Thermodynamic modeling of aqueous systems containing amines and amine hydrochlorides: Application to methylamine, morpholine, and morpholine derivatives

Łencka, Małgorzata M.; Kosinski, Jerzy J.; Wang, Peiming; Anderko, Andrzej

doi:10.1016/j.fluid.2015.10.025

Cited by 23 publications

(9 citation statements)

References 76 publications

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“…The accurate values for the ionization constants of H 2 O, CO 2 , and many amines have been reported in the literature, but only a limited number of carbamate formation constants for these amines, K carbam , are known. − As a result, the values for K carbam must be approximated from the semiempirical relationships or omitted from the chemical equilibrium models. There are currently no data in the literature for the carbamate formation constants of any MP.…”

Section: Introductionmentioning

confidence: 99%

Formation Constants and Conformational Analysis of Carbamates in Aqueous Solutions of 2-Methylpiperidine and CO₂ from 283 to 313 K by NMR Spectroscopy

et al. 2018

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Quantitative C nuclear magnetic resonance (NMR) spectroscopy was used to investigate the speciation in (2-methylpiperidine + HO + CO) systems at 283.2-313.2 K. The carbamate of 2-methylpiperidine(2-methylpiperidine- N-carboxylate) was shown for the first time to be a stable species in aqueous solutions. The spectroscopic results were used to obtain temperature-dependant formation constants for the carbamate using a simplified model for the activity coefficients from which the standard molar enthalpy of reaction was estimated. The results were incorporated into a self-consistent chemical equilibrium model, which includes vapor-liquid equilibria and all aqueous species, including the formation of carbamate. The predominant conformation of the sterically hindered carbamate, which was determined using two-dimensional exchange spectroscopy NMR, has the methyl group in the axial orientation and is in agreement with the density functional theory quantum chemical calculations.

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Section: Introductionmentioning

confidence: 99%

Formation Constants and Conformational Analysis of Carbamates in Aqueous Solutions of 2-Methylpiperidine and CO₂ from 283 to 313 K by NMR Spectroscopy

et al. 2018

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“…Modeling the behavior of such systems is challenging as it requires the simultaneous representation of aqueous amine hydrochloride phases from dilute solutions to the fused salt limit as well as vapor, solid and hydrocarbon-rich phases. 270 The importance of thermodynamics for electrochemical processes is not limited to corrosion and extends to batteries and fuel cells. For example, as a starting point in the analysis of batteries, thermodynamic analysis based on the standard-state properties of species makes it possible to calculate the theoretical energy density of possible battery systems.…”

Section: Modeling and Estimation Of Mixture Phase Equilibriummentioning

confidence: 99%

“…However, the combination of amines and HCl may lead to the presence of amine hydrochlorides, which may form very concentrated ionic liquids and/or hydroscopic solids. Modeling the behavior of such systems is challenging as it requires the simultaneous representation of aqueous amine hydrochloride phases from dilute solutions to the fused salt limit as well as vapor, solid and hydrocarbon-rich phases …”

Section: Modeling and Estimation Of Mixture Phase Equilibriummentioning

confidence: 99%

Current Practices and Continuing Needs in Thermophysical Properties for the Chemical Industry

Gupta

Elliott

Anderko

et al. 2023

Ind. Eng. Chem. Res.

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The status of thermophysical property needs of the chemical industry is reviewed and updated relative to similar observations from 20 years ago. The paper is informed by a series of symposia held over several years in conjunction with the American Institute of Chemical Engineers (AIChE) national meetings. Experiences of the authors are also incorporated, including a discussion of the state of the art in this area, as well as references to several of the articles included in a recent special issue of Ind. Eng. Chem. Res. (2022, volume 61, issue 42) devoted to the subject. In general, the trend is toward more rigorous molecular methods but ingrained empirical methods tend to hold on for extended times by adding increasingly sophisticated multiparameter correlations. There is also a tendency for research in newer methods to end prematurely with anecdotal proofs of principle, undermining their ability to supersede tried and true methods. Significant gaps exist in experimental data, for the development of estimation methods and validation of models besides a general need for technical knowledge development. Although progress is clear, some of the goals articulated 20 years ago remain to be achieved, even as new needs are identified in estimation. modeling, and measurements. One possible solution, to close experimental data gaps and to provide a continuous stream of trained personnel, is to establish multidisciplinary research centers of excellence in this important methodology.

