Rossini debate


American chemical thermodynamicist Frederick Rossini at about the time of his famous 1971 Priestley Medal address “Chemical Thermodynamics in the Real World”.

American chemical thermodynamicist Frederick Rossini at about the time of his famous 1971 Priestley Medal address “Chemical Thermodynamics in the Real World”.

In human thermodynamics, the Rossini debate or "Rossini-Leonard-Wojcik debate" is a noted 2006 debate between American chemistry professors Harold Leonard, John Wojcik, and Todd Silverstein, on the legitimacy of American chemical thermodynamicist Frederick Rossini’s political thermodynamics arguments, expressed in his 1971 Priestley Medal address “Chemical Thermodynamics in the Real World”, in which Rossini argued that the first and second laws of thermodynamics could be used to understand the paradox between freedom and security in social life, as understood through enthalpy and entropy changes in society. [1] The following is Rossini's central message from his address:

“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.”

The debate took place in the form of letters and response letters in the Jan-Jun 2006 issues of The Journal of Chemical Education. Further discussions on the debate can be found in works of American chemical engineer Libb Thims (2007) and Chinese-born Canadian economic thermodynamicist Jing Chen (2008). [2]

Rossini address
The roots of the debate originated in when in 1971 American chemical thermodynamicist Frederick Rossini was awarded the Priestley Medal, the highest honor conferred by the American Chemical Society, and in his address, “Chemical Thermodynamics in the Real World”, argued that the first two laws of thermodynamics could explain the paradox between freedom, as in being free to do what one wants, and security, as in being safe from harm, in social life; in that the more secure one is, the less free he or she will be. The following is the excerpt from Rossini's lecture that started the debate: [3]

With the first and second laws of thermodynamics we can derive two important equations:

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

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

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:

$\ -RT \ln K = \Delta H^\circ - T \Delta S^\circ$

or
$\ \ln K = - \frac{\Delta H^\circ}{R} \left ( \frac{1}{T} \right ) + \frac{\Delta S^\circ}{R}$

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.

With the first and second laws of thermodynamics we can derive two important equations: $\ \Delta G^\circ = -RT \ln K$ $\ \Delta G^\circ = \Delta H^\circ - T \Delta S^\circ$ 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: $\ -RT \ln K = \Delta H^\circ - T \Delta S^\circ$ or $\ \ln K = - \frac{\Delta H^\circ}{R} \left ( \frac{1}{T} \right ) + \frac{\Delta S^\circ}{R}$ 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.

Leonard’s suggestion
In January 2006, American chemist Harold Leonard sent a one-page letter entitled “Chemical Thermodynamics in the Real World” the Journal of Chemical Education, which was published in the January 2006 issue, in which he made the suggestion that Rossini’s chemical thermodynamics views freedom and security might help the world leaders better understand terrorism in the post 9/11 world. The letter consisted of two short introductory comments, as shown below, with a reprint of the partial excerpt, as shown above, from Rossini’s Priestley Medal address: [4]

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.

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.

Wokcik’s response
In a response December letter to Leonard’s suggestion, entitled “A Response to Chemical Thermodynamics in the Real World”, American physical chemist John Wojcik objects greatly to the association of entropy with human freedom, argued that chemical thermodynamics has nothing to say about the human condition, calling the suggestion nothing but anthropomorphism in chemistry. The following is Wojcik’s three paragraph response letter: [5]

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.

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.

Silverstein’s response
In yet another follow up June letter entitled “State Functions vs State Governments” (a play on the term state functions), American chemist Todd Silverstein notes in Wojcik’s view that certainly caution must be taken in using science to guild social policies, citing the example of eugenics becoming a core tenet of Austrian-born German politician Adolf Hitler’s extermination policies, but disagrees with Wojcik’s view that such loose thinking should be purged from science altogether. The following is Silverstein’s response letter: [6]

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

$\ - \left ( \frac{\Delta H^\circ}{RT} \right ) + \frac{\Delta S^\circ}{R} = \ln (K_{eq})$

not –RTln(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 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 $\ - \left ( \frac{\Delta H^\circ}{RT} \right ) + \frac{\Delta S^\circ}{R} = \ln (K_{eq})$ not –RTln(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.

Leonard’s response
In response to Silverstein’s “State Functions vs State Governments” article, Leonard comments: [7]

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.

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.

See also
● Detractors
● Human thermodynamics (objections to)
● Human chemistry (objections to)
● Libb Thims (attack)

References
1. (a) Rossini, Frederick D. (1971). "Chemical Thermodynamics in the Real World", Priestley Medal Address, in: Chemical & Engineering News, April 5, 49 (14): 50-53, American Chemical Society.
(b) ElieL, Ernest L. (1999). “Frederick Dominic Rossini: 1899-1990, A Biographical Memoir” (Priestly Medal, freedom vs. security, pg. 14). Biographical Memoirs, Vol. 77. National Academy of Sciences.
(c) Anon. (2008). “The Priestley Medalists, 1923-2008.”, Chemical and Engineering News, Vol. 86, No. 14, pgs. 60-61, Apr 07.
(d) Priestley Medal – Wikipedia.
2. (a) Thims, Libb. (2007). Human Chemistry (Volume Two), (section: Rossini’s political thermodynamics, pgs. 679-88). (preview). Morrisville, NC: LuLu.
(b) Chen, Jing. (2008). “Understanding Social Systems: A Free Energy Perspective”, September, 16. pgs. 1-10. Social Science Resource Network.
3. Rossini, Frederick D. (1971). "Priestly Medal Address: Chemical Thermodynamics in the Real World". Chem. Eng. News., April 5, 49 (14): 50-53, American Chemical Society.
4. Leonard, Harold, E. (2006). “Chemical Thermodynamics in the Real World.” (PDF) Letters, Journal of Chemical Education, (83) 39, Jan, No. 1. pg. 39.
5. Wójcik, John F. (2006). ‘A Response to Chemical Thermodynamics in the Real World.’ (PDF) J. Chem. Educ. (83) 39.
6. Silverstein, Todd, P. (2006). “State Functions vs. State Governments”, Journal of Chemical Education, Jun. (83): 847, Letters.
7. Leonard, H. (2006). “Author replies to Silverstein”, J. Chem. Educ. (83): 39, Jun.

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