Search Results (13)

The work is devoted to the study of the influence of nitrogenous bases on the composition of oil and the structure of asphaltenes on their colloidal stability in solution. Model petroleum systems with a basic nitrogen content of 1, 2, and 3% wt. were used as objects of study. Asphaltene-like nitrogenous bases were obtained by thermolysis of model petroleum systems with different nitrogen contents. The results were obtained using elemental analysis, non-aqueous potentiometric titration, spectrophotometry, ¹H NMR spectroscopy, and liquid adsorption chromatography. It was established that the content of N_bas in asphaltenes increases by 0.3–1.3% wt. with the increase in quinoline content in petroleum components. Quinoline is incorporated into the supramolecular structure of asphaltenes and increases their average molecular weight by 650 amu. and aromaticity by 2%. The aggregative stability of asphaltenes decreases by 1.5–6 times with an increase in their average molecular weight and an increase in N_bas in their composition as a component of a dispersion medium. The colloidal stability of synthetic asphaltene-like substances, on the contrary, is due to the appearance of their molecular sequence of fragments containing N_bas in aromatic rings. Full article

This study involved the fabrication of a set of aluminum ion-grafted SBA-15 utilizing ethylenediamine and trimethylamine ionic liquids. The primary objective was to examine the impact of the fabrication environment on the physicochemical characteristics of the catalysts. Comprehensive characterization of the Al-SBA-15 catalysts was conducted using various techniques, including XRD, FTIR, surface area, pyridine FTIR, ²⁷Al-NMR, TGA, HRTEM, and FESEM, to analyze their physicochemical characteristics. Furthermore, the acidic characteristics were examined by conducting potentiometric titration in a nonaqueous solvent and employing FTIR spectroscopy to analyze the chemisorbed pyridine. The effectiveness of the fabricated acid materials was evaluated by testing their performance in acetic acid esterification with butanol. The findings obtained reveal that mesostructured SBA-15 remains intact following the successful inclusion of Al³⁺ ions into the silica frameworks. Additionally, a remarkable enhancement in the existence of both Bronsted and Lewis acid centers was noted due to the grafting process of Al³⁺ ions. At temperatures of 80 °C and 100 °C, the reaction in Al-SBA-15(T-120) proceeds swiftly, reaching approximately 32% and 38% conversion, respectively, within a span of 110 min. The excellent catalytic performance observed in the esterification reaction can be attributed to two factors: the homogeneous distribution of Al³⁺ ions within the SBA-15 frameworks and the acidic character of Al-SBA-15. The findings further indicate that the grafting process for incorporating Al³⁺ ions into the silica matrix is more efficient. Full article

The characterization and quantification of functional groups in technical lignins are among the chief obstacles of the utilization of this highly abundant biopolymer. Although several techniques were developed for this purpose, there is still a need for quick, cost-efficient, and reliable quantification methods for lignin. In this paper, three sampling techniques for fourier transform infrared (FTIR) spectroscopy were assessed both qualitatively and quantitatively, delineating how these affected the resultant spectra. The attenuated total reflectance (ATR) of neat powders and DMSO-d6 solutions, as well as transmission FTIR using the KBr pelleting method (0.5 wt%), were investigated and compared for eight lignin samples. The ATR of neat lignins provided a quick and easy method, but the signal-to-noise ratios in the afforded spectra were limited. The ATR of the DMSO-d6 solutions was highly concentration dependent, but at a 30 wt%, acceptable signal-to-noise ratios were obtained, allowing for the lignins to be studied in the dissolved state. The KBr pelleting method gave a significant improvement in the smoothness and resolution of the resultant spectra compared to the ATR techniques. Subsequently, the content of phenolic OH groups was calculated from each FTIR mode, and the best correlation was seen between the transmission mode using KBr pellets and the ATR of the neat samples (R² = 0.9995). Using the titration measurements, the total OH and the phenolic OH group content of the lignin samples were determined as well. These results were then compared to the FTIR results, which revealed an under-estimation of the phenolic OH groups from the non-aqueous potentiometric titration, which was likely due to the differences in the pK_a between the lignin and the calibration standard 4-hydroxybenzoic acid. Further, a clear correlation was found between the lower $M_n$ and the increased phenolic OH group content via SEC analyses. The work outlined in this paper give complementary views on the characterization and quantification of technical lignin samples via FTIR. Full article

