scholarly journals Technical note: Estimating aqueous solubilities and activity coefficients of mono- and <i>α</i>,<i>ω</i>-dicarboxylic acids using COSMO<i>therm</i>

2020 ◽  
Vol 20 (21) ◽  
pp. 13131-13143
Author(s):  
Noora Hyttinen ◽  
Reyhaneh Heshmatnezhad ◽  
Jonas Elm ◽  
Theo Kurtén ◽  
Nønne L. Prisle
Keyword(s):  
Activity Coefficients ◽  
Equilibrium Constants ◽  
Hydrate Formation ◽  
Dicarboxylic Acids ◽  
Aqueous Solubility ◽  
Technical Note ◽  
Acid Water ◽  
Monocarboxylic Acids ◽  
Wide Range ◽  
Experimental Values

Abstract. We have used the COSMOtherm program to estimate activity coefficients and solubilities of mono- and α,ω-dicarboxylic acids and water in binary acid–water systems. The deviation from ideality was found to be larger in the systems containing larger acids than in the systems containing smaller acids. COnductor-like Screening MOdel for Real Solvents (COSMO-RS) underestimates experimental monocarboxylic acid activity coefficients by less than a factor of 2, but experimental water activity coefficients are underestimated more especially at high acid mole fractions. We found a better agreement between COSMOtherm-estimated and experimental activity coefficients of monocarboxylic acids when the water clustering with a carboxylic acid and itself was taken into account using the dimerization, aggregation, and reaction extension (COSMO-RS-DARE) of COSMOtherm. COSMO-RS-DARE is not fully predictive, but fit parameters found here for water–water and acid–water clustering interactions can be used to estimate thermodynamic properties of monocarboxylic acids in other aqueous solvents, such as salt solutions. For the dicarboxylic acids, COSMO-RS is sufficient for predicting aqueous solubility and activity coefficients, and no fitting to experimental values is needed. This is highly beneficial for applications to atmospheric systems, as these data are typically not available for a wide range of mixing states realized in the atmosphere, due to a lack of either feasibility of the experiments or sample availability. Based on effective equilibrium constants of different clustering reactions in the binary solutions, acid dimer formation is more dominant in systems containing larger dicarboxylic acids (C5–C8), while for monocarboxylic acids (C1–C6) and smaller dicarboxylic acids (C2–C4), hydrate formation is more favorable, especially in dilute solutions.

scholarly journals Technical note: Estimating aqueous solubilities and activity coefficients of mono- and <i>α</i>, <i>ω</i>-dicarboxylic acids using COSMO-RS-DARE

2020 ◽  
Author(s):  
Noora Hyttinen ◽  
Reyhaneh Heshmatnezhad ◽  
Jonas Elm ◽  
Theo Kurtén ◽  
Nønne L. Prisle
Keyword(s):  
Activity Coefficients ◽  
Equilibrium Constants ◽  
Hydrate Formation ◽  
Dicarboxylic Acids ◽  
Water Systems ◽  
Technical Note ◽  
Monocarboxylic Acids ◽  
Binary Solutions ◽  
Experimental Activity ◽  
Aqueous Solubilities

Abstract. We have used the COSMOtherm program to estimate activity coefficients and solubilities of mono- and α, ω-dicarboxylic acids, and water in binary acid-water systems. The deviation from ideality was found to be larger in the systems containing larger acids than in the systems containing smaller acids. We found a better agreement between estimated and experimental activity coefficients of monocarboxylic acids when the water clustering with a carboxylic acid and itself was taken into account using the dimerization, aggregation and reaction extension (COSMO-RS-DARE) of COSMOtherm. Based on effective equilibrium constants of different clustering reactions in the binary solutions, acid dimer formation is more dominant in systems containing larger dicarboxylic acids (C5–C8), while for monocarboxylic acids (C1–C6) and smaller dicarboxylic acids (C2–C4), hydrate formation is more favorable, especially in dilute solutions.

