The Chemistry of Separations Ligand Degradation by Organic Radical Cations

Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexants and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normal alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R^•+), carbon-centered radicals (R^•), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R^•+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with various ligands. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved.     

Subcritical water extraction of organic matter from sedimentary rocks

Subcritical water extraction of organic matter containing sedimentary rocks at 300 °C and 1500 psi produces extracts comparable to conventional solvent extraction. Subcritical water extraction of previously solvent extracted samples confirms that high molecular weight organic matter (kerogen) degradation is not occurring and that only low molecular weight organic matter (free compounds) are being accessed in analogy to solvent extraction procedures. The sedimentary rocks chosen for extraction span the classic geochemical organic matter types. A type I organic matter-containing sedimentary rock produces n-alkanes and isoprenoidal hydrocarbons at 300 °C and 1500 psi that indicate an algal source for the organic matter. Extraction of a rock containing type II organic matter at the same temperature and pressure produces aliphatic hydrocarbons but also aromatic compounds reflecting the increased contributions from terrestrial organic matter in this sample. A type III organic matter-containing sample produces a range of non-polar and polar compounds including polycyclic aromatic hydrocarbons and oxygenated aromatic compounds at 300 °C and 1500 psi reflecting a dominantly terrestrial origin for the organic materials. Although extraction at 300 °C and 1500 psi produces extracts that are comparable to solvent extraction, lower temperature steps display differences related to organic solubility. The type I organic matter produces no products below 300 °C and 1500 psi, reflecting its dominantly aliphatic character, while type II and type III organic matter contribute some polar components to the lower temperature steps, reflecting the chemical heterogeneity of their organic inventory. The separation of polar and non-polar organic compounds by using different temperatures provides the potential for selective extraction that may obviate the need for subsequent preparative chromatography steps. Our results indicate that subcritical water extraction can act as a suitable replacement for conventional solvent extraction of sedimentary rocks, but can also be used for any organic matter containing mineral matrix, including soils and recent sediments, and has the added benefit of tailored extraction for analytes of specific polarities.     

Rapid Extraction of Volatile Compounds Using a New Simultaneous Microwave Distillation: Solvent Extraction Device

Simultaneous distillation–extraction (SDE) is routinely used by analysts for sample preparation prior to gas chromatography analysis. In this work, a new process design and operation for microwave assisted simultaneous distillation–solvent extraction (MW-SDE) of volatile compounds was developed. Using the proposed method, isolation, extraction and concentration of volatile compounds can be carried out in a single step. To demonstrate its feasibility, MW-SDE was compared with the conventional technique, SDE, for gas chromatography-mass spectrometry (GC-MS) analysis of volatile compounds in a fresh aromatic herb, Zygophyllum album L., a wild salty desert herb belonging to the family Zygophyllaceae. SDE method required a long time (3 h) to isolate the volatile compounds, and large amounts of organic solvent (200 mL of hexane) for further extraction, while MW-SDE needed shorter time (only 30 min) to prepare the sample, and less amount of organic solvent (10 mL of hexane). These results show that MW-SDE–GC-MS is a simple, rapid and solvent-less method for the determination of volatile compounds from aromatic plants.     

Comparison of the effectiveness of solid-phase and ultrasound-mediated liquid-liquid extractions to determine the volatile compounds of wine

Two ultrasound-assisted liquid–liquid extraction (LLE-I, LLE-II) methods were compared to a solid-phase extraction (SPE) protocol to assess their effectiveness for the analysis of up to 44 volatile compounds in a synthetic and several commercial white, red and “cream” wines produced in the southwest of Spain. Regardless of the extraction protocol used the highest recoveries corresponded to acids and terpene alcohols and the lowest to lactones and alcohols. In any case, it was concluded that one of the liquid–liquid extraction protocols evaluated led to higher recoveries for a greater number of odorants that could be implicated in the aroma of the wines than the solid-phase extraction. However, the SPE method also presented some advantages that should not be overlooked, like higher repeatability and throughput and lower solvent consumption.     

Synergic extraction of some lanthanide and actinide elements by a mixture of bis/2-ethyl hexyl/phosphoric acid and dinonylnaphthalene-sulfonic acid in aromatic diluents

Extraction of lanthanides and actinides were found to be synergically enhanced by a mixture of bis/2-ethyl hexyl/phosphoric acid /HA/ and dinonylnaphthalene sulfonic acid /HD/ in aromatic diluents covering a wide range of dielectric constant. The main extracted species is found to be in the form MA₂H_m–1D_m. Experimental results indicate that the extraction mechanism is governed by the extraction of HD in the organic phase.     

