|Top: American chemical thermodynamicist Frederick Rossini at about the time of his famous 1971 Priestley Medal address “Chemical Thermodynamics in the Real World”. Right: an excerpt of American chemist Harold Leonard's suggestion to use Rossini's theory to develop post 9/11 freedom and security anti-terrorism theories.|
“The picture we have developed from thermodynamics is very simple: One cannot have a maximum of freedom and a maximum of security at the same time. If there is a maximum of freedom, there will be zero security.”
With the first and second laws of thermodynamics we can derive two important equations:
Since the term on the left side is the same in the two equations, the quantities on the right side are equal to one another. Hence we can write:
From this equation, K increases with increase in ∆S°; and K increases with decrease in ∆H°. Increase in ∆S° comes with increase in randomness, leading to greater “freedom” in the system. Decrease in ∆H° comes with increase in the energy of binding of the atoms in the molecular structure, leading to greater “security” in the system. These are opposing factors in the evaluation of K, and hence, for a given temperature, the final state of equilibrium is a compromise between the “freedom” term, ∆S°⁄R, and the “security” term, –∆H°⁄RT.
Here we have an interesting picture derived from our science of thermodynamics—equilibrium or stability is a compromise between freedom and security. In terms of human experience, the meaning of security can be interpreted to mean that one is secure and safe in his person, in his family, in his home, in control of his property, on the streets, and on his travels. The meaning of freedom is quite clear—the privilege of doing whatever one wants to do. However, in our civilized society, we have come to believe in behavior according to natural law—that one can do whatever he wishes so long as he does not abridge or infringe upon the rights and privileges of others. To me, all this means living with some rational kind of law and order.
The picture we have developed from thermodynamics is very simple: One cannot have a maximum of freedom and a maximum of security at the same time. If there is a maximum of freedom, there will be zero security. I interpret this to mean that if we have total freedom, everyone can do whatever he wishes, including injuring others, stealing property, and the like. On the other hand, if there is a maximum of security, there will be zero freedom. I take this to mean that if we have total security, we will be constrained at every step and have a virtual straitjacket life.
One sees that there is a trade-off between freedom and security. In a state of total freedom, we can afford to give up some freedom to obtain some security. The ideal situation would appear to be one in which we have established that amount of security necessary to have human beings live happily and in harmony with one another, through observance of an appropriate amount of law and order, and then to have as large an amount of freedom as can be accommodated in this situation.
“The everyday significance of thermodynamics is pointed out by Frederick Rossini in his Priestley Medal address, ‘Chemical Thermodynamics in the Real World’, reprinted in Chemical and Engineering News, Apri 5 (1971), pg. 50.”
“In 1971 [Rossini] received the Priestley Medal, the highest distinction conferred by the American Chemical Society. In his Priestly address ‘Chemical Thermodynamics in the Real World’ he made a clever comparison of the counterplay of enthalpy and entropy in thermodynamics with that of security vis-à-vis freedom in the world at large.”
One of the world’s greatest challenges, at present, is to find a formula for fighting terrorism, while preserving civil liberties. The March 2005 anti-terrorism conference in Madrid is but one example of officials and experts seeking to address the same paradox. Some 34 years ago, one part of a Priestly Medal Address by F. D. Rossini from the University of Notre Dame discussed an interesting application of thermodynamics to this paradox. Below [above on this page] are excerpts from the address. In light of the ever-increasing need for compromise, Rossini’s observation now seems all the more relevant.
By making available an excerpt from Rossini’s address, Harold Leonard has given us a good example of anthropomorphism in chemistry. The concepts of “freedom” and “security” (like “order” and “randomness”) were parts of our cultural heritage long before modern thermodynamics was formulated. Entropy was defined solely in response to the need to explain certain modern experimental observations. It was never necessary to invoke concepts like “freedom” and “security” to systematize these same specialized experiments. At best, associating “freedom” with entropy is similar on other loose associations as when we say a shaft moving in an oversize bearing has too much “freedom”. While there is a “freedom” for which one might die to defend, it is certainly not the “freedom” of an oversize bearing nor that of entropy. Such anthropomorphic associations might help some students absorb abstract concepts. They certainly are not part of the conceptual framework of the science.
