Thermodynamic analysis of synthesis of cyclopentanol from cyclopentene and comparison with experimental data

Abstract

Cyclopentanol is a very important chemical intermediate, which has been widely used in the chemical industry, and could be prepared from cyclopentene by two steps: an initial addition-esterification reaction of cyclopentene with acetic acid and the subsequent transesterification reaction with methanol. However, so far, no direct theoretical or experimental work has been reported on this process. In this work, we have carried out the thermodynamic calculation of the indirect process and also validated the thermodynamic prediction through experimental work. The liquid heat capacities of cyclopentanol and cyclopentyl acetate were estimated using the Ruzicka-Domalski group contribution method, the standard enthalpy of formation and standard entropy of gaseous cyclopentyl acetate by the Yoneda group contribution method, the standard vaporization enthalpy of cyclopentyl acetate by the Ducros group contribution method. The enthalpy changes, free energy changes, equilibrium constant and equilibrium conversion of the addition-esterification and transesterification reactions were calculated according to the principles of chemical thermodynamics in the temperature range from 273.15 to 373.15 K. The results showed that both the addition-esterification reaction and transesterification reaction were exothermic, the free energy changes increased with a rise on temperature, which indicated that low temperature was favorable for the reactions in the temperature range from 273.15 to 373.15 K. The optimal addition-esterification reaction conditions were a temperature range from 333.15 to 353.15 K, molar ratios of acetic acid to cyclopentene in the range from 2:1 to 3:1. For the transesterification reaction, the ideal temperature ranges from 323.15 to 343.15 K, with a molar ratio of methanol to cyclopentyl acetate in the range from 3:1 to 4:1. These thermodynamic calculation results for the addition-esterification reaction of cyclopentene and acetic acid experiments results are in good agreement with the experimental results.

Highly Efficient Indirect Hydration of Olefins to Alcohols Using Superacidic Polyoxometalate-Based Ionic Hybrids Catalysts

“…The feasibility of this methodology had been confirmed by Steyer and co-workers, indicating the advantages of high reaction selectivity, low pollution and corrosion, and mild reaction conditions. Moreover, it is worth noting that the esterification of cyclohexene with carboxylate acid is the determining step in the whole indirect hydration . That is to say, improving the rate of the first step of indirect hydration can effectively increase the yield of target product alcohol, in which the activity of catalysts employed is particularly important.…”

“…Moreover, it is worth noting that the esterification of cyclohexene with carboxylate acid is the determining step in the whole indirect hydration. 10 That is to say, improving the rate of the first step of indirect hydration can effectively increase the yield of target product alcohol, in which the activity of catalysts employed is particularly important. However, the conventional solid acid catalyst ion-exchange resins Indion-130 and Amberlyst-15 were found to induce <50% conversions of cyclohexene in the esterification of cyclohexene and formic acid.…”

Recent progress on CO2 separation membranes

“…This type of membrane has promising application possibilities. 84 The inorganic materials that are frequently utilized for the preparation of composite membranes include zeolite molecular sieves, 85 metal-organic frameworks 86 and carbon nanotubes. 87 Jiang et al 88 introduced a zeolite thin layer into a PSF/Matrimid hollow ber membrane and found that the selectivity for CO 2 in a CO 2 /CH 4 mixed system was enhanced by 50%.…”

Unraveling the reaction route and kinetics of 3‐methyl‐3‐penten‐2‐one synthesis for synthetic ketone fragrances

“…Using a thermodynamic analysis of chemical equilibrium is helpful to understand the significance of each reaction. [42][43][44] The group contribution method proposed by Yoneda et al is a widely-used approach to predict the thermodynamic properties for chemical equilibrium analysis. [45][46][47][48] Here we have applied a combination of experimental and theoretical investigations: analyzing the reaction routes by experiments and identifying the considerable side reactions by thermodynamics calculation, which is an effective and low-cost way to determine the routes for a complex reaction system.…”

“…Although the analysis and testing methods could accurately quantify all the components and help identify the significance of each side reaction, they are costly and time‐consuming, especially in case of many complex components. Using a thermodynamic analysis of chemical equilibrium is helpful to understand the significance of each reaction 42–44 . The group contribution method proposed by Yoneda et al .…”