Chemical modification of biochars can improve their adsorption capacity relative to antibiotics, posing a serious threat to the environment. Therefore, this research is aimed at the treatment of sunflower husk biochar (BC) by vitamin C, hydrogen peroxide or silver nanoparticles and the impact of this procedure on the biochar porosity, surface chemistry, and ability to remove tetracycline (TC). During the study, BC was produced by pyrolysis of sunflower husks at 650 °C. All solids were characterized using potentiometric titration, nitrogen adsorption/desorption, Fourier transform infrared spectroscopy, etc. The experimental adsorption data was described by kinetics equations: pseudo-first order, pseudo-second order, and particle internal diffusion (IPD) models as well as by isotherms of Langmuir, Langmuir-Freundlich, and Redlich-Peterson. The obtained results indicated that the biochar upgraded by vitamin C (BCV) had the highest ability to attract antibiotic molecules and, as a result, the TC adsorption on its surface was the largest. Furthermore, the TC desorption from this material was minimal. The measured TC adsorbed amounts for the modified BCs were as follows: 47.75% (7.47 mg/g) for BCV, 37.35% (8.41 mg/g)-for biochar treated by hydrogen peroxide (BCH), and 42.04% (9.55 mg/g) for biochar modified by silver nanoparticles (BCA). The lowest adsorption level was noted for non-modified biochar, i.e., 34.17% (6.83 mg/g). Based on the presented results it can be stated that the upgraded biochars had a good potential to improve the tetracycline removal from aqueous media, e.g., groundwater. Full article

Six novel 3-alkyl(aryl)-4-(p-nitrobenzoylamino)-4,5-dihydro-1H-1,2,4-triazol-5- ones (2a-f) were synthesized by the reactions of 3-alkyl(aryl)-4-amino-4,5-dihydro-1H- 1,2,4-triazol-5-ones (1a-f) with p-nitrobenzoyl chloride and characterized by elemental analyses and IR, ¹H-NMR, ¹³C-NMR and UV spectral data. The newly synthesized compounds 2 were titrated potentiometrically with tetrabutylammonium hydroxide in four non-aqueous solvents such as acetone, isopropyl alcohol, tert-butyl alcohol and N,Ndimethylformamide, and the half-neutralization potential values and the corresponding pKa values were determined for all cases. Thus, the effects of solvents and molecular structure upon acidity were investigated. In addition, isotropic ¹H and ¹³C nuclear magnetic shielding constants of compounds 2 were obtained by the gauge-including-atomic-orbital (GIAO) method at the B3LYP density functional level. The geometry of each compound has been optimized using the 6-311G basis set. Theoretical values were compared to the experimental data. Furthermore, these new compounds and five recently reported 3-alkyl-4-(2- furoylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (3a-c,e,f) were screened for their antioxidant activities. Full article

Five novel 3-alkyl-4-phenylacetylamino-4,5-dihydro-1H-1,2,4-triazol-5-ones (2) were synthesized by the reactions of 3-alkyl-4-amino-4,5-dihydro-1H-1,2,4-triazol-5-ones (1) with phenylacetyl chloride and characterized by elemental analyses and IR, ¹HNMR, ¹³C-NMR and UV spectral data. The newly synthesized compounds 2 were titrated potentiometrically with tetrabutylammonium hydroxide in four non-aqueous solvents such as isopropyl alcohol, tert-butyl alcohol, acetonitrile and N,N-dimethylformamide, and the half-neutralization potential values and the corresponding pKa values were determined for all cases. In addition, these new compounds and five recently reported 3-alkyl-4-(pmethoxybenzoylamino)- 4,5-dihydro-1H-1,2,4-triazol-5-ones (3) were screened for their antioxidant activities. Full article

The synthesis of 3-alkyl(aryl)-4-(3-ethoxy-4-hydroxybenzylidenamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones 3 from the reactions of 3-alkyl(aryl)-4-amino-4,5-dihydro-1H-1,2,4-triazol-5-ones 2 with 3-ethoxy-4-hydroxybenzaldehyde is described.The acetylation and methylation reactions of the compounds 3 giving compounds of type4 and 5, respectively, were investigated. The newly synthesized compounds werecharacterized using elemental analyses and IR, ¹H-NMR, ¹³C-NMR and UV spectral data.In addition, to investigate the effects of solvents and molecular structure upon acidity,compounds 3 were titrated potentiometrically with tetrabutylammonium hydroxide infour non-aqueous solvents (isopropyl alcohol, tert-butyl alcohol, acetonitrile and N,N-dimethylformamide). The half-neutralization potential values and the corresponding pKavalues were determined for all cases. Full article

A number of Sm (III) selective membranes of varying compositions using tin (IV) boratophosphate as electroactive material were prepared. Polyvinyl chloride, polystyrene and epoxy resin were used as binding materials. Membrane having composition of 40% exchanger and 60% epoxy resin exhibited best performance. This membrane worked well over a wide concentration range of 1x10^-5M to 1x10^-1 M of samarium ions with a Super-Nernstian slope of 40 mV/decade. It has a fast response time of less than 10 seconds and can be used for at least six months without any considerable divergence in potentials. The proposed sensor revealed good selectivities with respect to alkali, alkaline earth, some transition and rare earth metal ions and can be used in the pH range of 4.0-10.0. It was used as an indicator electrode in the potentiometric titration of Sm (III) ions against EDTA. Effect of internal solution was studied and the electrode was successfully used in non-aqueous media, too. Full article

