Eduardo Humeres, Marília Isabel Tarnowski Correia, Nito Angelo Debacher, Regina de F. P. M. Moreira
{"title":"碳上还原二氧化硫的脱硫途径的机理。二硫和四硫的二聚反应","authors":"Eduardo Humeres, Marília Isabel Tarnowski Correia, Nito Angelo Debacher, Regina de F. P. M. Moreira","doi":"10.1002/poc.4610","DOIUrl":null,"url":null,"abstract":"<p>The desulfurization of carbons modified with SO<sub>2</sub> was studied as a dispersion in boiling cyclohexane (81°C) using activated carbon (mAC) and graphene oxide (mGO), modified by SO<sub>2</sub>. The steady-state species in the carbon matrix after the catalytic reduction of SO<sub>2</sub> was considered a trisulfane. For mAC, there was a burst of a sulfur species identified as S<sub>2</sub> by UV spectrum with a maximum at 217 nm (ε<sub>M</sub> at 217 nm = 2.56 × 10<sup>3</sup>) that showed a second-order decay of absorbance with \n<span></span><math>\n <msub>\n <mi>k</mi>\n <msub>\n <mi>S</mi>\n <mn>2</mn>\n </msub>\n </msub></math> = 47.29 M<sup>-1</sup>·sec<sup>-1</sup> (\n<span></span><math>\n <msubsup>\n <mi>ΔG</mi>\n <mn>354</mn>\n <mo>‡</mo>\n </msubsup></math>= 18.1 kcal·mol<sup>-1</sup>). The product was postulated to be S<sub>4</sub>. No other consecutive reaction was observed because of the possible adsorption of S<sub>4</sub> in the carbon matrix. The desulfurization of mGO was shown by XPS and the kinetics were a second-order decay up to 16 min (\n<span></span><math>\n <msub>\n <mi>k</mi>\n <msub>\n <mi>S</mi>\n <mn>2</mn>\n </msub>\n </msub>\n <mo>=</mo></math> 18.41 M<sup>-1</sup>·sec<sup>-1</sup>;\n<span></span><math>\n <mspace></mspace>\n <msubsup>\n <mi>ΔG</mi>\n <mn>354</mn>\n <mo>‡</mo>\n </msubsup></math>= 18.8 kcal·mol<sup>-1</sup>) followed by a second-order increase of absorbance with \n<span></span><math>\n <msub>\n <mi>k</mi>\n <msub>\n <mi>S</mi>\n <mn>4</mn>\n </msub>\n </msub></math> = 3.84 M<sup>-1</sup>·sec<sup>-1</sup> (\n<span></span><math>\n <msubsup>\n <mi>ΔG</mi>\n <mn>354</mn>\n <mo>‡</mo>\n </msubsup></math>= 19.9), where the product showed a double maximum at 260-285 nm typical of S<sub>8</sub>. These results are consistent with a mechanism of consecutive thermodynamically favorable dimerizations of S<sub>2</sub> and S<sub>4</sub> and with the desulfurization mechanism that has been previously postulated.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 7","pages":""},"PeriodicalIF":1.9000,"publicationDate":"2024-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Mechanism of the desulfurization route of the reduction of SO2 on carbons. Dimerization of Disulfur and Tetrasulfur\",\"authors\":\"Eduardo Humeres, Marília Isabel Tarnowski Correia, Nito Angelo Debacher, Regina de F. P. M. Moreira\",\"doi\":\"10.1002/poc.4610\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The desulfurization of carbons modified with SO<sub>2</sub> was studied as a dispersion in boiling cyclohexane (81°C) using activated carbon (mAC) and graphene oxide (mGO), modified by SO<sub>2</sub>. The steady-state species in the carbon matrix after the catalytic reduction of SO<sub>2</sub> was considered a trisulfane. For mAC, there was a burst of a sulfur species identified as S<sub>2</sub> by UV spectrum with a maximum at 217 nm (ε<sub>M</sub> at 217 nm = 2.56 × 10<sup>3</sup>) that showed a second-order decay of absorbance