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Laws of thermodynamics

The laws of thermodynamics form an axiomatic basis of thermodynamics. They define


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.