ORALS

SESSION: EnergyMonPM2-R11	Mauntz International Symposium (7th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, & storage for all energy production technologies; Energy conservation)
Mon. 28 Nov. 2022 / Room: Game
Session Chairs: Leo Eskin; Session Monitor: TBA

17:10: [EnergyMonPM212] OS
Some of the Basic Aspects of Transition State Theory (TST) of Bimolecular Reaction Rates Revisited with an Input From Nonequilibrium Thermodynamics
Anil A. Bhalekar¹ ; Bjarne Andresen² ; ¹Department of Chemistry, R. T. M. Nagpur University, NAGPUR, India; ²University of Copenhagen, COPENHAGEN, Denmark;
Paper Id: 133 [Abstract]

In view of the prevailing over skepticism about the sound thermodynamic base of the expression of the rate constant given by the traditional transition state theory (TST) of bimolecular reactions, its foundational ingredients are revisited in this paper. The inference drawn earlier of the existence of <i><i>quasiequilibrium</i></i> between the reactants and activated complexes has been properly amended. The need for this has been elucidated by showing that the use of <i>quasiequilibrium</i> amounts to use it as a pre-equilibrium step hence it implies that the conversion of activated complexes to the product molecules must be a slow step according to the basic principles of chemical kinetics. However, it has been demonstrated that the existence time of an activated complex is less than the time required to complete half of the molecular vibration of the activated complex. Which means they are highly reactive ones. Therefore, it is not the case of <i>pre-equilibrium </i>but, indeed, is the case of a steady state for the forward moving activated complexes, which is what Arnot had advocated earlier. However, we have demonstrated that the said steady state for the concentration of the forward moving activated complexes is a case of <i>dynamic chemical equilibrium</i> between the reactants and the forward moving activated complexes whose sound thermodynamic base has been elucidated by describing the corresponding nonequilibrium thermodynamics. Thus, the much-needed description of the thermodynamic base of TST given expression of the rate constant has been accomplished.

References:
<b>Bibliography</b>\n1. A. A. Bhalekar, Nonequilibrium thermodynamics of dynamic chemical equilibria, (Preceding Paper) (2020)\n2. H. Eyring, Activated Complex in Chemical Reactions, <i>J. Chem. Phys.</i>, 3, 107-115 (1935).\n3. M. G. Evans and M. Polanyi, Some applications of the transition state method to the calculation of reaction velocities, especially in solution, <i>Trans. Faraday Soc.</i>, 31, 875-894 (1935)\n4. S. Glasstone, K. J. Laidler, and H. Eyring, <i>Theory of Rate Processes</i>, McGraw-Hill, New York, 1941\n5. K. J. Laidler and J. C. Polanyi, <i>Theories of the Kinetics of Bimolecular Reactions</i>, Vol 3, of <i>Progress in Reaction Kinetics</i>, ch. 1, Pergomon Press, London, 1965\n6. K. J. Laidler and M. C. King, The development of transition-state theory, <i>J. Phys. Chem.</i>, 87, 2657-2664 (1983)\n7. C. L. Arnot, Activated complex theory of bimolecular gas reactions, <i>J. Chem. Educ.</i>, 49, 480-482 (1972)\n8. I. Prigogine and R. Defay, <i>Chemical Thermodynamics</i>, D. H. Everett, Transl., Longmans-Green, London, 1954\n9. A. A. Bhalekar, The transition state theory of bimolecular reaction rates via the Bodenstein steady state for activated complexes, <i>CACAA</i>, 4, 309-340 (2015)

SESSION: EnergyMonPM3-R11	Mauntz International Symposium (7th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, & storage for all energy production technologies; Energy conservation)
Mon. 28 Nov. 2022 / Room: Game
Session Chairs: Greg Baiden; Session Monitor: TBA

17:50: [EnergyMonPM313] OS
A Revisit to the Local Thermodynamic Equilibrium Assumption of Nonequilibrium Thermodynamics
Anil A. Bhalekar¹ ; Bjarne Andresen² ; ¹Department of Chemistry, R. T. M. Nagpur University, NAGPUR, India; ²University of Copenhagen, COPENHAGEN, Denmark;
Paper Id: 175 [Abstract]

The global level thermodynamic comprehension of the local thermodynamic equilibrium assumption of nonequilibrium thermodynamics is presented. How the Gibbs relation given by equilibrium thermodynamics also describes a passage on an irreversible path is demonstrated at the global thermodynamic level. Specifically it has been demonstrated that the Gibbs relation indeed also takes care of irreversibility for a spatially uniform system with internal source of irreversibility for example the chemical reactions at non-vanishing rates and the irreversibility originating in the gradients of intensities across the boundary of the system. Hence, thermodynamic functions appearing in Gibbs relation are those for equilibrium and nonequilibrium states. The former is the case when it is used to describe a passage through the succession of equilibrium states and the latter is the case while describing the the passage through the succession of nonequilibrium states, i.e. on irreversible trajectories. Thereby, it gets demonstrated that the scope of validity of the local thermodynamic equilibrium assumption of nonequilibrium thermodynamics is much wider than it has been understood so far.

