Coupling


A schematic of Iranian-born American Robert Kenoun's 2006 "internal energy coupling theory", an aspect of his social internal energy minimization theory, of social history, wherein he views each subsystem or society as tending to a thermodynamic potential of internal energy minimum (U → 0), and that these sub-system societies are energetically connected together in the larger global system. [3]

A schematic of Iranian-born American Robert Kenoun's 2006 "internal energy coupling theory", an aspect of his social internal energy minimization theory, of social history, wherein he views each subsystem or society as tending to a thermodynamic potential of internal energy minimum (U → 0), and that these sub-system societies are energetically connected together in the larger global system. [3]

In chemistry, coupling refers to reactions, i.e. coupled reactions, that are ‘coupled’ together in the sense that a thermodynamic coupling allows one of the reactions to progress in a direction contrary to that prescribed by its own affinity. [1]

History
In the 1890s, German physical chemist Wilhelm Ostwald, according to energetics historian John Edsall (1974), was the first, apparently, to discuss coupled reactions, whereby (to use modern terminology) the free energy released by an exergonic process can be used to drive an endergonic process that would not go by itself. [7]

In the years 1920 to 1936, Belgian physical chemist Theophile de Donder worked out the basics of "affinity coupling", such that if in a system two simultaneous reactions occur:

A1v1 < 0

A2v2 > 0

where A and v are the chemical affinity and chemical reaction rate, respectively, and the subscripts refer to reaction one and reaction two, respectively, that the overall reaction will occur as long as:

A1v1 + A2v2 > 0

at which point the reactions are said to be "coupled" reactions. In this sense, according to de Donder's protege Belgian chemist Ilya Prigogine, "thermodynamic coupling" allows one of the reactions to progress in a direction contrary to that proscribed by its own affinity. The rules for affinities of reaction are defined as follows: [5]

Measure
Description
$A > 0 \,$ reaction proceeds to the right
reaction proceeds to the left
$A = 0 \,$ reaction is in a state of equilibrium

Measure	Description
$A > 0 \,$	reaction proceeds to the right
	reaction proceeds to the left
$A = 0 \,$	reaction is in a state of equilibrium

The formula de Donder employs to measure affinity A is:

$A = - \sum_{i=1}^j \nu_i \mu_i \,$

where μ (mu) is the chemical potential, as defined in the work of Willard Gibbs (1876), of one associated molecular entity or mass ν (nu).

In 1961, Frederick Koenig, et al, published on thermodynamics of coupling, via citation to de Donder. [8]

Free energy coupling
In 1934, American physicochemical physiologist Harold Blum, in his “A Consideration of Evolution from a Thermodynamic View-Point”, outlined what seems to be the first version of free energy coupling theory as well as its first application toward a reformulation of a non-theological directive-based version of evolution via natural selection.

In 1941, German-born American biochemist Fritz Lipmann, in his "Metabolic Generation and Utilization of Phosphate Bond Energy", which itself was based on previous scatters works on the puzzle as to how to explain the energetics of frog leg movement, outlined a more robust free energy coupling model, which is summed up by the following equation:

Herein, this is called the Lipmann coupling inequality and states that as long as the sum of the Gibbs free energy changes for all "natural", symbol $N \,$ , processes or reactions, in a given coupled system, plus the the sum of the Gibbs free energy changes for all "unnatural", symbol $\tilde N \,$ , processes or reactions, in a given coupled system, is negative or has a measurement value less than zero then the process as a whole will be natural and spontaneously progress or occur.

In modern times, this is known popularly as the "free energy coupling" model of driven energy transformations, the textbook example being the model of ATP as a type of "energy currency".

A later spin-off the coupling model is English biochemist Peter Mitchell’s 1961 chemiosmotic theory, or chemiosmotic hypothesis, the theory which explains the coupling processes that made ATP in the first place as well as the thermodynamics of membrane transport in general.

