Frequency response study of the dynamics of the platinum catalyzed interconversion of methylcyclohexane, toluene, and
Sebastian C Reyes1, John H Sinfelt, Gregory J DeMartin
1Corporate Strategic Research, ExxonMobil Research and Engineering Company, 1545 Route 22 East, Annandale, New Jersey 08801, USA. sebastian.c.reyes@exxonmobil.com
Abstract:
The dynamics of the platinum catalyzed interconversion of methylcyclohexane, toluene, and hydrogen near equilibrium were investigated in a closed reactor system by a frequency response method at temperatures in the range of 433 to 473 K and at total pressures in the vicinity of 80 to 110 Torr. The gas phase in contact with the platinum catalyst was always hydrogen-rich, with hydrogen to hydrocarbon mole ratios maintained in the range of 3.2 to 4.6. The frequency response method utilized small perturbations (lower than 1%) of the volume of the system, with measurements of the total pressure being used to determine the response of the system. The range of perturbation frequencies investigated was approximately 0.002 to 3 Hz (0.013 to 19 rad s(-1)). The experiments revealed two characteristic relaxation frequencies that are associated with the dynamics of the interconversion. The dynamics of the system are interpreted in terms of a simple two-step interconversion sequence with the aid of a phenomenological frequency response theory formulated in terms of relaxation frequencies of the steps and equilibrium properties of the system. It is concluded that one of the steps, a toluene adsorption-desorption step, is much slower than the other, a step involving the interconversion of the gas-phase methylcyclohexane and chemisorbed toluene that releases or consumes hydrogen in the process.
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Stability of Substituted Cyclohexanes
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
