Chromatographic characterization of high‐boiling petroleum fractions

Detailed investigation of solvent‐separated fractions of petroleum vacuum residues is necessary for understanding the separation mechanism using different solvents and to prepare better feedstocks for secondary conversion processes. The efficiency of different solvents to remove polars and insolubles from vacuum residues (of two Indian crude oils) has been studied. The solvents used were n‐heptane, n‐hexane, and n‐pentane (non‐polar) and ethyl acetate (polar). Soluble fractions were characterized for hydrocarbon group type analysis using high performance liquid chromatography (HPLC), average molecular weights using size exclusion chromatography (SEC), and boiling point distribution using high temperature gas chromatography (HTGC). Method development for HPLC analysis involved the study of parameters such as columns, solvent polarity, detectors, model compounds study, calibration, flow, and solvent gradient programming. The study demonstrated that ultimate soluble fractions have the least content of polar structures of the kind which can cause problems, during cracking and are least prone to cracking. The HPLC, SEC, and simulated distillation (SIMDIS) methods developed and standardized are simple, accurate, and suitable for the rapid assay needed for quick compositional surveys.     

Internal standardization for the determination of cadmium,cobalt, chromium and manganese in saline produced water from petroleum industry by inductively coupled plasma optical emission spectrometry after cloud point extraction

In the present paper a procedure is proposed for the determination of traces of Cd, Co, Mn and Cr in petroleum industry produced water by inductively coupled plasma optical emission spectrometry. The procedure is based on cloud point extraction of these metals, as their dithizonate complexes, into the surfactant-rich phase of octylphenoxypolyethoxyethanol surfactant (Triton X-114). Extractions were carried out in solutions with salinities between 10‰ and 70‰. Since residual salinity in the surfactant-rich phase caused differences in its transport to the plasma, yttrium was used as an internal standard to correct for this effect. The simultaneous metal extraction procedure was optimized by response surface methodology using a Doehlert design and desirability function. Enhancement factors of 21, 21, 9 and 19, along with limits of quantification of 0.093, 0.20, 0.73 and 1.2 μg L^− 1, and precision expressed as relative standard deviation (n = 8, 20.0 μg L^− 1) of 5.8, 1.2, 1.7 and 5.7% were obtained for Cd, Co, Mn and Cr, respectively. The accuracy was evaluated by spike recovery tests on the high salinity water samples with salinity of 40 and 63‰.     

Difference in micellar properties of sodium dodecyl sulfonate from sodium 4-decyl naphthalene sulfonate in D2O solution studied by 1H NMR relaxation and 2D NOESY

¹H chemical shift changes of sodium 4-decyl naphthalene sulfonate (SDNS) at 313 K show that its critical micellar concentration lies between 0.82 and 0.92 mmol/dm³, which is in the same range as that of the previous study at 298 K. The spin–lattice relaxation time, spin–spin relaxation time and two-dimensional nuclear Overhauser enhancement spectroscopy experiments give information about the structure of the SDNS micelle and the dynamics of the molecules in the micelle. The size of the SDNS micelle remains almost unchanged in the temperature range from 298 to 313 K as deduced by analyzing the self-diffusion coefficient. Special arrangement of the naphthyl rings of SDNS in the micelles affects the packing of these hydrophobic chains. The methylene groups of the alkyl chain nearest the naphthalene groups penetrate into the aromatic region, which results in a more tightly packed hydrophobic micellar core than that of sodium dodecyl sulfonate.     

Hypervalent Iodine(III) Sulfonate Mediated Synthesis of Imidazo[1,2‐a]pyridines

A direct and efficient method for the conversion of alkyl aryl ketones to imidazo[1,2‐α]pyridines has been developed based on initial formation of α‐organosulfonyloxy ketones and their subsequent cyclocondensation by 2‐aminopyridines in one‐pot conditions.     

