Journal article
Alcohol Clustering Mechanisms in Supercritical Carbon Dioxide Using Pulsed-Field Gradient, Diffusion NMR and Network Analysis: Feedback on Stepwise Self-Association Models
The journal of physical chemistry. B, Vol.123(25), pp.5316-5323
06/27/2019
Handle:
https://hdl.handle.net/2376/110116
PMID: 31242744
Abstract
Co-solvent clustering in complex fluids is fundamental to solution phase processes, influencing speciation, reactivity, and transport. Herein, methanol (MeOH) clustering in supercritical carbon dioxide is explored with pulsed-field gradient, diffusion-ordered nuclear magnetic resonance spectroscopy (DOSY-NMR), and molecular dynamics (MD) simulations. Refinements on the application of self-association models to DOSY-NMR experiments on clustering species are presented. Network analysis of MD simulations reveals an elevated stability of cyclic tetrameric clusters across MeOH concentrations, which is consistent with experimental DOSY-NMR molecular cluster distributions calculated with self-association models that include both cooperative cluster assembly and entropic penalties for the formation of large clusters. Simulations also detail the emergence of cluster-assembly and cluster-disassembly reactions that deviate from stepwise monomer addition or removal. This combination of experiment, simulation, and novel analyses facilitates refinement of models that describe co-solvent aggregation with far-reaching impact on the prediction of solution phase properties of complex fluids.
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Details
- Title
- Alcohol Clustering Mechanisms in Supercritical Carbon Dioxide Using Pulsed-Field Gradient, Diffusion NMR and Network Analysis: Feedback on Stepwise Self-Association Models
- Creators
- Trent R GrahamDaniel J PopeYasaman GhadarSue ClarkAurora ClarkSteven R Saunders
- Publication Details
- The journal of physical chemistry. B, Vol.123(25), pp.5316-5323
- Academic Unit
- Chemistry, Department of; Chemical Engineering and Bioengineering, School of
- Publisher
- American Chemical Society
- Identifiers
- 99900547031801842
- Language
- English
- Resource Type
- Journal article