The laws of thermodynamics are a set of scientific laws which define a group of physical quantities, such as temperature, energy, and entropy, that characterize thermodynamic systems in thermodynamic equilibrium. The laws also use various parameters for thermodynamic processes, such as thermodynamic work and heat, and establish relationships between them. They state empirical facts that form a basis of precluding the possibility of certain phenomena, such as perpetual motion. In addition to their use in thermodynamics, they are important fundamental laws of physics in general and are applicable in other natural sciences. Traditionally, thermodynamics has recognized three fundamental laws, simply named by an ordinal identification, the first law, the second law, and the third law. A more fundamental statement was later labelled as the zeroth law after the first three laws had been established. The zeroth law of thermodynamics defines thermal equilibrium and forms a basis for the definition of temperature: if two systems are each in thermal equilibrium with a third system, then they are in thermal equilibrium with each other. The first law of thermodynamics states that, when energy passes into or out of a system (as work, heat, or matter), the system's internal energy changes in accordance with the law of conservation of energy. This also results in the observation that, in an externally isolated system, even with internal changes, the sum of all forms of energy must remain constant, as energy cannot be created or destroyed. The second law of thermodynamics states that in a natural thermodynamic process, the sum of the entropies of the interacting thermodynamic systems never decreases. A common corollary of the statement is that heat does not spontaneously pass from a colder body to a warmer body. The third law of thermodynamics states that a system's entropy approaches a constant value as the temperature approaches absolute zero. With the exception of non-crystalline solids (glasses), the entropy of a system at absolute zero is typically close to zero. The first and second laws prohibit two kinds of perpetual motion machines, respectively: the perpetual motion machine of the first kind which produces work with no energy input, and the perpetual motion machine of the second kind which spontaneously converts thermal energy into mechanical work.
History
The history of thermodynamics is fundamentally interwoven with the history of physics and the history of chemistry, and ultimately dates back to theories of heat in antiquity. The laws of thermodynamics are the result of progress made in this field over the nineteenth and early twentieth centuries. The first established thermodynamic principle, which eventually became the second law of thermodynamics, was formulated by Sadi Carnot in 1824 in his book Reflections on the Motive Power of Fire. By 1860, as formalized in the works of scientists such as Rudolf Clausius and William Thomson, what are now known as the first and second laws were established. Later, Nernst's theorem (or Nernst's postulate), which is now known as the third law, was formulated by Walther Nernst over the period 1906–1912. While the numbering of the laws is universal today, various textbooks throughout the 20th century have numbered the laws differently. In some fields, 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. Gradually, this resolved itself and a zeroth law was later added to allow for a self-consistent definition of temperature. Additional laws have been suggested, but have not achieved the generality of the four accepted laws, and are generally not discussed in standard textbooks.
Zeroth law The zeroth law of thermodynamics provides for the foundation of temperature as an empirical parameter in thermodynamic systems and establishes the transitive relation between the temperatures of multiple bodies in thermal equilibrium. The law may be stated in the following form:
If two systems are both in thermal equilibrium with a third system, then they are in thermal equilibrium with each other. Though this version of the law is one of the most commonly stated versions, it is only one of a diversity of statements that are labeled as "the zeroth law". Some statements go further, so as to supply the important physical fact that temperature is one-dimensional and that one can conceptually arrange bodies in a real number sequence from colder to hotter. These concepts of temperature and of thermal equilibrium are fundamental to thermodynamics and were clearly stated in the nineteenth century. The name 'zeroth law' was invented by Ralph H. Fowler in the 1930s, long after the first, second, and third laws were widely recognized. The law allows the definition of temperature in a non-circular way without reference to entropy, its conjugate variable. Such a temperature definition is said to be 'empirical'.
First law
The first law of thermodynamics is a version of the law of conservation of energy, adapted for thermodynamic processes. In general, the conservation law states that the total energy of an isolated system is constant; energy can be transformed from one form to another, but can be neither created nor destroyed.
In a closed system (i.e. there is no transfer of matter into or out of the system), the first law states that the change in internal energy of the system (ΔUsystem) is equal to the difference between the heat supplied to the system (Q) and the work (W) done by the system on its surroundings. (Note, an alternate sign convention, not used in this article, is to define W as the work done on the system by its surroundings): Δ U s y s t e m = Q − W . {\displaystyle \Delta U_{\rm {system}}=Q-W.}
For processes that include the transfer of matter, a further statement is needed.
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