Reduction of some organic compounds by electrochemically generated titanium(III)

Abstract. We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl−, Br−, NO3−, HSO4−, and SO42−. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with dicarboxylic acids and with levoglucosan. Overall, the new parameterization of AIOMFAC agrees well with a large number of experimental datasets. However, due to various reasons, for certain mixtures important deviations can occur. The new parameterization makes AIOMFAC a versatile thermodynamic tool. It enables the calculation of activity coefficients of thousands of different organic compounds in organic-inorganic mixtures of numerous components. Models based on AIOMFAC can be used to compute deliquescence relative humidities, liquid-liquid phase separations, and gas-particle partitioning of multicomponent mixtures of relevance for atmospheric chemistry or in other scientific fields.

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New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-11-15297-2011 ◽

2011 ◽

Vol 11 (5) ◽

pp. 15297-15416 ◽

Cited By ~ 3

Author(s):

A. Zuend ◽

C. Marcolli ◽

A. M. Booth ◽

D. M. Lienhard ◽

V. Soonsin ◽

...

Keyword(s):

Liquid Phase ◽

Functional Groups ◽

Organic Compounds ◽

Activity Coefficients ◽

Atmospheric Aerosols ◽

Atmospheric Chemistry ◽

Inorganic Ions ◽

Aqueous Mixtures ◽

Organic Functional Groups ◽

Ether Ester

Abstract. We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl−, Br−, NO3−, HSO4−, and SO42−. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with dicarboxylic acids and with levoglucosan. Overall, the new parameterization of AIOMFAC agrees well with a large number of experimental datasets. However, due to various reasons, for certain mixtures important deviations can occur. The new parameterization makes AIOMFAC a versatile thermodynamic tool. It enables the calculation of activity coefficients of thousands of different organic compounds in organic-inorganic mixtures of numerous components. Models based on AIOMFAC can be used to compute deliquescence relative humidities, liquid-liquid phase separations, and gas-particle partitioning of multicomponent mixtures of relevance for atmospheric chemistry or in other scientific fields.

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pH Dependent Sensitization of Europium in a Hydrogen Bonded Three-Dimensional Metal-Organic Compounds with (4966)2(4462)3 Topology: Luminescence Titration and Time-resolved Studies

Materials Advances ◽

10.1039/d1ma00980j ◽

2021 ◽

Author(s):

Sudip Kumar Mondal ◽

Partha Mahata ◽

Pooja Daga ◽

Sayani Hui ◽

Sourav Sarkar ◽

...

Keyword(s):

Rare Earth ◽

Organic Compound ◽

Dicarboxylic Acid ◽

Organic Compounds ◽

Three Dimensional ◽

Time Resolved ◽

Hydrothermal Technique ◽

Pyridine Dicarboxylic Acid ◽

Metal Organic ◽

Ph Dependent

A rare-earth-based metal-organic compound (MOC), [Y2(pydc)6(H2pip)3]·20H2O (pydc = 2,6-pyridine dicarboxylate, H2pip = diprotonated piperazine), (1), was prepared by hydrothermal technique using 2,6-pyridine dicarboxylic acid, piperazine, and Y(III) ions. Applying the...

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Improved AIOMFAC model parameterisation of the temperature dependence of activity coefficients for aqueous organic mixtures

Atmospheric Chemistry and Physics ◽

10.5194/acp-15-447-2015 ◽

2015 ◽

Vol 15 (1) ◽

pp. 447-493 ◽

Cited By ~ 25

Author(s):

G. Ganbavale ◽

A. Zuend ◽

C. Marcolli ◽

T. Peter

Keyword(s):

