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as follows:
The adiabatic isolation of the system from the remaining universe requires that the total sum of the entropy
fluctuations vanishes, or:
That is, entropy can only be exchanged between the N systems. This constraint can be used to rearrange the
expression for the total energy fluctuation and obtain:
where
is the temperature of any system j we may choose to single out among the N systems. Finally, equilibrium
Jacobi's theorem, the determinant of a NxN antisymmetric matrix is always zero if N is odd, although for N even we
find that all of the entries must vanish,
at equilibrium. This non-intuitive result means that an odd number of systems are always in equilibrium regardless of
their temperatures and entropy fluctuations, while equality of temperatures is only required between an even number
of systems to achieve equilibrium in the presence of entropy fluctuations.
The zeroth law solves this odd vs. even paradox, because it can readily be used to reduce an odd-numbered system to
an even number by considering any three of the N systems and eliminating one by application of its principle, and
hence reduce the problem to even N which subsequently leads to the same equilibrium condition that we expect in
every case, i.e.,
. The same result applies to fluctuations in any extensive quantity, such as volume
(yielding the equal pressure condition), or fluctuations in mass (leading to equality of chemical potentials). Hence
the zeroth law has implications for a great deal more than temperature alone. In general, we see that the zeroth law
breaks a certain kind of asymmetry present in the First and Second Laws.
Foundation of temperature
The zeroth law establishes thermal equilibrium as an equivalence relationship. An equivalence relationship on a set
(such as the set of thermally equilibrated systems) divides that set into a collection of distinct subsets ("disjoint
subsets") where any member of the set is a member of one and only one such subset. In the case of the zeroth law,
these subsets consist of systems which are in mutual equilibrium. This partitioning allows any member of the subset
to be uniquely "tagged" with a label identifying the subset to which it belongs. Although the labeling may be quite
arbitrary,[5] temperature is just such a labeling process which uses the real number system for tagging. The zeroth
law justifies the use of suitable thermodynamic systems as thermometers to provide such a labeling, which yield any
number of possible empirical temperature scales, and justifies the use of the second law of thermodynamics to
provide an absolute, or thermodynamic temperature scale. Such temperature scales bring additional continuity and
ordering (i.e., "hot" and "cold") properties to the concept of temperature.[3]
In the space of thermodynamic parameters, zones of constant temperature form a surface, that provides a natural
order of nearby surfaces. One may therefore construct a global temperature function that provides a continuous
ordering of states. The dimensionality of a surface of constant temperature is one less than the number of
thermodynamic parameters, thus, for an ideal gas described with three thermodynamic parameters P, V and n, it is a
two-dimensional surface.
For example, if two systems of ideal gases are in equilibrium, then P1V1/N1 = P2V2/N2 where Pi is the pressure in the
ith system, Vi is the volume, and Ni is the amount (in moles, or simply the number of atoms) of gas.
The surface PV/N = const defines surfaces of equal thermodynamic temperature, and one may label defining T so
that PV/N = RT, where R is some constant. These systems can now be used as a thermometer to calibrate other
systems. Such systems are known as "ideal gas thermometers".
History
Temperature has long been known as a quality of heat, for example, to Galileo and to Newton. Carnot took it as a
presupposition for his work. Thermometers may be described as empirical or absolute. Absolute thermometers are
calibrated numerically by the thermodynamic absolute temperature scale. It was not until the middle of the
nineteenth century that absolute thermodynamic temperature was recognized, long after the recognition of empirical
thermometry.
Empirical thermometry recognizes hotness as a fundamental character of temperature and thermometers.[6] [7] [8]
Empirical thermometers are not in general necessarily in exact agreement with each other or with absolute
thermometers as to their numerical scale readings, but to qualify as thermometers at all they must agree with absolute
thermometers and with each other in the following way: given any two bodies isolated in their separate respective
thermodynamic equilibrium states, all thermometers agree as to which of the two has the higher temperature, or that
the two have equal temperatures. For any two empirical thermometers, this does not require that the relation between
their numerical scale readings be linear, but it does require that relation to be strictly monotonic.[9]
Truesdell reports that Rankine wrote in 1853:
Definition of equal temperatures.
Two portions of matter are said to have equal temperatures, when neither tends to communicate heat to the
other.[10]
Discussing the concept of temperature, James Clerk Maxwell in 1872 wrote: "If when two bodies are placed in
thermal communication, one of the two bodies loses heat, and the other gains heat, that body which gives out heat is
said to have a higher temperature than that which receives heat from it." He drew the corollary "If when two bodies
are placed in thermal communication neither of them loses or gains heat, the two bodies are said to have equal
temperatures or the same temperature. The two bodies are then said to be in thermal equilibrium."
Further, Maxwell stated, as the "Law of equal temperatures" the following triviality: "Bodies whose temperatures are
equal to that of the same body have themselves equal temperatures".[11] Maxwell then offered an argument that this
statement was "not a truism". Later in the same text, Maxwell wrote: "Hence the result of the conduction and
radiation of heat from one part of a system to another is to diminish the entropy of the system, or the energy,
available as work, which can be obtained from the system." This statement was surrounded in Maxwell's text by
several others like it that show that it was no slip of the pen. In the same textbook, Maxwell wrote[12] that he was
following Tait in re-defining the word entropy that had been introduced by Clausius. In contrast with what Maxwell
wrote then, Tait had changed his mind by 1884 when in his text he accepted Clausius's original definition of
entropy.[13]
Subsequent writers made statements like Maxwell's. Tait in 1884 wrote "if A is at the same temperature as B and
also at the same temperature as C no transfer of heat takes place between B and C, whatever be these bodies."[14]
A similar statement was made by Max Planck in 1897, not labeled as a law but as an important proposition: "If a
body, A, be in thermal equilibrium with two other bodies, B and C, then B and C are in thermal equilibrium with one
another."[15] Planck repeated this important proposition in the seventh edition of his treatise in 1922.