Thermodynamic potentials
System	Potential	Conditions	Equilibrium
Isolated system	Entropy (negative) Negentropy		dS = 0 (S = max)
(add)	Internal energy (dS = 0, dV = 0)	Quantities of extensity constant	dU = 0 (U = min)
Closed isentropic isobaric system	Enthalpy (dS = 0, dP = 0)	Entropy, pressure, and amount of substance constant	dH = 0 (H = min)
Closed isochoric isothermal system	Helmholtz free energy (dT = 0, dV = 0)	Temperature, volume, and amount of substance constant	dF = 0 (F = min)
Closed isobaric isothermal system	Gibbs free energy (dT = 0, dP = 0) Note: (freely running)	Temperature, pressure, and amount of substance constant	dG = 0 (G = min)
Open isobaric isothermal system	Gibbs free energy (dT = 0, dP = 0) Addition factors: (chemical potential: μ) (turnover rate)	Temperature and pressure constant; amount of substance varies	dG = 0 (G = min)

Human thermodynamics
In 2006, Iranian-born American material science electrical engineer Robert Kenoun outlined a generalized model of social coupling, i.e. his "social internal energy minimization theory, where in so-called "relational bonds" are posited to exist between societies or systems, exchanging energy and matter, and the tendency for each system is towards an internal energy minimum (U → 0). [3] The main difficulty in Kenoun's coupling theory is that he is using the wrong is

In 2007, Russian bioelectrician Octavian Ksenzhek outlined a crude type of economic coupling theory, viewing money as a type of "virtual energy" analogous to the way in which ATP acts a a power or energy source in the cell driving a variety of endergonic processes in the cell. [4]

References
1. Prigogine, Ilya. (1955). Introduction to Thermodynamics of Irreversible Processes (section: 3.6: Coupling of Chemical Reactions, pgs. 23-25). Interscience Publishers.
2. De Donder, Theophile and Van Rysselberghe Pierre. (1936). Thermodynamic Theory of Affinity: A Book of Principles (pg. 2; affinity coupling, pg. 113). Oxford University Press.
3. Kenoun, Robert. (2006). A Proposition to Theory of History and Social Evolution (abs) (pg. 147). Trafford Publishing.
4. Ksenzhek, Octavian S. (2007). Money: Virtual Energy - Economy through the Prism of Thermodynamics. Universal Publishers.
5. Kondepudi, Dilip and Prigogine, Ilya. (1998). Modern Thermodynamics – from Heat Engines to Dissipative Structures (4.1: Chemical potential and Affinity: the Driving Force of Chemical Reactions, pgs. 103-13). New York: John Wiley & Sons.
6. Blum, Harold F. (1934). “A Consideration of Evolution from a Thermodynamic View-Point” (abs), presented at the 94th meeting of the American Association for the Advancement of Science, Jun 20, in: The American Naturalist, 69(723):354-69, Jul-Aug, 1935.
7. Edsall, John T. (1974). “Some Notes and Queries on the Development of Bioenergetics. Notes on some ‘Founding Fathers’ of Physical Chemistry: J. Willard Gibbs, Wilhelm Ostwald, Walther Nernst, Gilbert Newton Lewis” (abs) (energetic imperative, pg. 104), Molecular and Cellular Biochemistry, 5(1-2): 103–12, Nov 15.
8. Koenig, Frederick O., Horne, Frederick H., and Mohilner, David M. (1961). “On Thermodynamic Coupling of Chemical Reactions” (abs), Journal of the American Chemical Society, 83(5):1029-33.

Further reading
● Delbruck, Max. (1944). “Problems of Modern Biology in Relation to Atomic Physics: Part III: Energy-Coupling”, A Series of Lectures, April and May, Vanderbilt University School of Medicine.
● Pings, C.J. Nebeker, E.B. (1965). “Thermodynamics of Chemical Coupling”, Ind. Eng. Chem. Fundamen. 4(4): 376-381.
● Bierbaum V. and Lipowsky R. (2011). “Chemomechanical Coupling and Motor Cycles of Myosin v.” (abs), Biophys. J. 100(7): 1747-55.

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