References:
Bibliography:\n[1] S. R. De Groot and P. Mazur, Non-Equilibrium Thermodynamics. Amsterdam: North Holland, 1962.\n[2] R. Clausius, The Mechanical Theory of Heat. London: Macmillan & Co., 1879. Translated by W. R. Browne.\n[3] H. A. Bumstead and R. G. V. Name, eds., The Scientific Papers of J. Willard Gibbs, vol. I. Thermodynamics. London and Bombay: Longmas, Green and Company, 1906.\n[5] J. N. Brønsted, “On the concept of heat,” Det. Kgl. Danske Videnskab. Seleskab. Math-Fys. Medd., vol. 19(8) (1941) 1 – 79.\n[6] I. Prigogine and R. Defay, Chemical Thermodynamics. London: Longmans Green, 1954. Translated by D. H. Everett.\n[7] B. C. Eu, “Form of uncompensated heat giving rise to a pfaffian differential form in thermodynamic space,” Phys. Rev. E, 51 (1995) 768 – 771.\n[8] A. A. Bhalekar, “Irreversible thermodynamic framework using compatible equations from thermodynamics and fluid dynamics. A second route to generalized phenomenological irreversible thermodynamic theory (GPITT),” Bull. Cal. Math. Soc., 94(2) (2002) 209 – 224. \nNote: This abstract is dedicated to Prof. Ferid Murad, Nobel Laureate in Medicine and the Symbol of Unified Science.

SESSION: EnergyTueAM-R11	Mauntz International Symposium (7th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, & storage for all energy production technologies; Energy conservation)
Tue. 29 Nov. 2022 / Room: Game
Session Chairs: Hussein Hoteit; Session Monitor: TBA

11:55: [EnergyTueAM02] OS
NONEQUILIBRIUM THERMODYNAMICS OF DYNAMIC CHEMICAL EQUILIBRIA
Anil A. Bhalekar¹ ; ¹Department of Chemistry, R. T. M. Nagpur University, NAGPUR, India;
Paper Id: 132 [Abstract]

This presentation for the first time discusses the nonequilibrium thermodynamics of dynamic chemical equilibrium in a wide number of chemical reactions. They include two-step consecutive reactions and multi-step chain reactions. From chemical kinetics we learn that the dynamic chemical equilibria get established when there are (i) fast pre-equilibrium steps or (ii) produced highly reactive intermediate chemical species during the course of a reaction and for their concentrations the Bodenstein steady state approximation gets established. There result <i>Q</i>'s, the quotients of concentration, as <i>f(T, p)</i> which generates stoichiometric equivalence of chemical potentials of the chemical species involved therein. In some cases one or more chemical affinities, <i>A</i> 's, of the steps involved in the reaction vanish but it is not true in all cases. Irrespective of vanishing or non-vanishing of <i>A</i> 's of the involved steps one still can use corresponding standard thermodynamic relation between corresponding dynamic equilibrium constant and the corresponding standard state chemical affinity, which is the thermodynamic condition of dynamic chemical equilibrium, corresponding chemical affinities are (i) that of some steps and they assume a zero value or (ii) when none of chemical affinities of the steps of the reaction vanish but one or more internal chemical affinities, become equal to zero. Also in such cases the <i>Q(T,p)</i> 's can be equally calculated using the volume independent partition functions, <i>q</i>_k^* 's, and the Avogadro number <i>L</i>. A thermodynamic condition of explosion in a chemical reaction gets described by the attainment of very large, positive or negative, values of chemical affinities of the steps involved.

References:
<b>Bibliography</b>\n1. I. Prigogine, <i>Introduction to Thermodynamics of Irreveersible Processes</i>, John Wiley-Interscience, New York, 1967\n2. S. R. De Groot and P. Mazur, <i>Non-Equilibrium Thermodynamics</i>, North Holland, Amsterdam, 1962\n3. R. P. Rastogi, <i>Introduction to Non-equilibrium Physical Chemistry. Towards Complexity and Non-linear Sciences</i>, Elsevier, Amsterdam, 2008\n4. G. N. Lewis and M. Randall, <i>Thermodynamics</i>, Second Edition, McGraw-Hill Book Co., Inc., 1961. Revised by K. S. Pitzer and L. Brewer\n5. A. A. Frost and R. G. Pearson, <i>Kinetics and Mechanism</i>, Second Edition, John Wiley and & Sons Inc., London, 1961\n6. K. J. Laidler, <i>Chemical Kinetics</i>, Tata McGraw-Hill, New Delhi, 1967\n7. R. Schmid and V. N. Sapunov, <i>Non-Formal Kinetics</i>, Verlag Chemie GmbH, Weinheim, 1982\n8. T. L. Hill, <i>An Introduction to Statistical Thermodynamics</i>, First Edition, Addison-Wesley Publishing Company, INC., Reading, MA, 1960\n9. K. J. Laidler and M. T. H. Liu, The mechanism of the acetaldehyde pyrolysis, <i>Proc. Royal Soc. London A</i>, 297, 365-375 (1967)