Highly Sensitive Determination of Carbon- and Hydrogen-Containing Impurities in Silicon Tetrachloride by Gas Chromatography

Procedures were developed for the direct gas-chromatographic determination of impurities of organochlorine substances, chlorosilane, and alkylchlorosilane in silicon tetrachloride and for the gas-chromatographic analysis with matrix subtraction by preliminary hydrolysis of silicon tetrachloride and subsequent extraction of organochlorine impurities with an organic solvent. It was found that the major impurities in high-purity silicon tetrachloride obtained by the rectification of the by-product in the production of trichlorosilane are trichlorosilane, methyltrichlorosilane, methyldichlorosilane, chloroform, and carbon tetrachloride. Detection limits of impurities are 10^–5–10^–7wt %, which is lower than those reported in the literature by 1–2 orders of magnitude.     

Magnetic nanoparticles used in headspace extraction coupled with DSI-GC-IT/MS for analysis of VOCs in dry Traditional Chinese Medicine

A novel magnetic method using polystyrene modified magnetic nanoparticles to perform thermoheadspace extraction was successfully developed for extraction and preconcentration of volatile organic components in dry Traditional Chinese Medicine(TCM) based on gas chromatography-ion trap/mass spectrometry with a Chromato Probe direct sample introduction device. The dried fruit of Amomum testaceum Ridl. was used as the object TCM. The optimum parameters of headspace magnetic solid-phase extraction were investigated, in which desorption solvent ethyl acetate played a key role in this method,and the headspace extraction temperature of 90℃ and the headspace extraction time of 15 min finally decided. Headspace solid-phase microextraction method was also used to analyze volatile compounds in the TCM to compare with the proposed method. The results show that 60 components were identified totally by two methods; most of the low boiling point chemical compounds are isolated by this new method. In this work, an environmental-friendly and cheap analytical method was established, and a new approach to analyze volatile compounds in dry Traditional Chinese Medicine was also provided.     

Microwave extraction of phthalate esters from marine sediment and soil

Summary As part of an on-going ASEAN⁺⁾-Canada Cooperative Programme on Marine Science, microwave-assisted solvent extraction has been employed for the extraction of six phthalate esters from marine sediment and soil samples. Five of the six esters studied are among the United States Environmental Protection Agency's list of top priority pollutants. The effects of extraction solvent, extraction temperature, duration of extraction and extraction volume on the mean recoveries of the six phthalate esters were quantitatively evaluated by means of an analysis of variance, followed by testing the differences among the level means for each condition with least significant difference method. Microwave-assisted solvent extraction allowed comparable or higher recoveries of the six phthalate esters (70.1–91.0%) in comparison with conventional soxhlet (65.5–89.5%) and sonication (64.6–88.6%). The precision of results by microwave-assisted solvent extraction was improved significantly compared to the conventional techniques. The microwave extraction system has many advantages over the soxhlet and sonication extraction, e.g., no laborious clean-up procedure, lower usage of hazardous organic solvent, and larger sample throughput. The technique has been employed for the analysis of native marine sediment and soil samples in Singapore.     

Kinetics of hydrolysis of some new heterocyclic azomethines

Kinetics of base hydrolysis of new heterocyclic azomethines derived from active methyl quaternary salts and aromatic nitroso compounds were investigated in the presence of 70% (wt/wt) water-methanol. The base hydrolysis of these compounds is strictly first-order with respect to OH^– and azomethine. The rate determining step is suggested to be the attack of the hydroxide ion on the free base. Effects of water content and nature of organic hydroxylic solvent have been studied. It is concluded that specific solute-solvent interactions through dispersion forces play a major role in the base hydrolysis rate of the azomethines investigated. The effect of pH (2.98 – 12.24) on hydrolysis rates of compounds having a diethylamino substituent in the presence of 30% methanol has been studied. In acidic media, the rate determining step is probably the water attack on the protonated substrate.     

Determination of selected polycyclic aromatic hydrocarbons and oxygenated polycyclic aromatic hydrocarbons in aerosol samples by high-performance liquid chromatography and liquid chromatography–tandem mass spectrometry

Fine and ultrafine particles are probably responsible for numerous health effects, but it is still unclear whether and to what extent the particle itself or organic compounds adsorbed or condensed on the particle are responsible for the effects observed. One important class of particle-bound substances are the polycyclic aromatic hydrocarbons (PAH) and their oxygenated derivatives. To improve the tools used for chemical characterization of particulate matter analytical methods for the determination of PAH and oxygenated PAH in aerosol samples of different origin have been developed and optimized. PAH on high-volume filters and on soot aerosols were analyzed by using accelerated solvent extraction for extraction and high-performance liquid chromatography with fluorescence detection for separation and quantification. Total PAH concentrations were in the range 0.3–9.3 ng m^–3. For analysis of selected oxygenated PAH on high-volume filters a liquid chromatography–tandem mass spectrometric method was developed and optimized. Preliminary investigations showed that oxygenated PAH at pg m^–3 concentrations can be determined.     