with \\n<span></span><math>\\n <msub>\\n <mi>k</mi>\\n <msub>\\n <mi>S</mi>\\n <mn>2</mn>\\n </msub>\\n </msub></math> = 47.29 M<sup>-1</sup>·sec<sup>-1</sup> (\\n<span></span><math>\\n <msubsup>\\n <mi>ΔG</mi>\\n <mn>354</mn>\\n <mo>‡</mo>\\n </msubsup></math>= 18.1 kcal·mol<sup>-1</sup>). The product was postulated to be S<sub>4</sub>. No other consecutive reaction was observed because of the possible adsorption of S<sub>4</sub> in the carbon matrix. The desulfurization of mGO was shown by XPS and the kinetics were a second-order decay up to 16 min (\\n<span></span><math>\\n <msub>\\n <mi>k</mi>\\n <msub>\\n <mi>S</mi>\\n <mn>2</mn>\\n </msub>\\n </msub>\\n <mo>=</mo></math> 18.41 M<sup>-1</sup>·sec<sup>-1</sup>;\\n<span></span><math>\\n <mspace></mspace>\\n <msubsup>\\n <mi>ΔG</mi>\\n <mn>354</mn>\\n <mo>‡</mo>\\n </msubsup></math>= 18.8 kcal·mol<sup>-1</sup>) followed by a second-order increase of absorbance with \\n<span></span><math>\\n <msub>\\n <mi>k</mi>\\n <msub>\\n <mi>S</mi>\\n <mn>4</mn>\\n </msub>\\n </msub></math> = 3.84 M<sup>-1</sup>·sec<sup>-1</sup> (\\n<span></span><math>\\n <msubsup>\\n <mi>ΔG</mi>\\n <mn>354</mn>\\n <mo>‡</mo>\\n </msubsup></math>= 19.9), where the product showed a double maximum at 260-285 nm typical of S<sub>8</sub>. These results are consistent with a mechanism of consecutive thermodynamically favorable dimerizations of S<sub>2</sub> and S<sub>4</sub> and with the desulfurization mechanism that has been previously postulated.</p>\",\"PeriodicalId\":16829,\"journal\":{\"name\":\"Journal of Physical Organic Chemistry\",\"volume\":\"37 7\",\"pages\":\"\"},\"PeriodicalIF\":1.9000,\"publicationDate\":\"2024-04-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Physical Organic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/poc.4610\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Physical Organic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/poc.4610","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Mechanism of the desulfurization route of the reduction of SO2 on carbons. Dimerization of Disulfur and Tetrasulfur
The desulfurization of carbons modified with SO2 was studied as a dispersion in boiling cyclohexane (81°C) using activated carbon (mAC) and graphene oxide (mGO), modified by SO2. The steady-state species in the carbon matrix after the catalytic reduction of SO2 was considered a trisulfane. For mAC, there was a burst of a sulfur species identified as S2 by UV spectrum with a maximum at 217 nm (εM at 217 nm = 2.56 × 103) that showed a second-order decay of absorbance with
= 47.29 M-1·sec-1 (
= 18.1 kcal·mol-1). The product was postulated to be S4. No other consecutive reaction was observed because of the possible adsorption of S4 in the carbon matrix. The desulfurization of mGO was shown by XPS and the kinetics were a second-order decay up to 16 min (
18.41 M-1·sec-1;
= 18.8 kcal·mol-1) followed by a second-order increase of absorbance with
= 3.84 M-1·sec-1 (
= 19.9), where the product showed a double maximum at 260-285 nm typical of S8. These results are consistent with a mechanism of consecutive thermodynamically favorable dimerizations of S2 and S4 and with the desulfurization mechanism that has been previously postulated.
期刊介绍:
The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.