Kinetic, mechanistic and thermodynamic investigations on Iridium (III) catalyzed oxidation of D-Mannitol by N-chloro-p-toluenesulfonamide in perchloric acid medium
The present paper deals with the kinetics and mechanism of homogeneously Ir(III) chloride catalyzed oxidation of D-mannitol by chloramine-T [CAT] in perchloric acid medium in the temperature range of 30 to 45 0C. The reaction is carried out in the presence of mercuric acetate as a scavenger for chlo...
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Iranian Association of Chemical Engineering (IAChE)
2017-12-01
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| Series: | Iranian Journal of Chemical Engineering |
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| Online Access: | https://www.ijche.com/article_58604_ebb8cacb072571b0e5fdd47f6914d011.pdf |
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| author | J. Pandey A. Verma R. Patel Sh. Srivastava |
| author_facet | J. Pandey A. Verma R. Patel Sh. Srivastava |
| author_sort | J. Pandey |
| collection | DOAJ |
| description | The present paper deals with the kinetics and mechanism of homogeneously Ir(III) chloride catalyzed oxidation of D-mannitol by chloramine-T [CAT] in perchloric acid medium in the temperature range of 30 to 45 0C. The reaction is carried out in the presence of mercuric acetate as a scavenger for chloride ion. The experimental results show first order kinetics with respect to the oxidant [CAT] and catalyst [Ir(III)] while zero order with respect to substrate, i.e., D-Mannitol was observed. The reaction shows negligible effect of [Hg(OAc)2], [H+] and ionic strength of the medium. Chloride ion positively influence the rate of reaction. The reaction between chloramine-T and D-Mannitol in acid medium shows 2:1 stoichiometry. To calculate activation parameters, the reactions have been studied at four different temperatures between 30 to 45ºC. A mechanism involving the complex formation between catalyst and oxidant has been proposed. Mannonic acid has been identified chromatographically and spectroscopically as the final product of oxidation of D-Mannitol. Based on the kinetic data, reaction stoichiometry and product analysis, a reaction mechanism has been proposed and rate law has been derived. |
| format | Article |
| id | doaj-art-4e159cd90a7b4b0fa6cb5efc3eb59bd9 |
| institution | OA Journals |
| issn | 1735-5397 2008-2355 |
| language | English |
| publishDate | 2017-12-01 |
| publisher | Iranian Association of Chemical Engineering (IAChE) |
| record_format | Article |
| series | Iranian Journal of Chemical Engineering |
| spelling | doaj-art-4e159cd90a7b4b0fa6cb5efc3eb59bd92025-08-20T02:25:08ZengIranian Association of Chemical Engineering (IAChE)Iranian Journal of Chemical Engineering1735-53972008-23552017-12-01144778958604Kinetic, mechanistic and thermodynamic investigations on Iridium (III) catalyzed oxidation of D-Mannitol by N-chloro-p-toluenesulfonamide in perchloric acid mediumJ. Pandey0A. Verma1R. Patel2Sh. Srivastava3Department of Applied Chemistry, BBAU, Lucknow-226025, U.P., IndiaDepartment of Applied Chemistry, BBAU, Lucknow-226025, U.P., IndiaDepartment of Applied Chemistry, BBAU, Lucknow-226025, U.P., IndiaChemical laboratories, Feroze Gandhi College, Raebareli-229001, U.P., IndiaThe present paper deals with the kinetics and mechanism of homogeneously Ir(III) chloride catalyzed oxidation of D-mannitol by chloramine-T [CAT] in perchloric acid medium in the temperature range of 30 to 45 0C. The reaction is carried out in the presence of mercuric acetate as a scavenger for chloride ion. The experimental results show first order kinetics with respect to the oxidant [CAT] and catalyst [Ir(III)] while zero order with respect to substrate, i.e., D-Mannitol was observed. The reaction shows negligible effect of [Hg(OAc)2], [H+] and ionic strength of the medium. Chloride ion positively influence the rate of reaction. The reaction between chloramine-T and D-Mannitol in acid medium shows 2:1 stoichiometry. To calculate activation parameters, the reactions have been studied at four different temperatures between 30 to 45ºC. A mechanism involving the complex formation between catalyst and oxidant has been proposed. Mannonic acid has been identified chromatographically and spectroscopically as the final product of oxidation of D-Mannitol. Based on the kinetic data, reaction stoichiometry and product analysis, a reaction mechanism has been proposed and rate law has been derived.https://www.ijche.com/article_58604_ebb8cacb072571b0e5fdd47f6914d011.pdfkineticsmechanismir(iii) catalysisd-mannitolchloramine-tacidic medium |
| spellingShingle | J. Pandey A. Verma R. Patel Sh. Srivastava Kinetic, mechanistic and thermodynamic investigations on Iridium (III) catalyzed oxidation of D-Mannitol by N-chloro-p-toluenesulfonamide in perchloric acid medium Iranian Journal of Chemical Engineering kinetics mechanism ir(iii) catalysis d-mannitol chloramine-t acidic medium |
| title | Kinetic, mechanistic and thermodynamic investigations on Iridium (III) catalyzed oxidation of D-Mannitol by N-chloro-p-toluenesulfonamide in perchloric acid medium |
| title_full | Kinetic, mechanistic and thermodynamic investigations on Iridium (III) catalyzed oxidation of D-Mannitol by N-chloro-p-toluenesulfonamide in perchloric acid medium |
| title_fullStr | Kinetic, mechanistic and thermodynamic investigations on Iridium (III) catalyzed oxidation of D-Mannitol by N-chloro-p-toluenesulfonamide in perchloric acid medium |
| title_full_unstemmed | Kinetic, mechanistic and thermodynamic investigations on Iridium (III) catalyzed oxidation of D-Mannitol by N-chloro-p-toluenesulfonamide in perchloric acid medium |
| title_short | Kinetic, mechanistic and thermodynamic investigations on Iridium (III) catalyzed oxidation of D-Mannitol by N-chloro-p-toluenesulfonamide in perchloric acid medium |
| title_sort | kinetic mechanistic and thermodynamic investigations on iridium iii catalyzed oxidation of d mannitol by n chloro p toluenesulfonamide in perchloric acid medium |
| topic | kinetics mechanism ir(iii) catalysis d-mannitol chloramine-t acidic medium |
| url | https://www.ijche.com/article_58604_ebb8cacb072571b0e5fdd47f6914d011.pdf |
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