Zygfryd Witkiewicz

Capillary gas chromatography–atomic emission spectroscopy–mass spectrometry analysis of sulphur mustard and transformation products in a block recovered from the Baltic Sea

A block of yperite fished up from the Baltic Sea was analysed by gas chromatography coupled with atomic emission spectrometry and mass spectrometry. In the samples of the block about 50 compounds were detected, out of which 30 were identified. The identification of the compounds was performed by using the element chromatograms of the investigated compounds, and the data obtained by mass spectrometric detection. Thiodiglycol was not found among the compounds present in the investigated block. The calculations of the contents of sulphur mustard and some products in the block were performed by an external calibration method using bis(2-chloroethyl) sulphide as the standard. A satisfactory precision of elements determinations was obtained (RSD from 4.4 to 14.3%).

Rate of dibutylsulfide decomposition by ozonation and the O3/H2O2 advanced oxidation process

A process of dibutylsulfide (DBS) oxidation using advanced methods of oxidation with ozone and hydrogen peroxide was studied. It was demonstrated that depending on pH value there are two mechanisms of DBS oxidation present: ionic and radical. The ionic mechanism predominates in acidic environment and the radical mechanism predominates in alkaline environment. At high pH ozone stability decreases and hydrogen peroxide has a deciding effect on DBS oxidation rate. At pH 9, and at high concentration of hydrogen peroxide (ranging from 0.1 to 1 mol/L), a clear increase in DBS decomposition rate was observed. That was caused by production of hydroperoxide radicals in reaction of hydrogen peroxide and ozone. In solutions pH value of which is close to 2, the rate of DBS oxidation by ozone alone is slower than in a O(3)/H(2)O(2) system, regardless the H(2)O(2) concentration. For higher H(2)O(2) concentrations (ranging from 0.1 to 1 mol/L), regardless the pH value of the solution, oxidation in a O(3)/H(2)O(2) system is faster, compared to a situation in which ozone is a sole oxidizer. For H(2)O(2) concentrations below 0.1 mol/L and when pH>2DBS oxidation in O(3)/H(2)O(2) system is slower compared to the situation in which ozone was the only oxidizer.

Chromatographic determination of the differential isosteric adsorption enthalpies and differential entropies on ordered silica materials

The adsorption properties of the ordered mesoporous siliceous materials: MCM-41C16 (denoted as C16), MCM-41C16-SH and MCM-41C16-NH(2) (known as MCMs) having different surface functionalities were studied by inverse gas chromatography to assess their suitability for adsorption of analytes from gas and liquid phases. Polar and non-polar adsorbates were employed. The differential isosteric enthalpies, -DeltaH(ads), and differential entropies, -DeltaS(ads), of adsorption of different molecular probes were determined chromatographically. A mathematical link between the -DeltaH(ads), and -DeltaS(ads) magnitudes and experimental data was derived through an Antoine-type equation. The present studies have been entirely restricted to the region of low adsorbate concentration. The problem of the interrelationship between the -DeltaH(ads), and -DeltaS(ads) values, known as the thermodynamic compensation effect, and interpretation of chromatographic data for the adsorption of different adsorbates on the MCMs have been considered in the light of both experimental data obtained in the present studies and the data available in the literature for siliceous adsorbents with randomly ordered structures. It was shown chromatographically that there is substantial parallelism between the magnitudes of the differential isosteric enthalpy and differential entropy for some molecular probes chromatographed on C16 and its derivatives. Complementary information was obtained by atomic-force microscopy (AFM), X-ray photoelectron spectroscopy and X-ray diffraction (XRD) spectroscopy.

Effect of temperature and initial dibutyl sulfide concentration in chloroform on its oxidation rate by ozone.

A scheme of dibutyl sulfide (DBS) oxidation with ozone and generation of transitional products was determined in this study. The main identified intermediate product was dibutyl sulfoxide (DBSO), and the main end product of DBS oxidation was dibutyl sulfone (DBSO2). It was determined that for three temperatures: 0, 10 and 20 degrees C there was certain initial DBS concentration for which half-times observed in experimental conditions were equal and independent from temperature. Generation of phosgene and water as by-products was confirmed for the reaction of DBS with ozone in chloroform. Results of the described study allowed to present generalized mechanism of sulfide oxidation with ozone.

