Determination of all <i>pK<sub>a</sub></i> Values of Some di- and Tri-Carboxylic Unsaturated and Epoxy Acids and Their Polylinear Correlation with the Carboxylic Group Atomic Charges

Pfendt, Lidija B.; Dražić, Branka; Popovic, G.; Drakulić, Branko J.; Vitnik, Željko J.; Juranić, Ivan O.

doi:10.3184/030823403103173732

Cited by 7 publications

(7 citation statements)

References 3 publications

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“…Aconitic acid is described in AIOMFAC using a functional group contribution method, which assumes that organic acid functionalities remain protonated. This assumption is reasonable for our experimental conditions as predictions of particle pH from the Extended AIM Aerosol Thermodynamics Model (E-AIM, ) , indicate a pH < 2, and the first p K a of trans -aconitic acid is 2.91, so we do not expect that the carboxylic acid groups are significantly deprotonated. For the organic systems studied here, we neglect ionic strength effects on the O 3 Henry’s law constant (see section ) and on the ozone–organic reaction rate coefficients.…”

Section: Model Formulationsupporting

confidence: 69%

Coupled Interfacial and Bulk Kinetics Govern the Timescales of Multiphase Ozonolysis Reactions

Willis

Wilson

2022

J. Phys. Chem. A

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Chemical transformations in aerosols impact the lifetime of particle phase species, the fate of atmospheric pollutants, and both climate- and health-relevant aerosol properties. Timescales for multiphase reactions of ozone in atmospheric aqueous phases are governed by coupled kinetic processes between the gas phase, the particle interface, and its bulk, which respond dynamically to reactive consumption of O3. However, models of atmospheric aerosol reactivity often do not account for the coupled nature of multiphase processes. To examine these dynamics, we use new and prior experimental observations of aqueous droplet reaction kinetics, including three systems with a range of surface affinities and ozonolysis rate coefficients (trans-aconitic acid (C6H6O6), maleic acid (C4H4O4), and sodium nitrite (NaNO2)). Using literature rate coefficients and thermodynamic properties, we constrain a simple two-compartment stochastic kinetic model which resolves the interface from the particle bulk and represents O3 partitioning, diffusion, and reaction as a coupled kinetic system. Our kinetic model accurately predicts decay kinetics across all three systems, demonstrating that both the thermodynamic properties of O3 and the coupled kinetic and diffusion processes are key to making accurate predictions. An enhanced concentration of adsorbed O3, compared to gas and bulk phases is rapidly maintained and remains constant even as O3 is consumed by reaction. Multiphase systems dynamically seek to achieve equilibrium in response to reactive O3 loss, but this is hampered at solute concentrations relevant to aqueous aerosol by the rate of O3 arrival in the bulk by diffusion. As a result, bulk-phase O3 becomes depleted from its Henry’s law solubility. This bulk-phase O3 depletion limits reaction timescales for relatively slow-reacting organic solutes with low interfacial affinity (i.e., trans-aconitic and maleic acids, with k rxn ≈ 103–104 M–1 s–1), which is in contrast to fast-reacting solutes with higher surface affinity (i.e., nitrite, with k rxn ≈ 105 M–1 s–1) where surface reactions strongly impact the observed decay kinetics.

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Section: Model Formulationsupporting

confidence: 69%

Coupled Interfacial and Bulk Kinetics Govern the Timescales of Multiphase Ozonolysis Reactions

Willis

Wilson

2022

J. Phys. Chem. A

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“…OA has two free protons with pK a1 and pK a2 values of 1.27 and 4.27, respectively, 17 and TaA has three protons with pK a1 , pK a2 , and pK a3 values of 2.91, 4.33, and 6.16, respectively. 18 Both acids have similar structures and stronger acidity than H 3 PO 4 . We systematically determine the effect of acid doping on the physical properties of PBI (such as density, thermal stability, and free volume) and gas transport properties (such as pure-gas sorption and pure-and mixed-gas permeability) at various temperatures.…”

Section: = × P S Dmentioning

confidence: 99%

“…Herein, we chose two polycarboxylic acids for PBI doping, namely oxalic acid (OA) and trans -aconitic acid (TaA), as shown in Figure a,b. OA has two free protons with p K a1 and p K a2 values of 1.27 and 4.27, respectively, and TaA has three protons with p K a1 , p K a2 , and p K a3 values of 2.91, 4.33, and 6.16, respectively . Both acids have similar structures and stronger acidity than H 3 PO 4 .…”

Section: Introductionmentioning

confidence: 99%

Facilely Cross-Linking Polybenzimidazole with Polycarboxylic Acids to Improve H₂/CO₂ Separation Performance