Use of less polar organic solvents for the polarographic determination of metals after extraction of their diethyldithiocarbamates

Summary Physico-chemical parameters of various organic solvents, such as conductivity, viscosity, available potential range and phase-separation characteristics, have been evaluated for the use of direct polarographic analysis after liquid-liquid extracxtion. Due to its higher conductivity of 1.16 mS cm^–1 and a wide available potential range of 0.81 –1.72 V vs. Ag/AgCl, a dichloromethane solution containing 0.1 mol/l tetrabutylammonium perchlorate is chosen as the best organic solvent solution for the purpose of this study. Bismuth(III) is extracted into the organic phase and gives well-defined anodic and cathodic waves at –0.12 V and –0.51 V, respectively. A selective polarographic determination of the metal after the dichloromethane extraction has been developed.     

Paper chromatography of noble metals in mixed chloride-nitrate media with use of solutions of liquid anion exchangers as mobile phases

Summary The chromatographic behaviour of nine noble metals on paper strips impregnated with mixtures of HCl and HNO₃ and developed with solutions of secondary and tertiary amine salts or quatermary alkylammonium salts in organic diluents was investigated. It was found that very sharp separation of the pair Pt–Pd is obtainable at development of chromatograms with 0.1 Aliquat 336 in xylene or with 0.1 mol dm^–3 TOA in kerosene at high concentrations of the acids in the stationary phase. The increase of concentration of HNO₃ in acids mixture decreases the R_F or R_M values for the platinum metals more distinctly than increase of concentration of HCl.     

Radiochemical studies of iodine behaviour under conditions relevant to nuclear reactor accidents

Radiochemical methods are quite suitable for studying the behaviour of radioiodine under the dilute conditions relevant to nuclear reactor accidents. Species selective adsorbents are able to distinguish between various inorganic and organic gas-phase iodine species. A solvent extraction procedure for determining aqueous phase organic iodide, free iodine, I^– and IO ₃ ^– fractions has been investigated and found to be valuable, although large inaccuracies in the separation of I^– and IO ₃ ^– can occur for solutions of pH above 10. The extraction of potentially-volatile species in the aqueous phase gives a measure of iodine species volatility consistent with observed values of the partition coefficient. Indirect measurement suggest that the partition coefficient of HOI at room temperature exceeds 30,000.     

The effect of diluents on extraction of uranium(VI) with petroleum-sulfoxides (PSO)

The effect of diluents on the extraction of uranium(VI) with petroleum sulfoxides (PSO) was studied. The decreasing order of extraction ability of PSO is as follows: benzene, toluene, cyclohexane, heptane, kerosene, carbon tetrachloride and chloroform. The effect of temperature on the extraction equilibrium was also investigated and enthalpy of the extraction was obtained. The relationship between the extraction equilibrium constantsK _ex and the physical parameters of diluents can be derived.     

Ionic Liquids Based on the Concept of Melting Point Lowering Due to Ethoxylation

Most of the commonly used Ionic Liquids (ILs) contain bulky organic cations with suitable anions. With our COMPLET (Concept of Melting Point Lowering due to Ethoxylation), we follow a different approach. We use simple, low-toxic, cheap, and commercially available anions of the type C_x(EO)_yCH₂COO^– to liquefy presumably any simple metal ion, independently of its charge. In the simplest case, the cation can be sodium or lithium, but synthesis of Ionic Liquids is also possible with cations of higher valences such as transition or rare earth metals. Anions with longer alkyl chains are surface active and form surface active ionic liquids (SAILs), which combine properties of ionic and nonionic surfactants at room temperature. They show significant structuring even in their pure state, i.e., in the absence of water or any other added solvent. This approach offers new application domains that go far beyond the common real or hypothetical use of classical Ionic Liquids. Possible applications include the separation of rare earth metals, the use as interesting media for metal catalysis, or the synthesis of completely new materials (for example, in analogy to metal organic frameworks).     

Analysis of hydrocarbons in coal and rock samples by on-line combination of thermodesorption,gas chromatography and mass spectrometry

Summary GC-MS analysis of hydrocarbons, thermally mobilized from rock and coal samples (“thermodesorption”) at 320°C, provides valuable and readily available information of organic geochemical significance. Two oil shale and three coal samples of different rank have been selected for this study. The molecular patterns of compound classes of various saturated and aromatic hydrocarbons are recorded here by employing mass chromatography of selected ions. The method described is of particular importance for the detection of those volatile constituents in coals and sedimentary rocks, which are usually not recovered during elaborate workup procedures (i.e. solvent extraction, liquid chromatography) due to evaporation losses.     

