Boreskov Institute of Catalysis of the Siberian Branch of Russian ...

PP-III-38NON-ARRHENIUS MECHANISMS OF VERY FAST SOLID PHASECHEMICAL TRANSFORMATIONS IN «UNIVERSE-REACTOR» NEARABSOLUTE ZERO OF TEMPERATURESBarelko V.V. 1 , Kiryukhin D.P. 1 , Barkalov I.M. 1 , Pumir A. 21 Institute of Problems of Chemical Physics RAS, Chernogolovka, Russiae-mail: barelko@icp.ac.ru2 University of Nice, CNRS, France, e-mail: Alain.PUMIR@unice.frThe presented here work are connected with an absolutely new field of applications offracture problem in solid phase chemistry. Main Non-Arrhenius goal of the works isinteracting (feedback coupling) between of fracture and activation of solid matrix in chemicalprocesses in solids, in particular, in a such global reactor as chemical transformations inUniverse.Autowaves of fracture as a reason of fast chemical evolution of matter in Universe.The work proposes new approaches for explanation of a many-centuries mysteryconcerning of nature of super-fast chemical solid state evolution of matter in the «Universe-Reactor» under temperatures near to absolute zero and also chemical mechanisms of formingof the solid crust on the cold planets of the Solar system.The concept is based on discovered two decades ago non-usual autowave self-propagationphenomena of anomalous fast transformations in the cryo-chemical reactions [1,2]. Thesetravelling waves had velocities equal to ones in most fast high temperature processes ofcombustion nevertheless the transformations were realised under temperatures 4-77 K (inliquid helium and nitrogen). The chemical solid state waves initiated by local brittle fracturepropagated layer by layer over the frozen sample of reagents. The chemical reaction starts onthe surface resulting from local brittle fracture of the solid matrix. Temperature gradientsarising during the reaction lead to further dispersion of the reacting sample. This feedbackmechanism leads to propagation of autowaves of chemical conversion. Such an autowaveregime is observed for several classes of reactions (hydrocarbon chlorinating, olefinhydrobrominating, polymerization and copolymerization). The classical Arhenius conceptcould not explain the phenomenon. These observations lead to a completely new autowaveconcept of chemical activity in solid state.The developed theory of the phenomenon rests on the assumption that a mechanicalenergy accumulated in solid matrix can be transformed into a chemical energy even atextremely low temperatures, therefore leading to rates of chemical transformation many375