Chemical Thermodynamics in the Real World

Chemical Thermodynamics in the Real World
The opening page Journal of Chemical & Engineering News 5 Apr 1971 four-page article reprint of American chemical engineer and physical chemist Frederick Rossini's 29 March “Chemical Thermodynamics in the Real World” Priestley Medal Address, wherein he applies chemical thermodynamics to explain freedom and security of people in society. [1]
In famous publications, “Chemical Thermodynamics in the Real World” is a 1971 Priestley Medal Address—the precipitate to the 2006 to present Rossini debate—given by American chemical engineer, physical chemist, and Gilbert Lewis protege Frederick Rossini, wherein he argues, using the combined law of thermodynamics, equilibrium constant, and internal energy atomic binding forces descriptions, that the interplay between enthalpy and entropy explain the paradox between freedom and security in society.

Overview
The following is Rossin's opening abstract: [1]

“For my talk this evening, I have selected the subject ‘Chemical Thermodynamics in the Real World, because it represents an area in which I have worked a great deal and because it relates to present-day problems of our society. I will try to show that thermodynamics is a discipline highly relevant to the real world in which we live and that its fundamental laws may be related to human experience.”

In opening his physicochemical sociology [PCS] argument, following a short discussion on the thermodynamics of fuel cells and synthetic diamonds, Rossini explains the connection between internal energy and society in the following way; shown with added [PCS] insert clarifications:

“A simple description of energy is that the energy of a [social] system arises from the binding forces [exchange forces] that hold together the elementary particles—nuclei, ions, atoms, molecules, and macromolecules [people]—constituting the system. The greater the binding forces, the more tightly bound is the system, and the lower is its energy. This corresponds to a state of greater [interpersonal or socioeconomic] security. The smaller the binding forces, the less tightly bound is the system, and the higher is its energy. This corresponds to a system of lesser [interpersonal or socioeconomic] security.”

In short, Rossini goes through an example wherein he compares people to hydrogen molecules, according to which the association (H2) and disassociation (H + H) reaction of hydrogen molecules into their atoms:

 \text{H:H} \rightleftharpoons H + H \,

has an equilibrium constant K the value of which determines the point when the reaction process stops and the forward and reverse reactions occur equally in both directions, which corresponds to time periods of socio-economic equilibrium or the ‘end of a socioeconomic process’ as Vilfredo Pareto saw it, or as British-French economist Alan Kirman put it in 1987 ‘Pareto regarded equilibrium as the termination point of a process … The time taken for this process is not specified but it certainly is not regarded as … as negligible.’ [3]

In 1935, a similar example, to note, was done by American physiologist Lawrence Henderson, wherein, building on the work of Pareto, mixed with the chemical thermodynamics work of American engineer Willard Gibbs, goes through a comparison of the equilibrium properties of the following liquid phase chemical reaction, namely of reactants carbonic acid H2CO3 with disodium phosphate Na2HPO4 to form the products of sodium bicarbonate NaHCO3 and monosodium phosphate NaH2PO4:

 H_2CO_3 + Na_2HPO_4 \rightleftharpoons NaHCO_3 + NaH_2PO_4 \,

to that of the equilibrium properties of social systems, at the end of which he states: [4]

“This simple example illustrates [the] logical principles [physical chemistry] that find universal application in the physical, biological, and social sciences.”

Rossini, to continue, goes on to state that from the first law and second law we can derive the following two equations:

 \Delta G^\circ = -RT \ln K \,

 \Delta G^\circ = \Delta H^\circ - T \Delta S^\circ \,

The first of which was derived in the circa 1884 so-called ‘van’t Hoff equilibrium box’ experimental work of Dutch physical chemist Jacobus van’t Hoff, the second of which was first derived in the 1923 ‘free energy table’ work of American physical chemist Gilbert Lewis. Rossini then combines these two equations to arrive at the following governing equation:

\ln K = \frac{\Delta S^\circ}{R} - \frac{\Delta H^\circ}{RT} \,
Binding affinity
A depiction of binding affinity contributions—of a small molecule (green) to its target (red) amid solvent water (cyan)—of enthalpy ΔH and entropy ΔS, from American biophysical (chnops-physical) chemist Allen James' 2009 Biophysical Chemistry. [5] The Rossini corollary of this is that the green molecule is akin to a person (human molecule) being moved into or out of various binding sites.