Experimental Data ◽

Temperature Dependence ◽

Functional Groups ◽

Organic Compounds ◽

Activity Coefficients ◽

Low Temperatures ◽

Functional Group ◽

Organic Mixtures ◽

Organic Functional Groups ◽

Organic Solutions

Abstract. This study presents a new, improved parameterisation of the temperature dependence of activity coefficients in the AIOMFAC (Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients) model applicable for aqueous as well as water-free organic solutions. For electrolyte-free organic and organic–water mixtures the AIOMFAC model uses a group-contribution approach based on UNIFAC (UNIversal quasi-chemical Functional-group Activity Coefficients). This group-contribution approach explicitly accounts for interactions among organic functional groups and between organic functional groups and water. The previous AIOMFAC version uses a simple parameterisation of the temperature dependence of activity coefficients, aimed to be applicable in the temperature range from ~ 275 to ~ 400 K. With the goal to improve the description of a wide variety of organic compounds found in atmospheric aerosols, we extend the AIOMFAC parameterisation for the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon to atmospherically relevant low temperatures. To this end we introduce a new parameterisation for the temperature dependence. The improved temperature dependence parameterisation is derived from classical thermodynamic theory by describing effects from changes in molar enthalpy and heat capacity of a multi-component system. Thermodynamic equilibrium data of aqueous organic and water-free organic mixtures from the literature are carefully assessed and complemented with new measurements to establish a comprehensive database, covering a wide temperature range (~ 190 to ~ 440 K) for many of the functional group combinations considered. Different experimental data types and their processing for the estimation of AIOMFAC model parameters are discussed. The new AIOMFAC parameterisation for the temperature dependence of activity coefficients from low to high temperatures shows an overall improvement of 28% in comparison to the previous model version, when both versions are compared to our database of experimentally determined activity coefficients and related thermodynamic data. When comparing the previous and new AIOMFAC model parameterisations to the subsets of experimental data with all temperatures below 274 K or all temperatures above 322 K (i.e. outside a 25 K margin of the reference temperature of 298 K), applying the new parameterisation leads to 37% improvement in each of the two temperature ranges considered. The new parameterisation of AIOMFAC agrees well with a large number of experimental data sets. Larger model–measurement discrepancies were found particularly for some of the systems containing multi-functional organic compounds. The affected systems were typically also poorly represented at room temperature and further improvements will be necessary to achieve better performance of AIOMFAC in these cases (assuming the experimental data are reliable). The performance of the AIOMFAC parameterisation is typically better for systems containing relatively small organic compounds and larger deviations may occur in mixtures where molecules of high structural complexity such as highly oxygenated compounds or molecules of high molecular mass (e.g. oligomers) prevail. Nevertheless, the new parameterisation enables the calculation of activity coefficients for a wide variety of different aqueous/water-free organic solutions down to the low temperatures present in the upper troposphere.

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A MEMS µ-Preconcentrator Employing a Carbon Molecular Sieve Membrane for Highly Volatile Organic Compound Sampling

Chemosensors ◽

10.3390/chemosensors9050104 ◽

2021 ◽

Vol 9 (5) ◽

pp. 104

Author(s):

Hung-Yang Kuo ◽

Wei-Riu Cheng ◽

Tzu-Heng Wu ◽

Horn-Jiunn Sheen ◽

Chih-Chia Wang ◽

...

Keyword(s):

Organic Compound ◽

Organic Compounds ◽

Volatile Organic Compound ◽

Molecular Sieve ◽

Amplification Factor ◽

Microfluidic Channel ◽

Carbon Molecular Sieve ◽

Volatile Organic ◽

Chromatographic Peaks ◽

Gaseous Toluene

This paper presents the synthesis and evaluation of a carbon molecular sieve membrane (CMSM) grown inside a MEMS-fabricated μ-preconcentrator for sampling highly volatile organic compounds. An array of µ-pillars measuring 100 µm in diameter and 250 µm in height were fabricated inside a microfluidic channel to increase the attaching surface for the CMSM. The surface area of the CMSM was measured as high as 899 m2/g. A GC peak amplification factor >2 × 104 was demonstrated with gaseous ethyl acetate. Up to 1.4 L of gaseous ethanol at the 100 ppb level could be concentrated without exceeding the capacity of this microchip device. Sharp desorption chromatographic peaks (<3.5 s) were obtained while using this device directly as a GC injector. Less volatile compounds such as gaseous toluene, m-xylene, and mesitylene appeared to be adsorbed strongly on CMSM, showing a memory effect. Sampling parameters such as sample volatilities, sampling capacities, and compound residual issues were empirically determined and discussed.

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Non-Enzymatic Desymmetrization Reactions in Aqueous Media

Symmetry ◽

10.3390/sym13040720 ◽

2021 ◽

Vol 13 (4) ◽

pp. 720

Author(s):

Satomi Niwayama

Keyword(s):

Natural Products ◽

Total Synthesis ◽

Functional Groups ◽

Organic Compounds ◽

Recent Progress ◽

Aqueous Media ◽

Building Blocks ◽

Organic Reactions ◽

Environmentally Benign ◽

Enzymatic Desymmetrization

Symmetric organic compounds are generally obtained inexpensively, and therefore they can be attractive building blocks for the total synthesis of various pharmaceuticals and natural products. The drawback is that discriminating the identical functional groups in the symmetric compounds is difficult. Water is the most environmentally benign and inexpensive solvent. However, successful organic reactions in water are rather limited due to the hydrophobicity of organic compounds in general. Therefore, desymmetrization reactions in aqueous media are expected to offer versatile strategies for the synthesis of a variety of significant organic compounds. This review focuses on the recent progress of desymmetrization reactions of symmetric organic compounds in aqueous media without utilizing enzymes.

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