How to measure both primary and secondary hydrogen isotope effects in hydrogen abstraction from a substrate having two or more equivalent reactive hydrogen atoms

1981 ◽  
Vol 85 (9) ◽  
pp. 1099-1100 ◽  
Author(s):  
Rm. Subramanian ◽  
William H. Saunders
1962 ◽  
Vol 40 (4) ◽  
pp. 701-704 ◽  
Author(s):  
R. A. Bird ◽  
G. A. Harpell ◽  
K. E. Russell

The effect of six deuterated phenols on the rate and degree of polymerization of styrene has been studied. The rate and degree of polymerization are decreased by deuterated phenols to a much less extent than by the corresponding phenols. Approximate transfer constants are estimated, and it is found that the transfer constant for hydrogen abstraction from the deuterated phenol is less than 0.2 of the transfer constant for the normal phenol. The rates of reaction of 2,2-diphenyl-1-picrylhydrazyl with three deuterated phenols have been determined. The rate constants for deuterated 2,6-di-t-butylphenol and 4-bromophenol are less than 0.15 of those for the corresponding phenols, but the isotope effect appears to be small with 4-nitrophenol.


2021 ◽  
Author(s):  
Andrea Watzinger ◽  
Melanie Hager ◽  
Thomas Reichenauer ◽  
Gerhard Soja ◽  
Paul Kinner

AbstractMaintaining and supporting complete biodegradation during remediation of petroleum hydrocarbon contaminated groundwater in constructed wetlands is vital for the final destruction and removal of contaminants. We aimed to compare and gain insight into biodegradation and explore possible limitations in different filter materials (sand, sand amended with biochar, expanded clay). These filters were collected from constructed wetlands after two years of operation and batch experiments were conducted using two stable isotope techniques; (i) carbon isotope labelling of hexadecane and (ii) hydrogen isotope fractionation of decane. Both hydrocarbon compounds hexadecane and decane were biodegraded. The mineralization rate of hexadecane was higher in the sandy filter material (3.6 µg CO2 g−1 day−1) than in the expanded clay (1.0 µg CO2 g−1 day−1). The microbial community of the constructed wetland microcosms was dominated by Gram negative bacteria and fungi and was specific for the different filter materials while hexadecane was primarily anabolized by bacteria. Adsorption / desorption of petroleum hydrocarbons in expanded clay was observed, which might not hinder but delay biodegradation. Very few cases of hydrogen isotope fractionation were recorded in expanded clay and sand & biochar filters during decane biodegradation. In sand filters, decane was biodegraded more slowly and hydrogen isotope fractionation was visible. Still, the range of observed apparent kinetic hydrogen isotope effects (AKIEH = 1.072–1.500) and apparent decane biodegradation rates (k = − 0.017 to − 0.067 day−1) of the sand filter were low. To conclude, low biodegradation rates, small hydrogen isotope fractionation, zero order mineralization kinetics and lack of microbial biomass growth indicated that mass transfer controlled biodegradation.


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