Unsuccessful thermodynamic treatment of heat conduction and resistance heating led William Thomson, later Lord Kelvin, to neglect these irreversible processes and still get satisfactory results for thermoelectric phenomena.
APPLICATION of the second law of thermodynamics in its classical form requires that the heat of each process be convertible into work; that is, each process must be reversible. Since no real system meets this criterion, analysis is then made in terms of some imaginary limiting case in which the parameters have been adjusted to make the irreversible effects negligible. It is sometimes impossible, however, to imagine a limit in which the irreversible processes can be disregarded. This problem was first faced by William Thomson (later Lord Kelvin) in his thermoelectric researches. His dilemma was this: Even if he did ignore the irreversible processes, he found he could still apply the second law with what seemed to be very satisfactory results. This dilemma was sufficiently interesting to excite some of the best theoretical and experimental minds over the century that was to follow Thomson’s work.
References
1. T. J. Seebeck, Abhand. dent. Akad. Wiss. Berlin, p. 265 (1822–23); Ann. Physik 6, 1, 133 (1826); https://doi.org/ANPYA2 Ostwald Klassiker 70, Leipzig (1895).
2. Ibid, (Abhandhmgen) pp. 316, 353.
3. J. Cumming, Thomson’s Annals of Philosophy 6, 321 (1823).
9. J. P. Joule, W. Thomson, Proc. Roy. Soc. 7, 127 (1855); J. P. Joule, W. Thomson, Phil. Trans. Roy. Soc. 144, 321 (1854); J. P. Joule, W. Thomson, Ann. Chim. Phys. 65, 244 (1862); https://doi.org/ACPHAA W. Thomson, Mathematical and Physical Papers I, Cambridge (1882) p. 357, 433.
10. W. Thomson, Proc. Roy. Soc. Edin. 3, 91 (1857); https://doi.org/PRSEAE W. Thomson, Phil. Mag. 3, 529 (1852); https://doi.org/PHMAA4 Mathematical and Physical Papers I, Cambridge (1882) p. 316.
11. W. Thomson, Mathematical and Physical Papers I, Cambridge (1882), p. 319.
12. Ibid, p. 321.
13. W. Thomson, Proc. Roy. Soc. 7, 49 (1855); W. Thomson, Phil. Mag. 8, 62 (1854); https://doi.org/PHMAA4 Op cit, ref. 11, p. 460.
14. W. Thomson, Proc. Roy. Soc. 8, 50 (1856–67); W. Thomson, Phil. Trans. Roy. Soc. 146, 649 (1856); W. Thomson, Phil. Mag. 12, 393 (1856); https://doi.org/PHMAA4 W. Thomson, Ann. Chim. Phys. 54, 105 (1858); https://doi.org/ACPHAA Mathematical and Physical Papers II, Cambridge (1884) p. 189, 396.
15. W. Thomson, Mathematical and Physical Papers II, Cambridge (1884), p. 219.
16. Op cit ref. 10.
17. W. Thomson, Proc. Roy. Soc. Edin. 3, 255, (1857); https://doi.org/PRSEAE W. Thomson, Trans. Roy. Soc. Edin. 21, 123, (1857); W. Thomson, Phil. Mag. 11, 214, 281, (1856); https://doi.org/PHMAA4 Op cit, ref. 11, p. 232, 324.
18. Op cit, ref. 11, p. 250.
19. Ibid, p. 318.
20. H. A. Lorentz, Verslagen en Mendedeelingen der Koninklijke Akademie van Weltenschappen 1, 327 (1885); H. A. Lorentz, Arch Néerl. 20, 129 (1886).
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