The title "zeroth law of thermodynamics" began to appear in textbooks to refer to statements of this kind, though
now stripped of their explicit reference to heat; their implicit dependence on the notion of heat could not be removed
The statement of the zeroth law of thermodynamics by Serrin in 1977, though rather mathematically abstract, is more
informative for empirical thermometry: "Zeroth Law - There exists a topological line
which serves as a
coordinate manifold of material behaviour. The points
of the manifold
is
[23]
References
[1] Reif, F. (1965). "Chapter 3: Statistical Thermodynamics". Fundamentals of Statistical and Thermal Physics. New York: McGraw-Hill.
pp.102. ISBN07-051800-9.
[2] Chris Vuille; Serway, Raymond A.; Faughn, Jerry S. (2009). College physics. Belmont, CA: Brooks/Cole, Cengage Learning. pp. 355 (http:/
/ books. google. ca/ books?id=CX0u0mIOZ44C& pg=PT355). ISBN0-495-38693-6.
[3] H.A. Buchdahl (1966). The Concepts of Classical Thermodynamics. Cambridge University Press. p.73.
[4] D. Kondepudi (2008). Introduction to Modern Thermodynamics (http:/ / www. amazon. com/
Introduction-Modern-Thermodynamics-Dilip-Kondepudi). Wiley. p.7. .
[5] J. S. Dugdale (1996, 1998). Entropy and its Physical Interpretation. Tayler & Francis. ISBN9-7484-0569-0.
[6] Mach, E. (1900). Die Principien der Wrmelehre. Historisch-kritisch entwickelt, Johann Ambrosius Barth, Leipzig, section 22, pages 56-57.
[7] Truesdell, C.A. (1980). The Tragicomical History of Thermodynamics, 1822-1854, Springer, New York, ISBN 0-387-90403-4.
[8] Serrin, J. (1986). Chapter 1, 'An Outline of Thermodynamical Structure', pages 3-32, especially page 6, in New Perspectives in
Thermodynamics, edited by J. Serrin, Springer, Berlin, ISBN 3-540-15931-2.
[9] Thomsen, J.S. (1962). A restatement of the zeroth law of thermodynamics, Am. J. Phys. 30: 294-296.
[10] Truesdell, C.A. (1980). The Tragicomical History of Thermodynamics, 1822-1854, Springer, New York, ISBN 0-387-90403-4, page 262.
[11] Maxwell, J.C. (1872). Theory of Heat, third edition, Longmans, Green, London, page 32.
[12] Maxwell, J.C. (1872). Theory of Heat, third edition, Longmans, Green, London, page 186.
[13] Tait, P.G. (1884). Heat, Macmillan, London, Chapters 21-22.
[14] Tait, P.G. (1884). Heat, Macmillan, London, page 40.
[15] Planck, M. (1897/1903). Treatise on Thermodynamics, translated by A. Ogg, Longmans, Green, London, page 2.
[16] Fowler, R., Guggenheim, E.A. (1939/1965). Statistical Thermodynamics. A version of Statistical Mechanics for Students of Physics and
Chemistry, Cambridge University Press, Cambridge UK.
[17] Maxwell, J.C. (1872). Theory of Heat, third edition, Longmans, Green, London, pages 232-233.
[18] Bailyn, M. (1994). A Survey of Thermodynamics, American Institute of Physics Press, New York, ISBN 0-88318-797-3, page 79.
[19] Callen, G.B. (1960/1985). Thermodynamics and an Introduction to Thermostatistics, Wiley, New York.
[20] Truesdell, C., Bharatha, S. (1977). The Concepts and Logic of Classical Thermodynamics as a Theory of Heat Engines, Rigorously
Constructed upon the Foundation Laid by S. Carnot and F. Reech, Springer, New York, ISBN 0-387-07971-8.
[21] Sommerfeld, A. (1951/1955). Thermodynamics and Statistical Mechanics, vol. 5 of Lectures on Theoretical Physics, edited by F. Bopp, J.
Meixner, translated by J. Kestin, Academic Press, New York, page 1.
[22] Guggenheim, E.A. (1949/1967). Thermodynamics. An Advanced Treatment for Chemists and Physicists and Chemists, fifth edition,
North-Holland, Amsterdam, page 8.
[23] Serrin, J. (1978). The concepts of thermodynamics, in Contemporary Developments in Continuum Mechanics and Partial Differential
Equations. Proceedings of the International Symposium on Continuum Mechanics and Partial Differential Equations, Rio de Janiero, August
1977, edited by G.M. de La Penha, L.A.J. Medeiros, North-Holland, Amsterdam, ISBN 0-444-85166-6, pages 411-451.
Further reading
Atkins, Peter (2007). Four Laws That Drive the Universe. New York: Oxford University Press.
ISBN0199232369.
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