The danger of such anthropomorphisms is that we really come to believe that there is substance in them. In this particular case, there is the danger that true human freedom will be reduced to some sort of physical freedom on the same par with entropy. There is the danger that some will think that true human freedom can be measured in terms of some sort of calculus of simultaneous maximums and minimums. And worst of all, there is the danger that chemical thermodynamics will have ascribed to it a power that it simply does not have, namely, the power to “explain” the human condition. There may be a sense in which chemistry is the “central science”. This is certainly not it.
It is possible that Rossini did not intend his associations to be taken as seriously as suggested here. Nonetheless, rather than encourage loose thinking through the use of such anthropomorphisms, it would be wise to purge them from science. Let chemistry solve those problems for which it was created. Let true wisdom solve the problems arising from the human condition.
I found the discussion by Leonard, Rossini, and Wójcik of the validity of thermodynamic anthropomorphisms to be quite fascinating. Leonard presented an excerpt from the 1971 Priestley Medal Address given by F. D. Rossini, in which he likened entropy to personal freedom (cf. molecular motional freedom) and enthalpy to personal security (cf. bond formation and a more stable or “secure” system). Wójcik, in his response letter, warned against anthropomorphizing science: Models that work well in explaining experimental observations are not meant to shed light on the human condition. In fact, it can be dangerous to assume that they do. The rise of social darwinism in the late 19th century and eugenics in the early 20th century are just two examples of scientific theories that were mistakenly extended into misguided social policies. Although Wójcik’s point is well-taken, I do not agree that such “loose thinking” should be “purged” from science altogether. A well-drawn analogy between two surprisingly dissimilar concepts can not only be helpful in the classroom, it can be pleasing and instructive on its own merits, as long as one is cognizant of its limitations.
On the surface, Rossini’s analogy relating enthalpy, entropy, and the equilibrium constant to freedom and security in the modern nation-state seems like a good example of an unusual and instructive comparison. I was initially intrigued. Using the thermodynamic conclusion that (a) a reaction’s spontaneity (or Keq) increases when either ∆H gets more negative (stronger security) or ∆S gets more positive (more freedom), Rossini analogized that (b) “One cannot have a maximum of freedom and a maximum of security at the same time.” Sadly, point (a), although true, does not support point (b), not even in the limited realm of chemical thermodynamics, much less in the broader realm of political governance.
Unfortunately, two errors lurk within Rossini’s exposition. The first is a simple typo: The final part of the last equation should read
not –RT ln(Keq). More importantly, Rossini’s point (b) from above is that in any thermodynamic system, a negative ∆H or a positive ∆S can be maximized, but never both. This conclusion is only true, however, if Keq is constant; of course Keq (and ∆G°) are only constant if reactants and products and all reaction conditions are identical. Rossini does not specify, in his political governance thermodynamic system, the “reactants” and “products”. Let us assume, for argument’s sake, that the “reactants” are citizens living under an initial system (i) of political governance, and the “products” are citizens living under a final system (ƒ) of political governance. Then Rossini’s argument is that for different final systems of governance (ƒ1, ƒ2, ƒ3, etc.), ∆H° and ∆S° for the change in political systems can vary, but always in opposite directions: If, relative to political system i, ƒ features increased personal freedom (positive ∆S°), then ƒ must also feature decreased security (positive ∆H°). Conversely, if ƒ features increased security (negative ∆H°), then ƒ must also feature decreased personal freedom (negative ∆S°). In other words, Rossini seems to believe that ∆H° and ∆S° must have the same sign.
This conclusion may make a certain amount of political sense, but it is flawed from a purely thermodynamic perspective. Although it is true that ∆H° and ∆S° are the same sign for many reactions (especially homogeneous reactions with no phase changes), this is by no means always the case. To present just two common counter-examples, for the combustion of solid glucose, ∆H° = –2803 kJ/mol and ∆S° = +260 J/mol•K; for the disproportionation of aqueous hydrogen peroxide (to dioxygen and water), ∆H° = –95 kJ/mol and ∆S° = +29 J/mol•K.
