation Theorem
Fluctuation theorem

The fluctuation theorem is a theorem from statistical mechanics dealing with the relative probability that the entropy of a system which is currently away from thermodynamic equilibrium will increase or decrease over a given amount of time....
).

Third law


In brief, this postulates that entropy is temperature dependent and leads to the formulation of the idea of absolute zero
Absolute zero

Absolute zero is a temperature marked by a 0 entropy configuration. It is the coldest temperature theoretically possible, and cannot be reached, by artificial or natural means....
.

Tentative fourth laws or principles

Over the years, various thermodynamic researchers have come forward to ascribe to or to postulate potential fourth laws of thermodynamics (either suggesting that a widely-accepted principle should be called the fourth law, or proposing entirely new laws); in some cases, even fifth or sixth laws of thermodynamics are proposed. Most fourth law statements, however, are speculative and far from agreed upon.

The most commonly proposed Fourth Law is the Onsager reciprocal relations
Onsager reciprocal relations

In thermodynamics, the Onsager reciprocal relations express the equality of certain relations between fluxs and forces in thermodynamic systems out of equilibrium , but where a notion of local thermodynamic equilibrium exists....
, which give a quantitative relation between the parameters of a system in which heat and matter are simultaneously flowing.

Other tentative fourth law statements are attempts to apply thermodynamics
Thermodynamics

In physics, thermodynamics is the study of the conversion of heat energy into different forms of energy ; different energy conversions into heat energy; and its relation to macroscopic variables such as temperature, pressure, and volume....
 to evolution
Evolution

In biology, evolution is change in the heritability trait of a population of organisms from one generation to the next. These changes are caused by a combination of three main processes: variation, reproduction, and selection....
. In the late 19th century, thermodynamicist Ludwig Boltzmann
Ludwig Boltzmann

Ludwig Eduard Boltzmann was an Austrian physicist famous for his founding contributions in the fields of statistical mechanics and statistical thermodynamics....
 argued that the fundamental object of contention in the life-struggle in the evolution of the organic world is 'available energy'. Another example is the maximum power principle
Maximum power principle

The maximum power principle has been proposed as the fourth Principles of energetics in Open system thermodynamics, where an example of an open system is a biological cell....
 as put forward initially by biologist Alfred Lotka in his 1922 article Contributions to the Energetics of Evolution. Most variations of hypothetical fourth laws (or principles) have to do with the environmental sciences, biological evolution, or galactic phenomena.

History

The first established principle which eventually became the Second Law
Second law of thermodynamics

The second law of thermodynamics is an expression of the universal law of increasing entropy, stating that the entropy of an isolated system which is not in Thermodynamic equilibrium will tend to increase over time, approaching a maximum value at equilibrium....
 was formulated by Sadi Carnot
Nicolas Léonard Sadi Carnot

Nicolas L?onard Sadi Carnot was a France physicist and military engineer who, in his 1824 Reflections on the Motive Power of Fire, gave the first successful theoretical account of heat engines, now known as the Carnot cycle, thereby laying the foundations of the second law of thermodynamics....
 in 1824. By 1860, as found in the works of those such as Rudolf Clausius
Rudolf Clausius

Rudolf Julius Emanuel Clausius , was a Germany physicist and mathematician and is considered one of the central founders of the science of thermodynamics....
 and William Thomson
William Thomson, 1st Baron Kelvin

William Thomson, 1st Baron Kelvin , Order of Merit , Royal Victorian Order, Privy Council of the United Kingdom, Presidents of the Royal Society, Royal Society of Edinburgh, was an Ireland-born United Kingdom of Great Britain and Ireland Mathematical physics and engineer....
, there were two established "principles" of thermodynamics, the first principle and the second principle. As the years passed, these principles turned into "laws." By 1873, for example, thermodynamicist Josiah Willard Gibbs
Josiah Willard Gibbs

Josiah Willard Gibbs was an American theoretical physicist, chemist, and mathematician. One of the greatest American scientists of all time, he devised much of the theoretical foundation for chemical thermodynamics as well as physical chemistry....
, in his “Graphical Methods in the Thermodynamics of Fluids”, clearly stated that there were two absolute laws of thermodynamics, a first law and a second law.

See also

  • Conservation law
    Conservation law

    In physics, a conservation law states that a particular measurable property of an isolated physical system does not change as the system evolves....
  • Heat death of the universe
    Heat death of the universe

    The heat death is a possible Fate of the universe, in which it has "Entropy" to a state of no thermodynamic free energy to sustain motion or life....
  • Laws of science
  • Philosophy of thermal and statistical physics
    Philosophy of thermal and statistical physics

    The philosophy of thermal and statistical physics is that part of the philosophy of physics whose subject matter is classical thermodynamics, statistical mechanics, and related theories....
  • Table of thermodynamic equations
    Table of thermodynamic equations

    The following page is a concise list of common thermodynamic equations and quantities:...


Further reading

  • Goldstein, Martin, and Inge F., 1993. The Refrigerator and the Universe. Harvard Univ. Press. A gentle introduction.