三硝基苯磺酸离子选择电极的制备和应用

三硝基苯磺酸是氨基酸分析常用试剂,在水溶液中它是稳定的一价阴离子。Sarantonis曾研制液膜型三硝基苯磺酸离子选择电极,间接测定氨基酸的浓度,其电极的线性响应范围为1.1×10~(-1)～5.1×10~(-5)mol·L~(-1)。     

Liquid crystalline ionomers. II. Main chain liquid crystalline polymers with terminal sulfonate groups

Liquid crystalline ionomers containing sulfonate groups on the terminal unit of the chain were synthesized by an interfacial condensation reaction of 4,4′-dihydroxy-α,α′-dimethyl benzalazine, the monofunctional dye fast yellow (FY), and a 50/50 mixture of sebacoyl and dodecanedioyl dichlorides. The weight-average molecular weights were estimated from inherent viscosity measurements to be between 6000–11,000 and the sodium sulfonate concentrations ranged from 0–18.4 meq/100 g polymer. Elemental analyses, however, indicated much higher molecular weights, which suggested that there was a distribution of chains with one, two, or no FY endgroups. The polymers were semicrystalline and melted at ca. 140°C to form nematic mesophases that were stable over a temperature range of ca. 80°C. They were thermally stable to about 350°C. The ionomeric nature of the polymers was confirmed by the presence of intermolecular associations in nonpolar solvents, as demonstrated by dilute solution viscosity measurements.     

Supercritical fluid chromatography of petroleum products using flameless sulfur chemiluminescence detection

Supercritical fluid chromatography using flameless sulfur chemiluminescence detection has been investigated for the analysis of sulfur compounds in petroleum products. The chromatography and detection system was easy to implement and exhibited good precision, linearity, selectivity, and sensitivity. A minimum detectable limit of 0.3 pg sulfur/s was obtained, and response to sulfur in different sulfur species was nearly equimolar.     

Coordination solids via assembly of adaptable components: systematic structural variation in alkaline earth organosulfonate networks

A family of alkaline earth organosulfonate coordination solids is reported. In contrast to more typical crystal engineering approaches, these solids are sustained by the assembly of building blocks that are coordinatively adaptable rather than rigid in their bonding preferences. The ligand, 4,5-dihydroxybenzene-1,3-disulfonate, L, progressively evolves from a 0D, 1D, 2D, to a 3D microporous network with the Group II cations Mg(2+), Ca(2+), Sr(2+), and Ba(2+), (compounds 1-4), respectively. This trend in dimensionality can be explained by considering factors such as hard-soft acid-base principles and cation radii, a rationalization which follows salient crystal engineering principles. The selective gas sorption properties of the microporous 3D network [Ba(L)(H(2)O)].H(2)O, 4, with different gaseous guests are also presented.     

Fluorocarbons in the global environment: a review of the important interactions with atmospheric chemistry and physics

Fluorocarbon impact on ozone depletion is reviewed together with the efficacy of the Montreal Protocol in acting to correct the imbalance between stratospheric ozone production and destruction. The Protocol is also helping to reduce global warming: CFCs are shown to be currently the largest fluorocarbon contributors to climate change. Relative contributions to climate change from CFCs and their HFC substitutes are discussed, together with the consequences of control of minor greenhouse gases on an environmental impact which is dominated by carbon dioxide emissions. Both the potencies of the materials for environmental change and their concentrations in the atmosphere are important and are considered here.Trifluoroacetic acid, a minor product of atmospheric decomposition of some HCFCs and HFCs and of the pyrolysis of fluoropolymers, has been shown to be uniformly distributed in seawater to a depth of over 4000 m and so is natural, although the actual source has yet to be identified.The Montreal Protocol is only one example of action to reduce undesirable impact from fluorocarbons. Other, less universal, actions include abatement of fluoroform greenhouse gas emissions from HCFC manufacturing, process changes to eliminate trifluoromethylsulfur pentafluoride emissions from electrochemical fluorination and ceasing manufacture of perfluorooctanyl sulfonate compounds due to their persistence in human tissue.     

Determination of hopane biomarkers in Arabian crude oils by gas chromatography-tandem mass spectrometry

Gas chromatography-mass spectrometry with the mass spectrometer operated in the tandem mode at a constant accelerating voltage was used to analyse for triterpanes in Arabian crude oils. Specific molecular parent-daughter ion pairs were selected for quantitative measurements owing to their metastable transitions in the first field-free region. More accurate relative distribution ratios of hydrocarbon biomarkers were determined by this sequential gating technique than by the conventional diagnostic daughter ion mass fragmentogram in common GC-MS. The data and spectra obtained from MS-MS operation may serve as unique “fingerprints” for these regional crudes