So to take Rossini’s analogy to its final conclusion, based on his own thermodynamic analysis, there could well be a political system out there that maximizes both personal freedom and security. From a chemical perspective, there does not have to be a tradeoff between security (negative ∆H) and freedom (positive ∆S). Although Rossini’s analogy is amusing and entertaining and makes some political sense, unfortunately, its thermodynamic conclusions are flawed.
I was pleased to see the response by T. P. Silverstein to my letter. I support his conclusions completely, especially that a “well drawn analogy between two surprisingly dissimilar concepts cannot only be helpful in the classroom, it can be pleasing and instructive on its own merits, as long as one is cognizant of its limitations”. We can assume that Rossini may have used this analogy in his teaching, as I did for over 30 years, as well as in his Priestley Medal Address.
“In response to Leonard’s suggestions about the use of Gibbsian-Rossini thermodynamics to better understand terrorism, a follow-up letter was published, in the same journal, by American physical chemistry professor John Wójcik, at Villanova University, Philadelphia, Pennsylvania, titled ‘A Response to Chemical Thermodynamics in the Real’. In this very abrupt letter, Wójcik ridicules Leonard for his suggestion. He starts out his response-letter with ‘Leonard has given us a good example of anthropomorphism in chemistry’. From here, his letter goes down hill where he argues that Leonard is wrong for naively thinking that chemical thermodynamics applies in human life. Now, Wójcik certainly has some set of balls for going up against figureheads such as Gibbs, Lewis, Randall, Giauque, and Rossini, among others. To this end, we give him credit for speaking his mind. Yet, as Rossini is not here to give his input, as he passed in 1990, here we will clarify the matter.”
“The few pioneering works about social conditions from detailed mathematical analysis of physical laws received little attention from the research community … In human society, E represents the amount of energy resources available for human consumption. Changes in entropy represent a change in randomness. Where an increase in randomness represents an increase in freedom in a system.”
“Thank you for the link to that debate. You are correct - the theme mirrors that of our argument. Your suggestion, however, that scientists are "split on the issue" is, as ever, a remarkable overstatement. Silverstein's observation is that "Although Rossini’s analogy is amusing and entertaining and makes some political sense, unfortunately, its thermodynamic conclusions are flawed." Even Leonard, in his closing response, appreciates the difference between drawing an *analogy* between thermodynamic functions of state and features of society, and the claim that one can **equate** a thermodynamic entropy/enthalpy/free energy with properties of human relationships/society. It is this distinction between analogy and mathematical/physical equivalence that is so important and which you seem unable to grasp.
Hence, you misinterpreted the analogy I drew in the Sixty Symbols YouTube video on entropy and argued that I was actually claiming that one could associate a thermodynamic entropy with the arrangement of students. That someone could confuse the analogy with the actual thermodynamic quantity just never occurred to me. Of the ~ 750 physics majors who took the 1st year Thermal and Kinetic Physics module I taught, not one made this fundamental error. Similarly, the number of professional scientists who have made this error is very small indeed.”
“I guess I generally agree with Frederick Rossini, though I see no chance to make a quantitative estimate of 'energy' and 'enthalpy' in social issues.”
“I don't know what the Rossini debate is but I hope to find out. No, your idea for a department for teaching two cultures would not be appreciated at Berkeley. In the social sciences and in some humanities, thermodynamics may be useful as an analogy, as a suggestion for looking at a problem (e.g., information theory) but beyond that, I see little use of thermodynamics outside science.”
“I am fundamentally sentimental to the notion raised by Rossini, albeit see both ends of the spectrum asymptotic in nature. I generally don't see in black and white, and colors often bleed into each other when I try to explain complex ideas.
I have come up with some pretty good analogies to help others better understand the varying "degrees of freedom" [DOF] found within the various levels of nature. For instance, imagine someone trying to get into an inner tube for a float down the river. This is often a big challenge. Why? and When? Well, there are many variables that contribute to a person being able to get into the tube, and stay put. The first challenge is to ensure that the tube contains enough air. If your hand sinks into the tube as you brace yourself, there may be too many DOF and you would have to use more energy in the form of a muscle contraction (quick leg swing or something). Technically, the tube need to have a high enough buoyant force which acts as a counterbalance to a human load.
