Pulse radiolysis study of dithio-oxamide in aqueous solutions

Pulse radiolysis study of dithio-oxamide in aqueous solutions The reactions of e− aq, H-atoms, OH radicals and some one electron oxidants and reductants were studied with dithio-oxamide (DTO) in aqueous solutions using pulse radiolysis technique. The transient species formed by the reaction of e− aq with DTO at pH 6.8 has an absorption band with λ max at 380 nm and is reducing in nature. H-atom reaction with DTO at pH 6.8 also produced the same transient species. The semi-reduced species was found to be neutral indicating that the electron adduct gets protonated quickly. However at pH 1, the species produced by H-atom reaction had a different spectrum with λ max at 360 and 520 nm. Reaction of acetone ketyl radicals and CO2 − radicals with DTO at pH 6.8 gave transient spectra which were identical to that obtained by e− aq reaction. However at pH 1, the spectrum obtained by the reaction of acetone ketyl radicals with DTO was similar to that obtained by H-atom reaction at that pH. The transient species formed by OH radical reaction with DTO in the pH range 1–9.2 also has two absorption maxima at 360 and 520 nm. This spectrum was identical with the spectrum obtained by H-atom reaction at pH 1. This means that all these radicals viz. OH, H-atom and (CH3)2COH radicals react with DTO at pH 1 by H-abstraction mechanism. The transient species produced was found to be sensitive to the presence of oxygen. One-electron oxidizing radicals such as Br2 −· and SO4 −· radicals reacted with DTO at neutral pH to give the same species as produced by OH radical reaction having absorption maxima at 360 to 520 nm. At acidic pHs, only Br2 −· and Cl2 −· radicals were able to oxidize DTO to give the same species as produced by OH radical reaction. The semioxidized species is a resonance stabilized species with the electron delocalized over the-N-C-S bond. This species was found to be neutral and non-oxidizing in nature. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Pulse radiolysis study of dithio-oxamide in aqueous solutions

Loading next page...
 
/lp/springer_journal/pulse-radiolysis-study-of-dithio-oxamide-in-aqueous-solutions-XmtKMn3c4D
Publisher
Brill Academic Publishers
Copyright
Copyright © 2000 by VSP
Subject
Chemistry; Catalysis; Physical Chemistry; Inorganic Chemistry
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1163/156856700X00264
Publisher site
See Article on Publisher Site

Abstract

The reactions of e− aq, H-atoms, OH radicals and some one electron oxidants and reductants were studied with dithio-oxamide (DTO) in aqueous solutions using pulse radiolysis technique. The transient species formed by the reaction of e− aq with DTO at pH 6.8 has an absorption band with λ max at 380 nm and is reducing in nature. H-atom reaction with DTO at pH 6.8 also produced the same transient species. The semi-reduced species was found to be neutral indicating that the electron adduct gets protonated quickly. However at pH 1, the species produced by H-atom reaction had a different spectrum with λ max at 360 and 520 nm. Reaction of acetone ketyl radicals and CO2 − radicals with DTO at pH 6.8 gave transient spectra which were identical to that obtained by e− aq reaction. However at pH 1, the spectrum obtained by the reaction of acetone ketyl radicals with DTO was similar to that obtained by H-atom reaction at that pH. The transient species formed by OH radical reaction with DTO in the pH range 1–9.2 also has two absorption maxima at 360 and 520 nm. This spectrum was identical with the spectrum obtained by H-atom reaction at pH 1. This means that all these radicals viz. OH, H-atom and (CH3)2COH radicals react with DTO at pH 1 by H-abstraction mechanism. The transient species produced was found to be sensitive to the presence of oxygen. One-electron oxidizing radicals such as Br2 −· and SO4 −· radicals reacted with DTO at neutral pH to give the same species as produced by OH radical reaction having absorption maxima at 360 to 520 nm. At acidic pHs, only Br2 −· and Cl2 −· radicals were able to oxidize DTO to give the same species as produced by OH radical reaction. The semioxidized species is a resonance stabilized species with the electron delocalized over the-N-C-S bond. This species was found to be neutral and non-oxidizing in nature.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Jan 1, 2000

References

You’re reading a free preview. Subscribe to read the entire article.


DeepDyve is your
personal research library

It’s your single place to instantly
discover and read the research
that matters to you.

Enjoy affordable access to
over 18 million articles from more than
15,000 peer-reviewed journals.

All for just $49/month

Explore the DeepDyve Library

Search

Query the DeepDyve database, plus search all of PubMed and Google Scholar seamlessly

Organize

Save any article or search result from DeepDyve, PubMed, and Google Scholar... all in one place.

Access

Get unlimited, online access to over 18 million full-text articles from more than 15,000 scientific journals.

Your journals are on DeepDyve

Read from thousands of the leading scholarly journals from SpringerNature, Elsevier, Wiley-Blackwell, Oxford University Press and more.

All the latest content is available, no embargo periods.

See the journals in your area

DeepDyve

Freelancer

DeepDyve

Pro

Price

FREE

$49/month
$360/year

Save searches from
Google Scholar,
PubMed

Create lists to
organize your research

Export lists, citations

Read DeepDyve articles

Abstract access only

Unlimited access to over
18 million full-text articles

Print

20 pages / month

PDF Discount

20% off