Membranes of 4-tert-butylcalix(8)arene-octaacetic acid octaethyl ester (I) as an electroactive material, sodium tetraphenyl borate (NaTPB) as an anion excluder, and tri-n-butyl phosphate (TBP) as a solvent mediator in poly(vinyl chloride) (PVC) matrix have been tried for a strontium-selective sensor. The best performance was exhibited by the membrane having a composition 5:100:150:2 (I: PVC: TBP: NaTPB (w/w)). This sensor exhibits a good potentiometric response to Sr²⁺ over a wide concentration range (3.2 × 10 ^–5 –1.0 × 10 ^–1 M) with a Nernstian slope (30 mV/ decade). The response time of the sensor is 10 s and it has been used for a period of four months without any drift in potentials. The selectivity coefficient values are in the order of 0.01 for mono-, bi-, and trivalent cations which indicate a good selectivity for Sr²⁺ over a large number of cations. The useful pH range for the sensor was found to be 3-10 and it works well in mixtures with non-aqueous content up to 25 % (v/v). The sensor has been used as an indicator electrode in the potentiometric titration of Sr²⁺ against EDTA. Full article

3-Alkyl(Aryl)-4-amino-4,5-dihydro-1H-1,2,4-triazol-5-ones (2) reacted with 2-furoyl chloride and thiophene-2-carbonyl chloride to afford the corresponding 3- alkyl(aryl)-4-(2-furoylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (3) and 3-alkyl(aryl)- 4-(2-thienylcarbonylamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (4), respectively. The new compounds synthesized were characterized by using IR, 1H-NMR, 13C-NMR and UV spectral data together with elemental analysis. In addition, to investigate the effects of solvents and molecular structure upon acidity, compounds 3 and 4 were titrated potentiometrically with tetrabutylammonium hydroxide in four non-aqueous solvents (isopropyl alcohol, tert-butyl alcohol, N,N-dimethylformamide and acetonitrile). The half-neutralization potential values and the corresponding pKa values were determined for all cases. Full article

PVC based membranes of disodium salt of porphyrin 3,7,12,17-tetramethyl-8, 13-divinyl 2,18-porphine dipropionic acid (I) as ionophore with sodium tetra phenyl borate (NaTPB) as anion excluder and dibutyl phthalate (DBP), dioctyl phthalate (DOP), dibutyl butyl phosphonate (DBBP), tris(2- ethyl hexyl)phosphate (TEP), tri-n-butylphosphate (TBP) and 1- chloronaphthalene (CN) as plasticizing solvent mediators were prepared and constructed for determination of Zn(II). The PVC based membrane of (I) with DBBP as plasticizer and having anion excluder, NaTPB in the ratio PVC: I: NaTPB: DBBP (150: 10: 2: 200) gave the best results in terms of working concentration range (1.3×10^-5-1.0 ×10^-1M) with a Nernstian slope (30.0 mV/decade of activity). The useful pH range of the sensor is 3.0 –7.4, beyond which a drift in potential was observed. The response time of the sensor is 10s and the lifetime was about 2 months during which it could be used without any measurable divergence. It had good stability and reproducibility. The membrane worked satisfactorily in non-aqueous medium up to 40% (v/v) non-aqueous content. The selectivity coefficient values indicate that the electrode is highly selective for Zn²⁺ over a number of other cations except Na⁺ and Cd²⁺. Although Na⁺ and Cd²⁺ are likely to cause some interference, they would not interfere if present at the concentrations < 1 ×10^-5 and < 5 ×10^-5 M, respectively. The electrode has been used as an indicator electrode to determine the end point in the potentiometric titration of Zn²⁺ with EDTA. Full article

Silver(I) selective sensors have been fabricated from polystyrene matrix membranes containing macrocycle, Me₆(14) diene.2HClO₄ as ionophore. Best performance was exhibited by the membrane having a composition macrocycle : Polystyrene in the ratio 15:1. This membrane worked well over a wide concentration range 5.0×10^-6–1.0×10^-1M of Ag⁺ with a near-Nernstian slope of 53.0 ± 1.0 mV per decade of Ag⁺ activity. The response time of the sensor is <15 s and the membrane can be used over a period of four months with good reproducibility. The proposed electrode works well in a wide pH range 2.5-9.0 and demonstrates good discriminating power over a number of mono-, di-, and trivalent cations. The sensor has also been used as an indicator electrode in the potentiometric titration of silver(II) ions against NaCl solution. The sensor can also be used in non-aqueous medium with no significant change in the value of slope or working concentration range for the estimation of Ag⁺ in solution having up to 25% (v/v) nonaqueous fraction. Full article