Physicists usually regard Boltzmann's statistical theory as a scheme to establish the connection from the dynamics of the basic process to the thermodynamics of the statistical system, but this scheme has not been able to give complete results, and its scope of application has always been ambiguous. This leads to the conflict between the two theoretical systems on the view of nature, in physics, we have been unable to establish the relations on the concepts of the direction of changes and time between dynamics and thermodynamics, the former describes to us a world without evolution, and the latter expresses the evolution as the unfolding of the second law. Since the explanation of thermodynamic probability cannot be applied to describe the direction of microscopic state change, this means that there will be no irreversibility in dynamics in the sense of the second law. The explanation of the state of thermodynamic probability further revealed the contradictory that the description about the direction of changes and time in thermodynamics and dynamics are different. Looking back to the second point, is this really saying that the activities of non-ideal solutions were inadequately being modeled?Īnother problem is: since there has been no monotonous function similar to thermodynamic entropy in dynamics, the general mathematical properties of the fundamental laws of dynamics (inversion symmetry) indicate that the dynamic "changes" are reversible.
That is, the point of concern isn't about the activities per se, but that the rate constant is found to variable (not constant) in that situation. Perhaps though the key is in the previous sentence which states that "the corresponding rate-constant will then be independent of composition" is the problem. For part one, I must confess I don't quite follow why the term misconceived was used - the discussion of Dr. one would be better served by using the concentration approach. Given the state of computing, data availability, analytic techniques, etc. I would suggest that this second part may have been the key take-home point at the time. At the risk of not adding a lot to the conversation and speculating about someone's thought process, an possibly being spectacularly wrong, I will point out the final bit of the Danckwerts quote has two parts: 1) This formulation is misconceived in principle and 2) and in practice the use of concentrations usually leads to somewhat better results that the use of activities.
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