Kinetics of Oxidation of Thiocarbohydrazide, its Metal Complex and Hydrazone by Chloramine-T in partial Aqueous Media
| Main Authors: | B. THIMME GOWDA, P. V. VELAYUDHAN NAMBIAR |
|---|---|
| Format: | Article Journal |
| Bahasa: | eng |
| Terbitan: |
, 1990
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| Subjects: | |
| Online Access: |
https://zenodo.org/record/6204395 |
| ctrlnum |
6204395 |
|---|---|
| fullrecord |
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<dc schemaLocation="http://www.openarchives.org/OAI/2.0/oai_dc/ http://www.openarchives.org/OAI/2.0/oai_dc.xsd"><creator>B. THIMME GOWDA</creator><creator>P. V. VELAYUDHAN NAMBIAR</creator><date>1990-09-30</date><description>Department of Post-Graduate Studies and Research in Chemistry, Mangalore University, Mangalagangothri-574 199
Manuscript received 3 January 1990, accepted 11 May 1990
Kinetics of oxidations of thiocarbohydrazide (TCH), its metal complex and hydra· zone by chloramine-T in 1 : 1 (v/v) water-methanol and water-acetic acid media have been investigated in the presence of perchloric acid. Oxidations of all the substrates in both the media showed first order kinetics in [oxidant] and varying fractional orders in [substrate]. Oxidation of TCH and its complex in water-methanol medium showed positive fractional order kinetics in [H+] while oxidations of hydrazone in water-methanol medium and those of both TCH and hydrazone in water-acetic acid medium showed inverse fractional order kinetics in [H+]. Variation in ionic strength of the medium had little effect on the rates of oxidations. in all the cases. Variation in solvent composition or the medium had considerable effect on rates of oxidations, but the effect was more pronounced in water-acetic acid medium Addition of the reduced product of the oxidant had no significant effect on the rates of reactions. Both two-pathway and Michaelis-Menten type mechanisms have been considered to explain the observed results and ~he related rate laws deduced. The rate-limting steps have been identified in all the cases ; the coefficients of these steps were calculated at different temperatures and the activation parameters computed. The rate constants have also been predicted from the rate Jaws as [substrate] and [H+] were varied. The results of the investigations have also been compared with those in aqueous medium.</description><identifier>https://zenodo.org/record/6204395</identifier><identifier>10.5281/zenodo.6204395</identifier><identifier>oai:zenodo.org:6204395</identifier><language>eng</language><relation>doi:10.5281/zenodo.6204394</relation><rights>info:eu-repo/semantics/openAccess</rights><rights>https://creativecommons.org/licenses/by/4.0/legalcode</rights><source>Journal of Indian Chemical Society Vol. 67(Sep 1990) 709-718</source><subject>Thiocarbohydrazide</subject><subject>Chloramine</subject><subject>Perchloric acid</subject><title>Kinetics of Oxidation of Thiocarbohydrazide, its Metal Complex and Hydrazone by Chloramine-T in partial Aqueous Media</title><type>Journal:Article</type><type>Journal:Article</type><recordID>6204395</recordID></dc>
|
| language |
eng |
| format |
Journal:Article Journal Journal:Journal |
| author |
B. THIMME GOWDA P. V. VELAYUDHAN NAMBIAR |
| title |
Kinetics of Oxidation of Thiocarbohydrazide, its Metal Complex and Hydrazone by Chloramine-T in partial Aqueous Media |
| publishDate |
1990 |
| topic |
Thiocarbohydrazide Chloramine Perchloric acid |
| url |
https://zenodo.org/record/6204395 |
| contents |
Department of Post-Graduate Studies and Research in Chemistry, Mangalore University, Mangalagangothri-574 199
Manuscript received 3 January 1990, accepted 11 May 1990
Kinetics of oxidations of thiocarbohydrazide (TCH), its metal complex and hydra· zone by chloramine-T in 1 : 1 (v/v) water-methanol and water-acetic acid media have been investigated in the presence of perchloric acid. Oxidations of all the substrates in both the media showed first order kinetics in [oxidant] and varying fractional orders in [substrate]. Oxidation of TCH and its complex in water-methanol medium showed positive fractional order kinetics in [H+] while oxidations of hydrazone in water-methanol medium and those of both TCH and hydrazone in water-acetic acid medium showed inverse fractional order kinetics in [H+]. Variation in ionic strength of the medium had little effect on the rates of oxidations. in all the cases. Variation in solvent composition or the medium had considerable effect on rates of oxidations, but the effect was more pronounced in water-acetic acid medium Addition of the reduced product of the oxidant had no significant effect on the rates of reactions. Both two-pathway and Michaelis-Menten type mechanisms have been considered to explain the observed results and ~he related rate laws deduced. The rate-limting steps have been identified in all the cases ; the coefficients of these steps were calculated at different temperatures and the activation parameters computed. The rate constants have also been predicted from the rate Jaws as [substrate] and [H+] were varied. The results of the investigations have also been compared with those in aqueous medium. |
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