Bui

Huang

et al. 2021

ACS Appl. Mater. Interfaces

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Polybenzimidazole (PBI) with a strong size-sieving ability exhibits attractive H 2 /CO 2 separation properties for blue H 2 production and CO 2 capture. Herein, we report that PBI can be facilely cross-linked with polycarboxylic acids, oxalic acid (OA), and trans-aconitic acid (TaA) to improve its separation performance. The acids react with the amines on the PBI chains, decreasing free volume and increasing size-sieving ability. The acid doping increases H 2 /CO 2 selectivity from 12 to as high as 45 at 35 °C. The acid-doped samples demonstrate stable H 2 /CO 2 separation performance when challenged with simulated syngas containing water vapor at 150 °C, which surpasses state-of-the-art polymers and Robeson's upper bound for H 2 /CO 2 separation.

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“…Effective mobility was calculated for each analyte at increments of 0.1 units of background electrolyte pH (from pH 4.7 to pH 7.5) based on eq using the p K a values, and the mobility of intermediate and totally ionised species embedded in Peakmaster 5.3 for 18 out of 23 analytes . Thermodynamic acidity constants for the remaining 5 analytes (galacturonate, quinate, α-ketoglutarate, cis -aconitate, and trans -aconitate) were extracted from the literature, − while the mobilities of the fully ionised species for these acids was experimentally measured using a background electrolyte of pH 8.80 with an ionic strength of 4.95 mM (30 mM Tris-30 mM CHES containing 0.1% PVP). The obtained mobilities were further extrapolated against the Peakmaster data in order to construct a uniform data set.…”

Section: Methodsmentioning

confidence: 99%

In Silico Screening of Two-Dimensional Separation Selectivity for Ion Chromatography × Capillary Electrophoresis Separation of Low-Molecular-Mass Organic Acids

et al. 2017

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A prerequisite for ordered two-dimensional (2D) separations and full utilization of the enhanced 2D peak capacity is selective exploitation of the sample attributes, described as sample dimensionality. In order to take sample dimensionality into account prior to optimization of a 2D separation, a new concept based on construction of 2D separation selectivity maps is proposed and demonstrated for ion chromatography × capillary electrophoresis (IC×CE) separation of low-molecular-mass organic acids as test analytes. For this purpose, 1D separation selectivity maps were constructed based on calculation of pairwise separation factors and identification of critical pairs for four IC stationary phases and 28 levels of background electrolyte pH in CE. The derived IC and CE maps were then superimposed and the effectiveness of the respective 2D separations assessed using an in silico approach, followed by testing examples of one successful and one unsuccessful 2D combination experimentally. The results confirmed the efficacy of the predictions, which require a minimal number of experiments compared to the traditional one-at-a-time approach. Following the same principles, the proposed framework can also be adapted for optimization of separation selectivity in various 2D combinations and for other applications.

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Determination of all pK_a Values of Some di- and Tri-Carboxylic Unsaturated and Epoxy Acids and Their Polylinear Correlation with the Carboxylic Group Atomic Charges

Cited by 7 publications

References 3 publications

Coupled Interfacial and Bulk Kinetics Govern the Timescales of Multiphase Ozonolysis Reactions

Coupled Interfacial and Bulk Kinetics Govern the Timescales of Multiphase Ozonolysis Reactions

Facilely Cross-Linking Polybenzimidazole with Polycarboxylic Acids to Improve H₂/CO₂ Separation Performance

In Silico Screening of Two-Dimensional Separation Selectivity for Ion Chromatography × Capillary Electrophoresis Separation of Low-Molecular-Mass Organic Acids

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Determination of all pKa Values of Some di- and Tri-Carboxylic Unsaturated and Epoxy Acids and Their Polylinear Correlation with the Carboxylic Group Atomic Charges

Cited by 7 publications

References 3 publications

Coupled Interfacial and Bulk Kinetics Govern the Timescales of Multiphase Ozonolysis Reactions

Coupled Interfacial and Bulk Kinetics Govern the Timescales of Multiphase Ozonolysis Reactions

Facilely Cross-Linking Polybenzimidazole with Polycarboxylic Acids to Improve H2/CO2 Separation Performance

In Silico Screening of Two-Dimensional Separation Selectivity for Ion Chromatography × Capillary Electrophoresis Separation of Low-Molecular-Mass Organic Acids

Contact Info

Product

Resources

About

Determination of all pK_a Values of Some di- and Tri-Carboxylic Unsaturated and Epoxy Acids and Their Polylinear Correlation with the Carboxylic Group Atomic Charges

Facilely Cross-Linking Polybenzimidazole with Polycarboxylic Acids to Improve H₂/CO₂ Separation Performance