Thermodynamic theory of kinetic overshoots

نویسندگان

  • Alexander N. Gorban
  • Gregory S. Yablonsky
چکیده

Everything that is not prohibited is permissible. So, what is prohibited in the course of chemical reactions, heat transfer and other dissipative processes? Is it possible to “overshoot” the equilibrium, and if yes, then how far? Thermodynamically allowed and prohibited trajectories of processes are discussed by the example of effects of equilibrium encircling. The complete theory of thermodynamically accessible states is presented. The space of all thermodynamically admissible paths is presented by projection on the “thermodynamic tree”, that is the tree of the related thermodynamic potential (entropy, free energy, free enthalpy) in the balance polyhedron. The stationary states and limit points for open systems are localized too.

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

منابع مشابه

Kinetic and thermodynamic study of substituent effect on the Claisen rearrangement of para-substituted SI aryl ether: a Hammett study via DFT

In order to find the susceptibility of the Claisen rearrangement and next proton shift reaction of ally) aryl etherto the substiment effects in pan position, the kinetic and the:rmodynamie parameters are calculated at The33 LTP level using 6-3110. b asis set. The calculated activation energies for the rearrangements and protonshift reactions are around 3133 kcaUmol and 52.16 kcal/mol, nap.. liv...

متن کامل

A density functional theory study of the region selectivity of the Diels –Aldercyclo addition of 2 methyl- substituted diene with selected dienophiles

In the present work, the regioselectivity for a series of Diels–Alder reactions (4 reactions) has beenstudied using hardness, electrophilicity and polarizability of products.Furthermore,thermodynamicand kinetic calculations have been done. In all results predicted pararegioisomer is more favorableregioisomerinthese investigated reactions.All calculations have been done at the DFT-B3LYP/6-31G(d)...

متن کامل

Kinetic Study of Reaction between Allyl Compounds of Mg and Ethylene: Computational Investigation

The reactions of propenyl magnesium halides with ethylene were studied using ab initio calculations. The structure of the transition state and the ground state were evaluated and obtained the structural properties, theoretical thermodynamic and kinetic data i.e. rate constants of the reactions. The methods used for calculations are RHF, B3LYP and MP2 with 6-31G* b...

متن کامل

Enhanced removal of humic acids (HAs) from aqueous solutions using MWCNTs modified by N-(3-nitro-benzylidene)-N-trimethoxysilylpropyl-ethane-1,2-diamine on Equilibrium, thermodynamic and kinetics

In this study, multi-walled carbon nanotubes modified by N-(3-nitro-benzylidene)-N-trimethoxysilylpropyl-ethane-1, 2-diamine (NBATSPED-MWCNTs) was prepared as a low-cost and non-toxic adsorbent. These  materials was characterized by different techniques such as SEM, XRD and FT-IR and subsequently was used for the removal of humic acids (HAs) from aqueous solution. The influence of various opera...

متن کامل

ذخیره در منابع من


  با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید

برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید

ثبت نام

اگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید

عنوان ژورنال:

دوره   شماره 

صفحات  -

تاریخ انتشار 2005