scholarly journals DFT calculation and assignment of vibrational spectra of aryl and alkyl chlorophosphates

2014 ◽  
Vol 12 (2) ◽  
pp. 153-163
Author(s):  
Viktor Anishchenko ◽  
Vladimir Rybachenko ◽  
Konstantin Chotiy ◽  
Andrey Redko
Keyword(s):  
Vibrational Spectra ◽  
Basis Sets ◽  
Heavy Atoms ◽  
Wide Range ◽  
Complete Assignment ◽  
Key Factor ◽  
Polarization Functions ◽  
Experimental Values ◽  
Semi Empirical ◽  
Good Agreement

AbstractDFT calculations of vibrational spectra of chlorophosphates using wide range of basis sets and hybrid functionals were performed. Good agreement between calculated and experimental vibrational spectra was reached by the combination of non-empirical functional PBE0 with both middle and large basis sets. The frequencies of the stretching vibrations of the phosphate group calculated using semi-empirical functional B3LYP for all basis sets deviate significantly from the experimental values. The number of polarization functions on heavy atoms was shown to be a key factor for the calculation of vibrational frequencies of organophosphates. The importance of consideration of all the stable rotamers for a complete assignment of fundamental modes was shown.

scholarly journals Towards an accurate description of perovskite ferroelectrics: exchange and correlation effects

2017 ◽  
Vol 7 (1) ◽  
Author(s):  
Simuck F. Yuk ◽  
Krishna Chaitanya Pitike ◽  
Serge M. Nakhmanson ◽  
Markus Eisenbach ◽  
Ying Wai Li ◽  
...  
Keyword(s):  
Density Functional ◽  
General Purpose ◽  
Correlation Effects ◽  
Lattice Constants ◽  
Bulk Solids ◽  
Wide Range ◽  
Exchange Enhancement ◽  
Experimental Values ◽  
Similar Accuracy ◽  
Ferroelectric Oxides

Abstract Using the van der Waals density functional with C09 exchange (vdW-DF-C09), which has been applied to describing a wide range of dispersion-bound systems, we explore the physical properties of prototypical ABO 3 bulk ferroelectric oxides. Surprisingly, vdW-DF-C09 provides a superior description of experimental values for lattice constants, polarization and bulk moduli, exhibiting similar accuracy to the modified Perdew-Burke-Erzenhoff functional which was designed specifically for bulk solids (PBEsol). The relative performance of vdW-DF-C09 is strongly linked to the form of the exchange enhancement factor which, like PBEsol, tends to behave like the gradient expansion approximation for small reduced gradients. These results suggest the general-purpose nature of the class of vdW-DF functionals, with particular consequences for predicting material functionality across dense and sparse matter regimes.

scholarly journals Thermal Conductivities of Choline Chloride-Based Deep Eutectic Solvents and Their Mixtures with Water: Measurement and Estimation

Molecules ◽  
2020 ◽  
Vol 25 (17) ◽  
pp. 3816
Author(s):  
Taleb H. Ibrahim ◽  
Muhammad A. Sabri ◽  
Nabil Abdel Jabbar ◽  
Paul Nancarrow ◽  
Farouq S. Mjalli ◽  
...  
Keyword(s):  
Atmospheric Pressure ◽  
Choline Chloride ◽  
Deep Eutectic Solvents ◽  
Standard Uncertainty ◽  
Heat Transfer Fluids ◽  
Wide Range ◽  
Different Temperatures ◽  
Experimental Values ◽  
Water Measurement ◽  
Thermal Conductivities

The thermal conductivities of selected deep eutectic solvents (DESs) were determined using the modified transient plane source (MTPS) method over the temperature range from 295 K to 363 K at atmospheric pressure. The results were found to range from 0.198 W·m−1·K−1 to 0.250 W·m−1·K−1. Various empirical and thermodynamic correlations present in literature, including the group contribution method and mixing correlations, were used to model the thermal conductivities of these DES at different temperatures. The predictions of these correlations were compared and consolidated with the reported experimental values. In addition, the thermal conductivities of DES mixtures with water over a wide range of compositions at 298 K and atmospheric pressure were measured. The standard uncertainty in thermal conductivity was estimated to be less than ± 0.001 W·m−1·K−1 and ± 0.05 K in temperature. The results indicated that DES have significant potential for use as heat transfer fluids.

