ICCAS OpenIR
Chemical reaction in binary mixtures near the critical region: Thermal decomposition of 2,2 '-azobis(isobutyronitrile) in CO(2)/ethanol
Li, HP; Han, BX; Liu, J; Gao, L; Hou, ZS; Jiang, T; Liu, ZM; Zhang, XG; He, J
2002-12-16
Source PublicationCHEMISTRY-A EUROPEAN JOURNAL
ISSN0947-6539
Volume8Issue:24Pages:5593-5600
AbstractThe effects of pressure and of the composition of the CO(2)/ethanol mixed solvent in the critical region on the kinetics of the decomposition of 2,2'-azobis(isobutyronitrile) (AIBN) were studied at 333.15 K. The rate constants (k(d)) in the mixed solvent far from the critical point and in liquid n-hexane and ethanol were also determined for comparison. It was found that k(d) is very sensitive to pressure in the mixed solvent near the critical point. However, in the mixed solvent outside the critical region k(d) is nearly independent of pressure. Interestingly, k(d) in the mixed solvent in the critical region can be higher than that in ethanol at the same temperature, suggesting that no significant enhancement in the reaction rate by a small pressure change in the critical region of the mixed solvent can be achieved by changing the composition of the liquid solvent in the traditional way. Transition-state theory can predict k(d) in the mixed solvent far from the critical point and in the liquid solvents well. However, it cannot predict k(d) in the mixed solvent in the critical region. The special intermolecular interaction between the solvent and the reaction species may contribute to this interesting phenomenon. This work also shows that if pure CO(2) or ethanol are used as solvents, the reaction cannot be carried out in the critical region of the solvents at the desired temperature, while it can be conducted in the critical region of the mixed solvent of suitable composition, where the solvent is highly compressible.
KeywordAzo Compounds Kinetics Phase Diagrams Supercritical Fluids
Indexed BySCI
Language英语
WOS IDWOS:000179955800010
PublisherWILEY-BLACKWELL
Citation statistics
Cited Times:21[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/78344
Collection中国科学院化学研究所
Corresponding AuthorHan, BX
AffiliationChinese Acad Sci, Inst Chem, Ctr Mol Sci, Beijing 100080, Peoples R China
Recommended Citation
GB/T 7714
Li, HP,Han, BX,Liu, J,et al. Chemical reaction in binary mixtures near the critical region: Thermal decomposition of 2,2 '-azobis(isobutyronitrile) in CO(2)/ethanol[J]. CHEMISTRY-A EUROPEAN JOURNAL,2002,8(24):5593-5600.
APA Li, HP.,Han, BX.,Liu, J.,Gao, L.,Hou, ZS.,...&He, J.(2002).Chemical reaction in binary mixtures near the critical region: Thermal decomposition of 2,2 '-azobis(isobutyronitrile) in CO(2)/ethanol.CHEMISTRY-A EUROPEAN JOURNAL,8(24),5593-5600.
MLA Li, HP,et al."Chemical reaction in binary mixtures near the critical region: Thermal decomposition of 2,2 '-azobis(isobutyronitrile) in CO(2)/ethanol".CHEMISTRY-A EUROPEAN JOURNAL 8.24(2002):5593-5600.
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