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Jun 09, 2016

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3 laws of thermodynamics

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3 laws of thermodynamics

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fundamental physical quantities, such as temperature, energy, and entropy, to describe

thermodynamic systems and describe the transport and conversion of heat and work in

thermodynamic processes.

The four principles, or laws, of thermodynamics are:[1][2][3][4][5][6]

The zeroth law of thermodynamics provides a basic definition of empirical temperature

based on the principle of thermal equilibrium.

The first law of thermodynamics mandates conservation of energy and states in particular

that the flow of heat is a form of energy transfer.

The second law of thermodynamics states that the entropy of an isolated macroscopic

system never decreases, or, equivalently, that perpetual motion machines are impossible.

The third law of thermodynamics concerns the entropy of a perfect crystal at absolute

zero temperature, and implies that it is impossible to cool a system to exactly absolute

zero.

Classical thermodynamics describes the thermal interaction of systems that are individually in a

state of thermodynamic equilibrium. Thermal equilibrium is a statistical condition of

macroscopic systems, while microscopically all systems undergo random fluctuations. The laws

of thermodynamics are strictly valid only in the thermodynamic limit when a macroscopic

system may be described practically by an infinite number of microscopic states to satisfy the

laws of statistics. Every finite system will exhibit statistical fluctuations in their thermodynamic

parameters (entropy, temperature, pressure, etc.), but these are negligible for macroscopic

systems, only becoming important for microscopic systems.

Zeroth law

The zeroth law of thermodynamics may be stated as follows:

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

in thermal equilibrium with each other.

When two systems, each internally in thermodynamic equilibrium at a different temperature, are

brought in diathermic contact with each other they exchange heat to establish a thermal

equilibrium between each other.

The zeroth law implies that thermal equilibrium, viewed as a binary relation, is a transitive

relation. Thermal equilibrium is furthermore an equivalence relation between any number of

system. The law is also a statement about measurability. To this effect the law allows the

establishment of an empirical parameter, the temperature, as a property of a system such that

systems in equilibrium with each other have the same temperature. The notion of transitivity

permits a system, for example a gas thermometer, to be used as a device to measure the

temperature of another system.

Although the concept of thermodynamic equilibrium is fundamental to thermodynamics, the

need to state it explicitly as a law was not widely perceived until Fowler and Planck stated it in

the 1930s, long after the first, second, and third law were already widely understood and

recognized. Hence it was numbered the zeroth law. The importance of the law as a foundation to

the earlier laws is that it defines temperature in a non-circular logistics without reference to

entropy, its conjugate variable.

First law

The first law of thermodynamics may be stated as in several ways:

Energy can be neither 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 of thermodynamics 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

processes of heat and 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. For processes in an isolated system, it is a conserved

quantity that is independent of any particular process path, meaning it is independent of the

system history. If an isolated system undergoes a thermodynamic cycle, whether it becomes

warmer, cooler, larger, or smaller, then it has the same amount of energy each time it returns to a

particular state. Energy is a state function, and infinitesimal changes in the energy are exact

differentials with respect to differentials of variables of state.

The first law may be expressed by several forms of the fundamental thermodynamic relation:

Increase in internal energy of a system = heat supplied to the system + work done on the

system

where U is the internal energy, Q is heat and W is work. The definition of the work is also often

given in terms of the work performed by a system on its surroundings.

This is a statement of conservation of energy. The net change in internal energy is the energy that

flows in as heat minus the energy that flows out as the work that the system performs on it

environment.

This is also often stated as a definition of the amount of heat of a process:

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

system

The definition of work and its sign is a matter of convention in particular fields of science. In

either case, a resulting increase of the internal energy of a system is represented by a positive

amount of work. The energy Q (heat) is the product of the temperature (T) and it conjugate

variable entropy (S), Q = TdS, and similarly work is the product of pressure (p) with volume (V)

change, W = -pdV. The internal energy then may be written as

Second law

The second law of thermodynamics may be summarized as follows:

When two isolated systems in separate but nearby regions of space, each in thermodynamic

equilibrium in itself, but not in equilibrium with each other at first, are at some time allowed to

interact, breaking the isolation that separates the two systems, and they exchange matter or

energy, they will eventually reach a mutual thermodynamic equilibrium. The sum of the

entropies of the initial, isolated systems is less than or equal to the entropy of the final

exchanging systems. In the process of reaching a new thermodynamic equilibrium, entropy has

increased, or at least has not decreased.

It follows that the entropy of an isolated macroscopic system never decreases. The second law

states that spontaneous natural processes increase entropy overall, or in another formulation that

heat can spontaneously flow only from a higher-temperature region to a lower-temperature

region, but not the other way around.

The second law defines entropy, which may be described as a measure of deficiency of

information, or uncertainty, about the microscopic details of the motion and configuration of the

system, given only predictable reproducibility of bulk or macroscopic behavior as specified by

macroscopic variables. For example, one has less knowledge about the separate fragments of a

broken cup than about an intact cup, 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.

Crystals, the most regularly structured form of matter, with considerable predictability of

microscopic configuration, as well as predictability of bulk behavior, have small values of

entropy; and gases, which behave predictably in bulk even when their microscopic motions are

unknown, have high entropy.

Third law

The third law of thermodynamics is usually stated as follows:

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

History

See also: Philosophy of thermal and statistical physics

In about 1797, Benjamin Thompson showed that mechanical action can generate indefinitely

large amounts of heat, so challenging the caloric theory. The historically first established

thermodynamic principle which eventually became the second law of thermodynamics was

formulated by Sadi Carnot during 1824. By 1860, as formalized in the works of those such as

Rudolf Clausius and William Thomson, two established principles of thermodynamics had

evolved, the first principle and the second principle, later restated as thermodynamic laws. By

1873, for example, thermodynamicist Josiah Willard Gibbs, in his memoir Graphical Methods in

the Thermodynamics of Fluids, clearly stated the first two absolute laws of thermodynamics.

Some textbooks throughout the 20th century have numbered the laws 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. Directly

defining zero points for entropy calculations was not considered to be a law. Gradually, this

separation was combined into the second law and the modern third law was widely adopted.

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