| NONEQUILIBRIUM THERMODYNAMICS OF DYNAMIC CHEMICAL EQUILIBRIA Anil A. Bhalekar1; 1DEPARTMENT OF CHEMISTRY, R. T. M. NAGPUR UNIVERSITY, NAGPUR, India; PAPER: 132/Energy/Regular (Oral) SCHEDULED: 11:55/Tue. 29 Nov. 2022/Game 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><sub>k</sub><sup>*</sup> '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><br />1. I. Prigogine, <i>Introduction to Thermodynamics of Irreveersible Processes</i>, John Wiley-Interscience, New York, 1967<br />2. S. R. De Groot and P. Mazur, <i>Non-Equilibrium Thermodynamics</i>, North Holland, Amsterdam, 1962<br />3. R. P. Rastogi, <i>Introduction to Non-equilibrium Physical Chemistry. Towards Complexity and Non-linear Sciences</i>, Elsevier, Amsterdam, 2008<br />4. 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<br />5. A. A. Frost and R. G. Pearson, <i>Kinetics and Mechanism</i>, Second Edition, John Wiley and & Sons Inc., London, 1961<br />6. K. J. Laidler, <i>Chemical Kinetics</i>, Tata McGraw-Hill, New Delhi, 1967<br />7. R. Schmid and V. N. Sapunov, <i>Non-Formal Kinetics</i>, Verlag Chemie GmbH, Weinheim, 1982<br />8. T. L. Hill, <i>An Introduction to Statistical Thermodynamics</i>, First Edition, Addison-Wesley Publishing Company, INC., Reading, MA, 1960<br />9. 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) |
