Kinetics of esterification of acetic acid and methanol using Amberlyst 36 cation-exchange resin solid catalyst

Mekala, Mallaiah; Goli, Venkat Reddy

doi:10.3184/146867815x14413752286146

Cited by 11 publications

(15 citation statements)

References 18 publications

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“…The synthesis and kinetics via microwave, membrane, batch, and microchannel reactors have also been addressed . Most recent experimental investigations (from 2011) have reported free energy of activation for this process with values ranging from ∼7.7 to 15.1 kcal mol −1 in different reaction media/solvents at temperature up to 333 K. In addition to this parameter, some studies also provided heat of reaction (enthalpy, Δ H ) and entropy (Δ S ) of activation values within −1.0 and 0.1 kcal mol −1 for Δ H while 1.0 E −5 and 0.1 cal (mol K) −1 for the reaction entropy …”

Section: Introductionmentioning

confidence: 99%

DFT study of the acid‐catalyzed esterification reaction mechanism of methanol with carboxylic acid and its halide derivatives

Lawal

Govender

Maguire

et al. 2017

Int J of Quantum Chemistry

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Extensive experimental studies have been dedicated to the esterification mechanisms from carboxylic acids and acid halides. However, attention on the theoretical aspect of the mechanism has been scarcely addressed. Herein, the acid-catalyzed esterification mechanism of methanol with acetic acid and its halide derivatives is described using density functional theoretical method and solvation model based on density. The mechanistic investigation involved formation of cyclic prereaction and 6-membered ring transition structures, which favors the esterification process and product formation. A good comparison with experimental data from literature for the esterification reaction of acetic acid with methanol was achieved through this in silico approach. Density Functional Theory-based quantum descriptors were applied to provide a better understanding on the reactivity, selectivity, and stability of this reaction. This theoretical results provide a crucial guide to study classical acid-catalyzed reaction mechanisms and applying a reasonable theoretical model to study similar organic reactions. In addition, it can be applied to larger systems such as enzymatic mechanism. K E Y W O R D S acetic acid (HOAc), acetyl halides (XAc), Density Functional Theory (DFT), esterification reaction 1 | I N TR ODU C TI ON Esters remained important intermediates in the chemical industry due to their widespread pharmaceutical applications and biodiesel production.Dating back to the 1890s, the Fischer esterification [1] reaction has remained a crucial process through which esters are formed via dehydrative coupling of carboxylic acids (RCOOH) with alcohol (ROH) in the presence of inorganic liquid acids. [2][3][4] Among studies on kinetics and mechanism of acid-catalyzed RCOOH esterification, methyl acetate (MeOAc) formation from acetic acid (HOAc) and methanol (MeOH) using homogeneous and heterogeneous acid catalysts are abundant. [4][5][6] R€ onnback et al. [2] had earlier hypothesized the nature of the acid-catalyzed esterification of HOAc with MeOH as a stepwise model involving 7 transition structures and 3 intermediates in acidic solution. This experimental study [2] was novel and serves as a basis for subsequent investigations.The overall reaction process is presented as:The production of MeOAc from HOAc and MeOH has been kinetically mediated by homogeneous [2,[6][7][8][9][10][11] or heterogeneous catalysts, [5,6,[12][13][14][15] with more research being performed on the latter due to increased reusability, [16] high selectivity, [17] and less product contamination. [6,16,18] The synthesis and kinetics via microwave, membrane, batch, and microchannel reactors have also been addressed. [12,13,19,20] Most recent experimental investigations (from 2011) have reported free energy of activation for this process with values ranging from 7.7 to 15.1 kcal mol 21[4-6,15,21-26] in Int J Quantum Chem. 2018;118:e25497.

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Section: Introductionmentioning

confidence: 99%

DFT study of the acid‐catalyzed esterification reaction mechanism of methanol with carboxylic acid and its halide derivatives

Lawal

Govender

Maguire

et al. 2017

Int J of Quantum Chemistry

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“…So that the assumption is not applicable in that cases. So the alternate method to measure the concentration of the multi component mixture is use of instruments like Gas Chromatography, which gives accurate composition of the mixtures [9] , [10] , [11] , [12] , [13] , [14] .…”

Section: Datamentioning

confidence: 99%

Data on acetic acid–methanol–methyl acetate–water mixture analysised by dual packed column Gas Chromatography

Mekala¹,

Goli

2018

Data in Brief

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The composition of multicomponent determination by colorimetric titration is difficult. This complexity is easily overcome by using Gas Chromatography technique instead of wet method for multi-component mixture analysis. In Gas Chromatography, first the standard chart is prepared by using the known amount sample concentration as the reference. Once calibration chart is prepared the unknown sample concentration easily measured by using the standard chart. In the present study a standard calibration chart developed for the four component system of acetic acid–methanol–methyl acetate–water. The samples were taken at various concentrations of all components and different chromatograms obtained under various concentrations respectively. The method of optimization was first carried out to get the sharp peaks of individual components and binary pairs also. By using those conditions, the multi components concentrations were estimated. From the present results, the area under gas chromatogram is linearly varying with mole% of the components compared to mass%.

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“…Cross-linked polymer resins, either unmodified or functionalized with specific groups, are used in a broad range of applications, including, among others, water treatment, chromatography, hydrogen storage, and hydrometallurgy. − Additionally, functionalized resins are increasingly used as high-performance heterogeneous catalysts for organic synthesis reactions, such as (trans)esterifications, etherifications, dehydrations, aldol reactions, Suzuki–Miyaura cross-couplings, phenol alkylations, and so forth. − It should, however, be noted that these materials exhibit a remarkable phenomenon as compared to other types of heterogeneous catalysts. Namely, when a dry resin is allowed to make contact with a liquid, it tends to swell, that is, a portion of the liquid is sorbed by the resin, resulting in an increase of its volume. ,,− The sorption phenomena occurring during the swelling of a resin can be classified into two categories: (i) absorption of liquid into the resin pores and (ii) adsorption of components onto functional groups.…”

Section: Introductionmentioning

confidence: 99%

Critical Assessment of the Thermodynamics in Acidic Resin-Catalyzed Esterifications

Lauwaert

Steene

Vermeir

et al. 2020

Ind. Eng. Chem. Res.

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Resins are interesting catalysts for organic reactions, which are characterized by a remarkable swelling behavior upon exposure to liquids, typically resulting in selective sorption in the case of mixtures. Hence, when constructing kinetic models for reactions catalyzed by such resins, the component partitioning between the bulk liquid and polymer liquid and its effect on their thermodynamic activities have to be properly taken into account. A kinetic model is developed for acidic resin-catalyzed esterification, while comparing two scenarios for capturing the thermodynamics within the resin pores. For the specific case study on a single resin with a specific solvent, compensation effects between the calculated thermodynamic activities in the resin and the estimated rate coefficients render only minor performance differences between the two scenarios. Still, aiming at extending the scope toward other solvents and/or resins, it is deemed crucial to explicitly account for the resin's selective sorption and swelling behavior.

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Kinetics of esterification of acetic acid and methanol using Amberlyst 36 cation-exchange resin solid catalyst

Cited by 11 publications

References 18 publications

DFT study of the acid‐catalyzed esterification reaction mechanism of methanol with carboxylic acid and its halide derivatives

DFT study of the acid‐catalyzed esterification reaction mechanism of methanol with carboxylic acid and its halide derivatives

Data on acetic acid–methanol–methyl acetate–water mixture analysised by dual packed column Gas Chromatography

Critical Assessment of the Thermodynamics in Acidic Resin-Catalyzed Esterifications

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