Laws of thermodynamics: Wikis


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Thermodynamic equations
Laws of thermodynamics
Zeroth law
First law
Second law
Third law
Conjugate variables
Thermodynamic potential
Material properties
Maxwell relations
Bridgman's equations
Table of thermodynamic equations

The laws of thermodynamics describe the transport of heat and work in thermodynamic processes. These laws have become some of the most important in all of physics and other types of science associated with thermodynamics.[citation needed]

Classical thermodynamics, which is focused on systems in thermodynamic equilibrium, can be considered separately from non-equilibrium thermodynamics. This article focuses on classical or thermodynamic equilibrium thermodynamics.

The four principles (referred to as "laws"):

The zeroth law of thermodynamics, which underlies the definition of temperature.[1]
The first law of thermodynamics, which mandates conservation of energy, and states in particular that the flow of heat is a form of energy transfer.
The second law of thermodynamics, which states that the entropy of an isolated macroscopic system never decreases, or (equivalently) that perpetual motion machines are impossible.
The third law of thermodynamics, which concerns the entropy of a perfect crystal at absolute zero temperature, and implies that it is impossible to cool a system all the way to exactly absolute zero.

During the last 80 years writers have suggested additional laws, but none of them have become well accepted.


Zeroth law

If two thermodynamic systems are each in thermal equilibrium with a third, then they are in thermal equilibrium with each other.

When two systems, each in its own thermodynamic equilibrium, are put in purely thermal connection, radiative or material, with each other, there will be a net exchange of heat between them unless or until they are in thermal equilibrium. That is the state of having equal temperature. Although this concept of thermodynamics is fundamental, the need to state it explicitly was not widely perceived until the first third of the 20th century, long after the first three principles were already widely in use. Hence it was numbered zero -- before the subsequent three. The Zeroth Law implies that thermal equilibrium, viewed as a binary relation, is a transitive relation. Since a system in thermodynamic equilibrium is defined to be in thermal equilibrium with itself, and, if a system is in thermal equilibrium with another, the latter is in thermal equilibrium with the former. Thermal equilibrium is furthermore an equivalence relation.

First law

Energy can neither be created nor destroyed. It can only change forms.
In any process in an isolated system, the total energy remains the same.
For a thermodynamic cycle the net heat supplied to the system equals the net work done by the system.

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 for a thermodynamic system. It refers to the two ways that a closed system 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, 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 and infinitesimal changes in the energy are exact differentials.

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.


Fundamental thermodynamic relation

The first law can be expressed as the fundamental thermodynamic relation:

Heat supplied to a system = increase in internal energy of the system + work done by the system

Increase in internal energy of a system = heat supplied to the system - work done by the system

dU = TdS - pdV\,

Here, U is internal energy, T is temperature, S is entropy, p is pressure, and V is volume. This is a statement of conservation of energy: The net change in internal energy (dU) equals the heat energy that flows in (TdS), minus the energy that flows out via the system performing work (pdV). the connection with cpis that of great

Second law

The entropy of an isolated system consisting of two regions of space, isolated from one another, each in thermodynamic equilibrium in itself, but not in equilibrium with each other, will, when the isolation that separates the two regions is broken, so that the two regions become able to exchange matter or energy, tend to increase over time, approaching a maximum value when the jointly communicating system reaches thermodynamic equilibrium.

In a simple manner, the second law states "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 appear to flow from cold to hot, for example, when a warm object is cooled in a refrigerator, but the transfer of energy is still from hot to cold. The heat from the object warms the surrounding air, which in turn heats and expands the refrigerant. The refrigerant is then compressed, expending electrical energy.

A way of thinking about the second law for non-scientists is to consider entropy as a measure of ignorance of the microscopic details of the system. So, for example, one has less knowledge about the separate fragments of a broken cup than about an intact one, because when the fragments are separated, one does not know exactly whether they will fit together again, or whether perhaps there is a missing shard. Solid crystals, the most regularly structured form of matter, have very low entropy values; and gases, which are very disorganized, have high entropy values. This is because the positions of the crystal atoms are more predictable than are those of the gas atoms.

The entropy of an isolated macroscopic system never decreases. However, a microscopic system may exhibit fluctuations of entropy opposite to that stated by the Second Law (see Maxwell's demon and Fluctuation Theorem).

Third law

As temperature approaches absolute zero, the entropy of a system approaches a constant minimum.

Briefly, this postulates that entropy is temperature dependent and results in the formulation of the idea of absolute zero.

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[2]. Most fourth law statements, however, are speculative and controversial.

The most commonly proposed Fourth Law is the Onsager reciprocal relations, 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 to evolution. In 1876, thermodynamicist Ludwig Boltzmann 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 as put forward initially by biologist Alfred Lotka in his 1922 article Contributions to the Energetics of Evolution.[3] Most variations of hypothetical fourth laws (or principles) have to do with the environmental sciences, biological evolution, or galactic phenomena.[4]


The first established principle which eventually became the Second Law was formulated by Sadi Carnot during 1824. By 1860, as formalized in the works of those such as Rudolf Clausius and William Thomson, there were two established "principles" of thermodynamics, the first principle and the second principle. As the years passed, these principles were termed "laws." By 1873, for example, thermodynamicist Josiah Willard Gibbs, 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. Some textbooks throughout the 20th century have also numbered the laws slightly differently. In some fields removed from chemistry, the second law was considered to deal with the efficiency of heat engines only, whereas what was called the third law dealt with entropy increases. (And directly defining zero points for entropy calculations was not considered to be a law.) Gradually the older second and third laws have been combined into the second law and the more modern third law has become widely adopted.

See also


  1. ^ Chris Vuille; Serway, Raymond A.; Faughn, Jerry S. (2009). College physics. Belmont, CA: Brooks/Cole, Cengage Learning. pp. 355. ISBN 0-495-38693-6. 
  2. ^ A Proposed 5th Law of Thermodynamics
  3. ^ A.J.Lotka (1922a) 'Contribution to the energetics of evolution' [PDF]. Proc Natl Acad Sci, 8: pp. 147–51.
  4. ^ Morel, R.E. ,Fleck, George. (2006). "Fourth Law of Thermodynamics" Chemistry, Vol. 15, Iss. 4

Further reading

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


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