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Radiation Chemistry of Aqueous Formic Acid Solutions. Effect of Concentration

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/ja01503a005· OSTI ID:4135206

The radiolysis of formic acid solutions by Co60 gamma rays at concentrations of 1.0 to 26.6 M pure formic acid, is reported. Carbon dioxide, carbon monoxide, and hydrogen are the sole gaseous products and formaldehyde is a reactive intermediate. G(CO2) reaches values as high as 12, increases as (HCOOH)1/2 at high dose rates, and as (dose rate)-1/2 at constant concentration. These results indicate a chain reaction. The reaction sequence explains the chain formation of carbon dioxide. G(H2) decreases from 3.2 in dilute solutions to 2.4 at 5 to 10M formic acid and then remains unchanged with increasing concentration. G(CO) rises from zero with increase of formic acid concentration, rapidly at first and then more gradually to 1.25 in pure formic acid. Direct excitation of formic acid by water sub-excitation electrons is suggested as the mechanism explaining the carbcn monoxide yields at low concentrations. Some supporting photochemical studies at 1860, 2537, and 2669 A are reported.

Research Organization:
Argonne National Lab., Ill.
Sponsoring Organization:
USDOE
NSA Number:
NSA-14-025510
OSTI ID:
4135206
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 18 Vol. 82; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
Country unknown/Code not available
Language:
English