BARC/PUB/2003/0420

 
 

Kinetics and spectral properties of electron and .OH adducts of dimethylpyridines: A pulse radiolysis study

 
     
 
Author(s)

Grover, R.; Mudaliar, M.; Rao, B. S. M.; Mohan, H.; Mittal, J. P.
(ChD)

Source

Research on Chemical Intermediates, 2003. Vol. 29: pp. 157-168

ABSTRACT

The reactions of e-aq,OH,O•- and SO4•−with 2,4-, 2,6- and 3,5-dimethylpyridines have been investigated in aqueous solution by pulse radiolysis with optical detection. Both eaq and OH radicals have high reactivity toward these compounds with k=(4–8)×109dm3mol-1s-1.The rates of O•- ¡and SO4 reactions (.1–3)×109dm3mol-1s-1 were lower compared to the rate observed with the.OH radical. The transient absorption spectra obtained in the reaction of e¡aq with three isomers exhibited a weak broad band around 340 – 410 nm. The absorption maxima of the intermediates formed in the.OH and SO.¡4reactions were centred around 320 – 330 nm("D2450– 3500 dm3mol¡1cm¡1/with an additional broad peak in the range 460 – 520 nm which are attributed to the corresponding .OH adducts. The spectra in the O.¡reaction have absorption maxima between 300 and 320 nm and it reacts both by addition and H-abstraction from the CH3 group. A reaction mechanism consistent with the observed results is proposed

 
 
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