Buquoy´s „Fundamental laws of phenomenon of heat” and their meaning

Dalibor Štys and Miroslava Vlačihová

Institute of Physical Biology, University of South Bohemia České Budějovice, Zámek 136, 373 33 Nové Hrady

stys@jcu.cz

The article „Fundamental laws of phemomenon of heat and their meaning (conceived in the spirit of dynamic-mathematic view, without the acceptance of heat impulse“ appeared in the second edition of the book „Sketches of the code book of Nature“ in 1818 [1]. It was several times re-publised, namely in Isis 1825 [2] where the subtitle “based on empirical observations” was added. Hovever, any reflection to Carnot´s work from 1824 [3] is not mentioned. It is extension of pages 195-206 of [1], however, for the full understanding also the pages 165-195 need to be read.

As for the heat itself, the article starts by general description of heat processes. Heat state is proportional to its internal tendency to acquire certain volume in the space, eigenene volumizierung which in its part may be exerted to another body as mitteilende volumisierung. The later may be both negative and positive. Eigene volumizierung may be decreased but its values 0 and negative are only fictive, may not be observed in nature. I modern terms mittheilende volumisierung is approximately mapped to enthalpy and eigene volumisierung to Gibbs energy. This view in itself contains the first law and joint second and first law of thermodynamic. These concepts are further described in detailed and illustrated by Buquoy´s own experiments. One of the conclusion is the indirect observation of absolute temperature and of the third law and correct statement for efficiency of the heat process. The later is described in most general way.

The main technical difference between Buquoys point of view and our contemporary lies in the fact that Buquoy considered heat moments and conservation of moments as the leading tendency. Contemporary themodynamics is energetic. Despite to it, one must admit that in all aspects Buquoy´s view of thermodynamic processes is more general than the textbook one, since it lacks the dominant reference to ideal gas and includes state transitions. In fact all Buquoy´s experiments were done in condensed phase.

For completeness, one should say that the second law is not explicitely mentioned from energetic point of view, but it is mentioned as the general tendency in the nature in the chapter “Combinatorismus” where the general tendency to mixing is clearly distinguished from chemical change. (Chemical change is by Buquoy understood as change in chemical harmony as analogy to resonance of strings. In chemistry, moment is exchanged in distinct amount. Does it sound familiar to quantum mechanics?)

Besides that, in Buquoy´s work is, at least conceptually correctly and mathematically consistently, expressed the equivalence of heat and light radiation and heat conductance.

Is Buquoys themodynamics contemporary? The phenomenological themodynamics – as distinguished from themodynamics based on statistical physics – is not a dead field. The latest big unification comes from the 2001 when the Lieb and Yngvasson article [4] appeared. Certainly the mathematic formalism introduced later is substantially more advanced, Buquoy´s thermodynamics is that of practical physical chemist of condensed phase.

Most contemporary, and exclusive, is Buquoy´s concept of infinite reservoir. This was first re-introduced (uniquely) by MacDonald in 1995 [5] and brings a natural definition of entropy as maximal heat that the system absorbs upon terminating the given state change. In Buquoy we read “ …besides that, it (the metal ball) accepts the same type of calorisation manifestation as the surrounding …without heating it.” According to [4] MacDonald´s theory suffers of unstated assumptions about differentiability of entropy which, however, seems to be the only objection against it. Buquoy used this concept for objective definition of absolute temperature. But we know that - in case that the only adiabatic work is the mechanical one. In the moment-based themodynamics this concept may, actually, be quite natural.

As a general concept, Buquoy considers phenomenon of heat as one of major principles governing the world, besides mechanical movement, field (he discusses gravitation field) and chemical changes. He lists distinctions between these phenomena but also considers analogy between partially elastic collision and thermal phenomena.

What would thermodynamic be if Buquoy´s theories were broadly accepted?

Starting from the end of the above argumentation, we may have had a conceptually different thermodynamic theory which naturally brings about the third law. The experiments would show different absolute zero entropies, there are indices to this notion in [1] and [2]. Joint first and second law, in mathematical expression the Gibbs or Helmholtz energies (well, related moments) would have been used from the very beginning. Would we really need entropy after all? Or, in another words, do we understand macroscopic temperature in description of non-equilibrium energy-based thermodynamics?

In practice, there would never be dominancy of ideal gas state equation in our reasoning. For Buquoy, the (moment) state equation was always unknown function to be determined experimentally. Actually, Buquoy´s experimentally devised state equations did not survive the test of time. As he expected in statement “….as far as we may say with our rather imprecise thermometers….”.

Finally, a bit outside of this article, Buquoy´s view of heat conductance and diffusion is certainly the one which is used in modern textbooks. Highly visionary is his chemistry and theory of light. For all this, his moment-based view of world was of a big help. At least it is interesting reading for critical minds.

References:

[1] G. F. Buquoy, Skizzen zu einem Gesetzbuche der Natur, zu einer sinnigen Auslegung desselben und zu einer hieraus hervorgehenden Charakteristik der Natur, Leipzig: Breitkopf und Härtel (1817, 1825), Leipziger Literaturzeitung (1819), ISIS (1819).

[2] G. F. Buquoy, Versuch einer mathematischen Entwickelung der Fundamentalgesetze der Wärmeerscheinung, wobey diese bloss als Resultate gewisser Actionen betrachtet werden, und kein Wärmestoff vorausgesetz wird, ISIS (1824); Neue Wärmetheorie, dynamisch-mathematisch entwickelt, ohne Annahme eines Wärmestoffs (einer bisher allgemeinen Hypothese), ISIS (1825).

[3] Carnot, Sadi, Réflexions sur la puissance motrice du feu et sur les machines propres à développer cette puissance. Paris: Bachelier. (1824)

[4] E.H. Lieb and J. Yngvasson, The Physics and Mathematics of the Second Law of Thermodynamics. J. Stat. Phys., 103, 509 (2001).

[5] Macdonald, A., A new statement of the second law of thermodynamics. Am. J. Phys. 63, 1122-1127 (1995)