Next, the tube needs to stay in place as to also limit the DOF. How are you going to get in a tube that is moving unless you are willing to learn some kind of ninja trick. If you can buttress the tube against a wall or at least hold it in place, it will require much less energy to get in. Obviously some DOF of available, like in the flexibility of the rubber and your arms. Overall, getting into a tube properly and floating down a river without falling out takes a balance of rigidity and flexibility.
I see it the same way for most of human behavior, especially running organizations such a politics and the economy. Some have talked about a steady-state economy that has a well-balanced DOF system that is not allowed to sway too far in any direction. Based on the Rossini page you sent, I think he was trying to get to this understanding.”
|A representative of the perceived "danger" associated with the ramifications inherent and embedded within the revolutionary subject of human chemical thermodynamics, whether discussed in reference to Goethe's 1809 Elective Affinities, Rossini's 1971 "Chemical Thermodynamics in the Real World", or Thims' 2008 Hmolpedia, a subject, namely the "moral symbols" of physical chemistry, in direct conflict to the religio-mythology based morality and belief system of modern the modern world; one example of this perceived danger being James Froude, pictured, and his 1849 Elective Affinities influenced Christian-faith renouncing Nemesis of Faith, which was publicly burned, after which he lost his post at Oxford, and thus resultantly did the first English translation of Goethe's revolutionary-doctrine containing, human chemical theory, self-defined "best book" anonymously. |
“Soviet orthodoxy [1917-1986] was shaped as a quasi-religion with Marx as God and the Spirit, Lenin as God the Father, and the party as collective God the Son.”— Yuri Tarnopolsky (1993), reflection, as a scientist, i.e. self-defined “human chemist” (or pattern chemist), on his time as a Russian citizen (1936-86) and Siberian concentration camp days (1983-85), prior to his 1987 immigration to America, amid the eventual “fall of communism” in 1989 (Ѻ) 
|A synopsis of Frederick Rossini’s 1971 “Chemical Thermodynamics in the Real World” argument, namely: slide #22 (Ѻ) of Libb Thims 2015 “Zerotheism for Kids Lecture”, wherein Rossini is shown explaining how freedom and security equate to entropy and enthalpy, respectively, in society, and how human "reactions" are larger types of chemical reactions, equilibrating in society; the contentions and ramifications of which acting to spark the Rossini debate (2007-present).|
“Froude’s semi-autobiographical Nemesis of Faith [a renunciation of Christian faith], published in 1848, owed much to Goethe’s novel of human and chemical reactions, Elective Affinities, which he translated. Nemesis lost him his fellowship at Exeter College, Oxford, where his book was publicly burned.”
|Kenneth Connors (2002) and later his co-author Sandro Mecozzi (2010) seem to have independently suppositioned the same premise as Rossini on freedom (or liberty), security, and thermodynamics.|
“It is not too fanciful to draw an analogy with a political science setting, in which each society must choose its own compromise position between the extremes of maximum security (the energy component) and maximum liberty (the entropy component).”In 2010, Connors, together with co-author Italian-born American pharmaceutical chemist Sandro Mecozzi (Ѻ), in their second edition, restated the above footnote, albeit in a little more organized fashion, with the footnote bottom page, versus end of chapter (2002), showing a free energy diagram concordantly; the newer presentation, with the footnote inserted, reads as follows: 
“The essential characteristic of the Gibbs free energy function is its combination of both energy and entropy components in a form that reveals how these two thermodynamic concepts complete to generate a compromise that determines the position of equilibrium in a chemical process. It is not too fanciful to draw an analogy with a political science setting, in which each society must choose its own compromise position between the extremes of maximum security (the energy component) and maximum liberty (the entropy component). A more negative ΔH favors spontaneous reaction, and a more positive ΔS favors spontaneous reaction, in both instances making ΔG more negative.”
|Connor’s figure 3.1 captioned as “free energy of a reacting chemical system, showing how the direction of the reaction depends on the initial state of the system”, amid his free energy and political science discussions. |