scholarly journals Technical note: GUARD – An automated fluid sampler preventing sample alteration by contamination, evaporation and gas exchange, suitable for remote areas and harsh conditions

2018 ◽  
Author(s):  
Arno Hartmann ◽  
Marc Luetscher ◽  
Ralf Wachter ◽  
Philipp Holz ◽  
Elisabeth Eiche ◽  
...  
Keyword(s):  
Gas Exchange ◽  
Field Experiments ◽  
Hydrological Cycle ◽  
Technical Note ◽  
Production Costs ◽  
Environmental Research ◽  
Remote Areas ◽  
Wide Range ◽  
Public And Private Sector

Abstract. Automated water sampling devices adapted to field operation have proven highly useful for environmental research as well as in the public and private sector, where natural or artificial waters need to be tested regularly for compliance with environmental and health regulations. Such autosamplers are already available on the market in slightly differing versions, but none of these devices are capable of sealing the collected samples to prevent sample alteration by contamination, evaporation or gas exchange. In many sampling cases, however, this feature is essential, for instance for studying the hydrological cycle based on isotopes in rainwater, or for monitoring waters contaminated with toxic gases or other volatile compounds detrimental to biota and human health. Therefore, we have developed a new mobile autosampler, which injects water samples directly into airtight vials, thus preventing any sample alteration. Further advantages include low production costs, compact dimensions and low weight allowing for easy transport, a wide range of selectable sampling intervals as well as a low power consumption, which make it suitable for long-term applications even in remote areas and harsh (outdoor) conditions due to its heavy-duty water-proof casing. In this paper, we demonstrate (1) the sampler's mechanical functioning, (2) the long-term stability of the collected samples with regard to evaporation and gas exchange and (3) the potential of our device in a wide variety of applications drawing on laboratory and field experiments in different karst caves, which represent one of the most challenging sampling environments.

scholarly journals VLE of Carbon Dioxide-Loaded Aqueous Potassium Salt of L-Histidine Solutions as a Green Solvent for Carbon Dioxide Capture: Experimental Data and Modelling

2019 ◽  
Vol 2019 ◽  
pp. 1-11 ◽  
Author(s):  
Afaf Syalsabila ◽  
Abdulhalim Shah Maulud ◽  
Humbul Suleman ◽  
Nik Abdul Hadi Md Nordin
Keyword(s):  
Carbon Dioxide ◽  
Potassium Salt ◽  
Carbon Dioxide Capture ◽  
Oxidative Degradation ◽  
Absorption Capacity ◽  
Similar Process ◽  
Process Conditions ◽  
Wide Range ◽  
Experimental Values ◽  
Biological Component

In this study, vapour-liquid equilibrium of CO2-loaded aqueous potassium salt of L-histidine was studied for a wide range of temperature (313.15–353.15 K), pressure (150–4000 kPa), and solvent concentrations (1–2.5 molar). The experimental results show that L-histidine has an excellent absorptive capacity for carbon dioxide. When compared to conventional solvent (monoethanolamine) and amino acid salt (potassium L-lysinate) at similar process conditions, L-histidine has superior absorption capacity. Moreover, modified Kent–Eisenberg model was used to correlate the VLE of the studied system with excellent agreement between the model and experimental values. The model exhibited an AARE% of 7.87%, which shows that it can satisfactorily predict carbon dioxide solubilities in aqueous potassium salt of L-histidine at other process conditions. Being a biological component in origin, almost negligibly volatile, and highly resistant to oxidative degradation, L-histidine offers certain operational advantages over other solvents used and has a promising potential for carbon dioxide capture.

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