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“…De Visscher and Vanderdeelen carefully document a specific but illuminating instance. However, nothing unveils the predicament more than the large number of different theoretical approaches that have been, and continue to be, described in the literature along with the frequent need for many of them subsequently to be extended or modified (for example, refs − and − ). There is general confusion implicit in having a multitude of ostensibly different, competing theoretical frameworks, some associated with major computer simulation packages but many just popping up in the literature as transient distractions.…”

Section: Thermodynamic Modeling Framework–unresolved Difficultiesmentioning

confidence: 99%

Thermodynamic Modeling of Aqueous Electrolyte Systems: Current Status

May

Rowland

2017

J. Chem. Eng. Data

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The current status of thermodynamic modeling in aqueous chemistry is reviewed. A number of recent developments hold considerable promise, but these need to be weighed against ongoing difficulties with existing theoretical modeling frameworks. Some key issues are identified and discussed. These include long-standing difficulties in choosing the right program code, in comparing alternatives objectively, in implementing models as published, and in wasting effort on numerous proposed “modifications” and/or “improvements”. There needs to be greater awareness of the major limitations that such assorted variations in modeling functions imply for practical thermodynamic modeling purposes. They typically lack proper substantiation, fail to distinguish between cause and effect, and are presented in ways that all-too-often cannot be falsified. Numerical correlations in particular permit overoptimistic assertions based only on “satisfactory” fits, neglecting the dictum that regression analyses can be used to discredit hypotheses but not to prove them. The risks of “model tuning” should always be acknowledged and minimized. Recognition of the uncertainties in data that have not been confirmed by independent measurement needs to be redoubled. Modeling frameworks incapable of explicit trace activity coefficient prediction should no longer be regarded as credible. The current modeling paradigm evidently has to be reassessed, hopefully to find better ways forward, including new protocols which command sufficient support to warrant IUPAC endorsement.

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Thermodynamic modeling of aqueous systems containing amines and amine hydrochlorides: Application to methylamine, morpholine, and morpholine derivatives

Cited by 23 publications

References 76 publications

Formation Constants and Conformational Analysis of Carbamates in Aqueous Solutions of 2-Methylpiperidine and CO₂ from 283 to 313 K by NMR Spectroscopy

Formation Constants and Conformational Analysis of Carbamates in Aqueous Solutions of 2-Methylpiperidine and CO₂ from 283 to 313 K by NMR Spectroscopy

Current Practices and Continuing Needs in Thermophysical Properties for the Chemical Industry

Thermodynamic Modeling of Aqueous Electrolyte Systems: Current Status

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Thermodynamic modeling of aqueous systems containing amines and amine hydrochlorides: Application to methylamine, morpholine, and morpholine derivatives

Cited by 23 publications

References 76 publications

Formation Constants and Conformational Analysis of Carbamates in Aqueous Solutions of 2-Methylpiperidine and CO2 from 283 to 313 K by NMR Spectroscopy

Formation Constants and Conformational Analysis of Carbamates in Aqueous Solutions of 2-Methylpiperidine and CO2 from 283 to 313 K by NMR Spectroscopy

Current Practices and Continuing Needs in Thermophysical Properties for the Chemical Industry

Thermodynamic Modeling of Aqueous Electrolyte Systems: Current Status

Contact Info

Product

Resources

About

Formation Constants and Conformational Analysis of Carbamates in Aqueous Solutions of 2-Methylpiperidine and CO₂ from 283 to 313 K by NMR Spectroscopy

Formation Constants and Conformational Analysis of Carbamates in Aqueous Solutions of 2-Methylpiperidine and CO₂ from 283 to 313 K by NMR Spectroscopy