Microwave-assisted solvent elution technique for the extraction of organic pollutants in water

Solid phase extraction (SPE) with appropriate solid sorbents has been commonly used in the routine extraction of organic pollutants in water. The elution of analytes from the solid sorbents normally takes place by organic solvents under an applied vacuum. In this study, a microwave-assisted solvent elution technique was developed for the elution of analytes from C₁₈ membrane disks during microwave irradiation from a microwave extraction system (MES). Several parameters, namely, elution solvent, elution temperature, duration of elution and the volume of solvent which may affect the elution efficiency of microwave-assisted solvent elution (MASE) technique towards organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), phthalate esters (PAEs), organophosphorus pesticides (OPs), fungicides, herbicides and insecticides from the membrane disk were investigated. Good recoveries above 75% were obtained for most of the organic pollutants using the optimum SPE-MASE technique. The effect of sodium chloride and humic acid on the recoveries on the target analytes were also investigated.     

Formation of peroxide compounds on the oxidation of lignin by oxygen in an organic solvent

The results are given of a determination of the steady-state concentrations of peroxide compounds on the oxidation of lignin by oxygen in dioxane. An iodometric method of determining peroxides was used, with spectrophotometric control of the amount of iodine formed. It was established that the achievable steady-state concentration of peroxide compounds on the oxidation of lignin is 0.28–0.44 wt. % of O_act (oxygen pressure 1 atm, temperature 50–80°C). With a rise in the temperature, the steady-state concentration of peroxide compounds decreased. The addition of water (30 vol. %) to the organic solvent led to an increase in the rate of accumulation of peroxide compounds. It has been shown that the presence of alkaline and acidic catalysts exerts no appreciable influence on the achievable steady-state concentration and the rate of accumulation of peroxide compounds during the oxidation of lignin.Bratsk Industrial Institute. All-Union Scientific Production Combine of the Pulp and Paper Industry, Leningrad. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 413–417, May–August, 1992.     

Screening method for phthalate esters in water using liquid-phase microextraction based on the solidification of a floating organic microdrop combined with gas chromatography-mass spectrometry

A simple and efficient liquid-phase microextraction (LPME) technique was developed using directly suspended organic microdrop coupled with gas chromatography–mass spectrometry (GC–MS), for the extraction and the determination of phthalate esters (dimethyl phthalate, diethyl phthalate, diallyl phthalate, di-n-butyl phthalate (DnBP), benzyl butyl phthalate (BBP), dicyclohexyl phthalate and di-2-ethylhexyl phthalate (DEHP)) in water samples. Microextraction efficiency factors, such as nature and volume of the organic solvent, temperature, salt effect, stirring rate and the extraction time were investigated and optimized. Under the optimized extraction conditions (extraction solvent: 1-dodecanol; extraction temperature: 60 °C; microdrop volume: 7 μL; stirring rate: 750 rpm, without salt addition and extraction time: 25 min), figures of merit of the proposed method were evaluated. The values of the detection limit were in the range of 0.02–0.05 μg L⁻¹, while the R.S.D.% value for the analysis of 5.0 μg L⁻¹ of the analytes was below 7.7% (n = 4). A good linearity (r² ≥ 0.9940) and a broad linear range (0.05–100 μg L⁻¹) were obtained. The method exhibited enrichment factor values ranging from 307 to 412. Finally, the designed method was successfully applied for the preconcentration and determination of the studied phthalate esters in different real water samples and satisfactory results were attained.     

Influence of the nature of organic diluents on the extraction of uranium(VI) by bis(2-ethylhexyl) sulfoxide from nitric acid solutions

The extraction of uranium(VI) from nitric acid solutions by bis(2-ethylhexyl) sulfoxide (BESO) has been examined using sixteen inert organic diluents in order to establish the correlation between its distribution coefficient and some physico-chemical properties of the diluents. The extracted solvated species is shown to be UO₂(NO₃)₂·2BESO, irrespective of their nature. The extraction rate is lower in halogen substituted hydrocarbons as compared to the other diluents used. Among benzene derivatives, extraction is found to decrease with number of substituted methyl groups. Extraction efficiency decreases as the organic solvent is varied in the order: benzene>nitromethane>toluene> >nitrobenzene>cyclohexane>p-xylene>monochlorobenzene>dodecane>o-dichlorobenzene> >hexane>decalin>1,2-dichloroethane>1,1,1-trichloroethane>carbon tetrachloride> >tetrachloroethane>chloroform. Among the properties showing good correlations with distribution coefficient are Hansen's three-dimensional solubility parameters and Dimroth's empirical solvent polarity parameters [E _T(30) ]. Polarizability indices are most satisfactorily applicable to a wide variety of solvents.