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Kinetic Study of Heterogeneous and Homogeneous Catalytic Reactions in Molecular and Ionic Solvents and Their Mixtures

Khodadadi Moghaddam, Mohammad | 2008

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  1. Type of Document: Ph.D. Dissertation
  2. Language: Farsi
  3. Document No: 39009 (03)
  4. University: Sharif University of Technology
  5. Department: Chemistry
  6. Advisor(s): Gholami, Mohammad Reza; Habibi Yangjeh, Aziz
  7. Abstract:
  8. Solvatochromic parameters (ETN: normalized polarity parameter, π*: dipolarity/polarizability, β: hydrogen-bond acceptor basicity, α: hydrogen-bond donor acidity) have been determined for binary mixtures of propan-2-ol, propan-1-ol, ethanol, methanol and water with recently synthesized ionic liquid (2-hydroxyethylammonium formate) at 25 ◦C. The applicability of nearly ideal combined binary solvent/Redlich-Kister equation was proved for the correlation of various solvatochromic parameters with solvent composition. Solute-solvent and solvent-solvent interactions were applied to interpret the results. Heterogeneous catalytic hydrogenation of cyclohexene, catalyzed by Pt/Al2O3, was carried out in solutions of 2-hydroxyethylammonium formate mixed with methanol, ethanol and propan-2-ol at 25 ºC. Single-parameter correlation of logk vs. π* gives reasonable results. The increase of the reaction rate with π* is attributed to the non-polar nature of the reactants. Synchronous heterogeneous catalytic hydrogenation of cyclohexene and acetone, catalyzed by Pt/Al2O3, was carried out in solutions of 2-hydroxy ethylammonium formate with ethanol and propan-1-ol at 25 ºC. Rate constants and selectivity of the reaction (relative to cyclohexene hydrogenation) increase with mole fraction of the ionic liquid. Single-parameter correlations of logk vs. π* (dipolarity/polarizibility) gives reasonable results in the solution. The increase of the reaction rate with π* is attributed to the non-polar nature of the reactants
  9. Keywords:
  10. Hydrogenation ; Solvatochromic Properties ; Pottasium Pholoride-Alumina Catalyst (KF-Al2o3) ; Ionic Liquids ; Cyclohexene ; Atmospheric Pressure

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