Unfortunately, Clausius did not see that his dq, an amount of ‘heat’ energy, initially relatively localized in a thermal reservoir, was transformed in any process that allowed heat to become more spread out in space. Thus, Clausius was observing phase change, but he made no statements about “orderly crystalline substances” being transformed into “disorderly” liquids, an obvious claim for him to make from his observation. Although Clausius described it and his equation of dq rev/T or q rev/T as a “Verwandlung” or “transformation”, he limited it and “disgregation” to discussions of fusion or vaporization where the “disgregation values” changed.
The original definition of entropy (change) involves a transfer of heat from a thermal reservoir to a system via a virtually reversible energy flow process. There is no basis in physical science for interpreting entropy change as involving order and disorder. Then you will understand what entropy ‘really is’.”
#Entropy chemistry how to#
Their response, because it was what had been taught to them, was “Learn how to calculate changes in entropy. They were not concerned with conceptual, non-mathematical answers to the question, “What is entropy, really?” that their students occasionally had the courage to ask. Why should they?īoltzmann’s concept of entropy change was accepted for a century primarily because skilled physicists and thermodynamicists focused on the fascinating relationships and powerful theoretical and practical conclusions arising from entropy’s relation to the behavior of matter. Boltzmann was the source and no one bothered to challenge him. Apparently never having read its astonishingly overly-simplistic basis, they believed that somewhere there was some profound base. Because of it, uncountable thousands of scientists and non-scientists have spent endless hours in thought and argument involving ‘disorder’and entropy in the past century.
That slight, innocent paragraph of a sincere man - but before modern understanding of q rev/T via knowledge of molecular behavior (Boltzmann believed that molecules perhaps could occupy only an infinitesimal volume of space), or quantum mechanics, or the Third Law - that paragraph and its similar nearby words are the foundation of all dependence on “entropy is a measure of disorder”. If liquid water at 273 K, with its 10 1,991,000,000,000,000,000,000,000 accessible microstates (quantized molelcular arrangements) is considered "disorderly", how can ice at 273 K that has 10 1,299,000,000,000,000,000,000,000 accessible microstates be considered "orderly"? Obviously, using such common words is inappropriate in measuring energetic microstates and thus in discussing entropy change conceptually. The common older textbook comparison of orderly crystalline ice to disorderly liquid water is totally deceptive, It is a visual "Boltzmann error" not a proper thermodynamic evaluation. Thus, today we know that no system above 0 K has any "order" in correct thermodynamic descriptions of systems of energetic molecules. When this is the case, then whenever two of more small parts of it come into interaction with each other, the system formed by these parts is also initially in an ordered state and when left to itself it rapidly proceeds to the disordered most probable state.” (Final paragraph of #87, p.
“In order to explain the fact that the calculations based on this assumption correspond to actually observable processes, one must assume that an enormously complicated mechanical system represents a good picture of the world, and that all or at least most of the parts of it surrounding us are initially in a very ordered - and therefore very improbable - state. I have inserted an explanatory clause from the preceding paragraph in brackets, and put in italics Boltzmann’s surprisingly naïve assumptions about all or most initial states as “ordered”.) (The preceding and following phrases and sentences, disappointingly, only expand on it or support it without additional meaningful technical details or indications of Boltzmann’s thought processes. The key paragraph should be quoted in full. The important question is “what are the bases for Boltzmann’s introduction of order to disorder as a key to understanding spontaneous entropy change?” That 1898 idea came from two to three pages of a conceptual description, a common language summary, that follow over 400 pages of detailed theory in Brush’s translation of Boltzmann’s 1896-1898 “Lectures on Gas Theory” (University of California Press, 1964). Planck’s nobility in allowing R/N to be called ‘Boltzmann’s constant’, k B, was uncharacteristic of most scientists of that day, as well as now. LnW \), and subsequently carved on Boltzmann’s tombstone.
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