Rossini then concludes rather boldly:

“The final state of equilibrium is a compromise between the ‘freedom’ term, ΔS°/R, and the ‘security’ term, a – ΔH°/RT. To repeat, the final state of equilibrium, then, is a compromise between two more or less opposing factors: greater freedom or greater entropy, as measure by ΔS°/R; and greater security or lesser energy, as measured by – ΔH°/RT.”

In short:

Freedom and securty

and:

Social reactions (Rossini)

Stated another way, as Swedish physical chemist Sture Nordholm put it, independently, in his 1997 “In Defense of Thermodynamics: An Animate Analogy”:

“Many economists and marketing executives would like to know what drives human behavior in the so-called marketplace. Thermodynamics explains what ‘drives’ inanimate behavior, that is, which processes will spontaneously occur and towards what equilibrium conditions they strive. Thus we might apply this theory also to economic behavior of humans. In thermodynamics the two quantities of greatest interest are the energy and the entropy.”

(add discussion)

Rossini debate
In 2006, American chemistry professor Harold Leonard suggested unearthed Rossini's relatively unknown lecture, via suggestion, in the Journal of Chemical Education, that Rossini's premise about chemical thermodynamic descriptions of freedom and security might have real-world application to anti-terrorism efforts in a post 9/11-world. This seemingly straight suggestion launched the ongoing "heated" Rossini debate, naturally enough, owing to the religious overhaul implications of the suggestion.

Discussion

Rossini, noted student of Gilbert Lewis, author of the 1950 Chemical Thermodynamics textbook, as we see, was the last of the great chemical thermodynamicists, not afraid to jump the vast gap and to bridge the two cultures using the universal rules of chemical thermodynamics. No chemical thermodynamics textbook author since—American chemical engineer Benjamin Kyle (Chemical and Process Thermodynamics, 1999) aside, to some extent—has had the ability, not to mention the mentality to attempt such a bold transition. [2]

References
1. Rossini, Frederick D. (1971). “Chemical Thermodynamics in the Real World” (abs) (pdf), Priestley Medal Address, delivered Mar 29 at the national American Chemical Society meeting, Los Angeles, California; in: Chemical Engineering News, April 5, 49 (14): 50-53.
2. (a) Kyle, Benjamin G. (1988). “The Mystique of Entropy” (abs) (pdf), Chemical Engineering Education, Vol. 22., pgs. 92-97. Spr.
(b) Kyle, Benjamin G. (1999). Entropy: Reflections of a Classical Thermodynamicist (ch. 8: The Mystique of Entropy, 15 pgs.). Kansas State University; first published on attached CD-ROM to Chemical and Process Thermodynamics (3rd ed.), Prentice Hall, 1999.
3. (a) Kirman, Alan P. (1987). “Pareto as an Economist”, in: The New Palgrave: A Dictionary of Economics, Volume Three (editors: J. Eatwell, M. Milgate, and P. Newman) (pgs. 804-09). MacMillan Press.
(b) Kirman, Alan (contributions) – DictionaryOfEconomics.com.
(c) Alan Kirman (curriculum vitae) – Les Universites a Aix en Provence.
4. Henderson, Lawrence J. (1935). Pareto's General Sociology: A Physiologists Interpretation (pgs. 80-81). Harvard University Press.
5. (a) Allen, James P. (2009). Biophysical Chemistry (figure 3.6: Binding affinity, pg. 57; Modified from Freire, 2004, figure 1). Wiley.
(b) James Allen (faculty) – Arizona State University.
(c) Freire, Ernesto. (2004). “Isothermal Titration Calorimetry: Controlling Binding Forces in Lead Optimization” (abs), Drug Discovery Today, 1:295-59.
(d) Original caption: “Figure 1.The binding affinity of a small molecule to its target (red) is determined by the balance of the magnitude of its interactions with the target and those with the solvent water (cyan). Isothermal titration calorimetry is the only technique that measures directly the magnitude of the forces associated with binding. The most important binding determinants that can be controlled by drug developers are the binding enthalpy, ΔH, the solvation entropy, ΔSsolv, and the conformational entropy, ΔSconf, changes.”

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