Chromatographic characterisation of ordered mesoporous silicas. Part II: Acceptor–donor properties

The ordered mesoporous siliceous materials: MCM41C16, MCM41C16-SH and MCM41C16-NH(2) (known as MCMs) having different surface functionalities were studied by inverse gas chromatography to characterise their acceptor-donor properties. The DN values denoting the donor number in the Gutmann scale and the AN* values denoting the acceptor number in the Riddle-Fowkes scale have been chosen in the estimation of the electron-acceptor parameter K(A) and electron-donor parameter K(D) values. The number and kind of the employed adsorbates have an influence on the results obtained. The problem of the number of adsorbates employed has been considered in the light of both results obtained in the present study and the data available in the literature for siliceous adsorbents with randomly ordered structures. Complementary information was obtained by X-ray photoelectron spectroscopy and energy dispersive X-ray spectroscopy.

Molecular Modelling of Selected Phthalates and Their Interactions with Stationary Phases in Solid-Phase Microextraction

In this work, solid-phase microextraction of six phthalates from methanol and aqueous solutions were carried out. Polar polyacrylate (PA) and non-polar polydimethylsiloxane (PDMS) were used as stationary phases. HyperChem 8.0 software was used for the optimization of the geometry of these six phthalates and their interactions with stationary phases. Extracted samples were analyzed using gas chromatography coupled with mass spectrometry. In the analysis of phthalates extracted from methanol solution, the best extraction efficiency was obtained for the PA phase, whereas for the extraction from aqueous solution, higher efficiency was obtained for the PDMS phase.

Investigation of mesoporous carbon materials by magnetic solid phase extraction of selected phthalates from water samples

In the present work ordered mesoporous carbon materials soft templating-acidic (STA) were applied as adsorbents in magnetic solid phase extraction technique for isolation of selected phthalates from water samples. STA materials were obtained by soft-templating method in acidic environment. Nickel nanoparticles were added on the STA synthesis stage, thus the obtained material acquired magnetic properties. The analysis of phthalates after the extraction was carried out by gas chromatography-mass spectrometry method. Fast and easy procedure was elaborated, obtaining recoveries close to 90% for some phthalates.

Synthesis of OMS Materials and Investigation of Their Acceptor–Donor Characteristics

Three ordered mesoporous siliceous (OMS) materials known as MCM41s—unmodified MCM-41C16 (“C16”), and two MCM41s with different surface functionalities: MCM-41C16-SH (“C16-SH”) and MCM-41C16-NH2 (“C16-NH2”)—were synthesized and studied by inverse gas chromatography in order to determine their acceptor–donor properties. The specific retention volumes of nonpolar and polar probes that were chromatographed on these ordered mesoporous silica adsorbents were evaluated under infinite dilution conditions. Two methods were employed to calculate the standard free energy of adsorption, ΔGads, of each chromatographed probe on the basis its specific retention volume. These ΔGads values were then employed to estimate the van der Waals contribution and the specific contribution of the free surface energy for each MCM41. DN values (donor numbers, based on the Gutmann scale) and AN* values (acceptor numbers, based on the Riddle–Fowkes scale) were employed to determine the values of parameters that characterize the ability of the MCM41s to act as electron acceptors (parameter: KA) and donors (parameter: KD). Considering the different compositions of the probes, each of which has different acceptor–donor properties, a new chromatographic test to supplement the Grob test is suggested.

Changes in the order of elution of some organic compounds in high-resolution gas chromatography on polar columns depending on the injection method and water content in the sample

During the GC analysis of apple aroma essence using a capillary column with polar stationary phases, i.e., bonded/crosslinked polyethylene glycol (HP-Innowax) and acid-modified polyethylene glycol (FFAP) the phenomenon of changing the elution order of some compounds was observed (cross-over phenomenon). The elution order within two pairs of closely eluting compounds: 2-methylbutyl acetate/pentan-3-ol (internal standard) and trans-2-hexen-1-al/2-methylbutan-1-ol differed between samples introduced onto the column with direct injection and with static headspace method. Experiments carried out on standard solutions of investigated compounds in water-acetone mixtures of gradually reduced water ratio (99:1 to 0:100) proved that changes of elution times leading first to co-elution and subsequently to reversion of elution order of compounds within both pairs depended on the amount of water in the injected sample. The same effect was observed while the amount of water was diminished by reducing the sample volume introduced into the column.