Rates and equilibria of ester hydrolysis: Combination of slow and rapid reactions

Jogunola, Olatunde; Salmi, Tapio; Eränen, Kari; Wärnå, Johan; Mikkola, Jyri‐Pekka

doi:10.1016/j.cep.2011.04.003

Cited by 16 publications

(19 citation statements)

References 17 publications

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“…Indeed, some of the earliest reports of autocatalysis involve such reactions 6. A common example is acid‐catalyzed ester hydrolysis,24 where the product of the hydrolysis is itself an acid. Autocatalysis has also been implicated in synthetically‐useful reactions, including esterification of alcohols and anhydrides,25 reduction of imines by SmI 2, 26 LDA‐mediated ortholithiation (LDA=lithium diisopropylamide),27 oxidative addition of aryl bromides to Pd 0 complexes,28 and C‐H activation by Ru II 29…”

Section: Examples Of Autocatalysismentioning

confidence: 99%

Mechanisms of Autocatalysis

Bissette¹,

Fletcher²

2013

Angew Chem Int Ed

358

268

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Self-replication is a fundamental concept. The idea of an entity that can repeatedly create more of itself has captured the imagination of many thinkers from von Neumann to Vonnegut. Beyond the sciences and science fiction, autocatalysis has found currency in economics and language theory, and has raised ethical fears memorably summed up by the "gray goo" trope. Autocatalysis is central to the propagation of life and intrinsic to many other biological processes. This includes the modern conception of evolution, which has radically altered humanity's image of itself. Organisms can be thought of as imperfect self-replicators which produce closely-related species, allowing for selection and evolution. Hence, any consideration of self-replication raises one of the most profound questions of all: what is life? Minimal self-replicating systems have been studied with the aim of understanding the principles underlying living systems, allowing us to refine our concepts of biological fitness and chemical stability, self-organization and emergence, and ultimately to discover how chemistry may become biology.

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Section: Examples Of Autocatalysismentioning

confidence: 99%

Mechanisms of Autocatalysis

Bissette¹,

Fletcher²

2013

Angew Chem Int Ed

358

268

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“…It may be observed first that the initial curvature is positive in the absence of autocatalysis or for low autocatalysis ratios (A < L according to (42)). Therefore, a negative initial curvature characterizes an autocatalytic behavior.…”

Section: Figurementioning

confidence: 99%

“…Some k u and k c values have been reported in the literature for auto-catalyzed hydrolyses (12,(36)(37)(38)(39)(40)(41)(42) . For instance, Krammer and Vogel (12) presented a plot for the hydrolysis of ethyl acetate, which displays a curvature from which A can be assessed by using (11) and the time for consuming half the initial esters.…”

Section: Figurementioning

confidence: 99%

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Crosslink Density Changes during the Hydrolysis of Tridimensional Polyesters

Richaud

Pierre

Coquillat

et al. 2014

Macro Theory & Simulations

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is an open access repository that collects the work of Arts et Métiers ParisTech researchers and makes it freely available over the web where possible. The hydrolysis of almost ideal networks based on macrodiols (poly(adipate of ethylene glycol)) of average molar mass about 2 kg/mol, with L=18 ester groups per chain has been studied. Tensile testing was used to evaluate the crosslink density through the statistical theory of rubber elasticity at two temperatures and three values of relative humidity. A kinetic model for ester consumption including an autocatalysis term was proposed and combined with two original approaches for modeling the crosslink density changes. This allowed kinetic parameters of hydrolysis to be determined, and very good predictions were obtained for the variations of crosslink density (or elastic modulus) in the three aging conditions considered.The initial curvature of elastic modulus vs. time was predicted positive for weak autocatalysis and negative for strong autocatalysis. The obtained conversion ratio at degelation was found to decrease sharply with the number of esters per elastically active chain.

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“…A suitable kinetic model was developed with consideration of the dissociation contributions of SA and propionic acid, and the effect of the temperature on the dissociation constant is described by the empirical correlations quoted from the literature. Jogunola et al 17, 18 investigated the autocatalytic hydrolysis kinetics for the hydrolysis of alkyl formates. An empirical kinetic model containing a kinetic factor was proposed.…”

Section: Introductionmentioning

confidence: 99%

Homogeneous Catalytic Kinetics of Methyl Glycolate Hydrolysis

Meh

Yang

et al. 2016

Chem Eng & Technol

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Catalytic hydrolysis of methyl glycolate is a promising way to produce glycolic acid with high purity. The hydrolysis of methyl glycolate was investigated both in a stirred-batch reactor and in a reactive distillation column. Batch hydrolysis distillation was found to be rather effective in improving the conversion of methyl glycolate. A mechanism model including the cooperative catalysis of sulfuric acid and the generated glycolic acid was developed based on the acid-catalyzed hydrolysis mechanism and the protolysis equilibrium; then, the model was further simplified according to the relationship between the concentrations of hydroxonium ions and their providers. This simplified model could be easily introduced to Aspen Plus and applied to simulating the homogeneous hydrolysis process of methyl glycolate with or without sulfuric acid as catalyst via the reactive distillation technique.

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Rates and equilibria of ester hydrolysis: Combination of slow and rapid reactions

Cited by 16 publications

References 17 publications

Mechanisms of Autocatalysis

Mechanisms of Autocatalysis

Crosslink Density Changes during the Hydrolysis of Tridimensional Polyesters

Homogeneous Catalytic Kinetics of Methyl Glycolate Hydrolysis

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