The radiolysis of mixtures of carbon dioxide and hydrogen
- 1 July 1972
- journal article
- research article
- Published by Wiley in International Journal of Chemical Kinetics
- Vol. 4 (4) , 463-477
- https://doi.org/10.1002/kin.550040409
Abstract
The self‐radiolysis of CO2 in excess tritium (3H2) has been studied at pressures of 0.1 to 1.0 atm, temperatures of −80° to +100°C, and in the presence of added H2O, He, or Ar. The primary products of decomposition are CO and 3H2O. Secondary products are C3H4, C23H4, and a white polymer. The rates of disappearance of CO2 and formation of products and G‐;values were measured. The disappearance of CO2 initially obeys first‐order kinetics, then slows down with time at a rate depending upon the initial pressure of 3H2. The initial rates are proportional to pressures of CO2 and 3H2. They are independent of temperature, decreased by addition of H2O vapor, and increased by addition of He or Ar. The proposed mechanism of decomposition of CO2 and formation of products involves ionization of CO2 followed by dissociative recombination forming CO and O. Then the O reacts with a hydrogen‐containing species forming OH and H2O, and a back reaction forms CO2 from CO and OH.Keywords
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