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Phenomenon of quantum low temperature limit of chemical reaction rates

Journal Article:

Abstract

The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius Law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerization, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerization reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau/sub 0/) required to add one new link to the polymer chain of formaldehyde during its polymerization by radiation and during postpolymerization and to establish that below 80K the increase of tau/sub 0/ slows down and that at T approximately equal to 10-4K the time tau/sub 0/ reaches a plateau (tau/sub 0/ approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon,  More>>
Authors:
Gol'danskii, V I [1] 
  1. AN SSSR, Moscow. Inst. Khimicheskoj Fiziki
Publication Date:
Dec 01, 1975
Product Type:
Journal Article
Reference Number:
AIX-09-349349; EDB-78-027988
Resource Relation:
Journal Name: Usp. Khim.; (USSR); Journal Volume: 44:12
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; FORMALDEHYDE; CHEMICAL RADIATION EFFECTS; ARRHENIUS EQUATION; BIBLIOGRAPHIES; CALORIMETRY; CHEMICAL REACTION KINETICS; LOW TEMPERATURE; POLYMERIZATION; REVIEWS; TUNNEL EFFECT; ALDEHYDES; CHEMICAL REACTIONS; CHEMISTRY; DOCUMENT TYPES; KINETICS; ORGANIC COMPOUNDS; RADIATION CHEMISTRY; RADIATION EFFECTS; REACTION KINETICS; 400600* - Radiation Chemistry
OSTI ID:
5404209
Country of Origin:
USSR
Language:
Russian
Other Identifying Numbers:
Journal ID: CODEN: USKHA
Submitting Site:
INIS
Size:
Pages: 2121-2149
Announcement Date:

Journal Article:

Citation Formats

Gol'danskii, V I. Phenomenon of quantum low temperature limit of chemical reaction rates. USSR: N. p., 1975. Web.
Gol'danskii, V I. Phenomenon of quantum low temperature limit of chemical reaction rates. USSR.
Gol'danskii, V I. 1975. "Phenomenon of quantum low temperature limit of chemical reaction rates." USSR.
@misc{etde_5404209,
title = {Phenomenon of quantum low temperature limit of chemical reaction rates}
author = {Gol'danskii, V I}
abstractNote = {The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius Law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerization, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerization reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau/sub 0/) required to add one new link to the polymer chain of formaldehyde during its polymerization by radiation and during postpolymerization and to establish that below 80K the increase of tau/sub 0/ slows down and that at T approximately equal to 10-4K the time tau/sub 0/ reaches a plateau (tau/sub 0/ approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon, which may be particularly common in combined electronic-confirmational transitions in complex biological molecules and may play a definite role in chemical and biological evolution (cold prehistory of life).}
journal = {Usp. Khim.; (USSR)}
volume = {44:12}
journal type = {AC}
place = {USSR}
year = {1975}
month = {Dec}
}