Measurement of water by oven evaporation using a novel oven design.

Using an automated oven evaporation technique combined with the coulometric Karl Fischer method, the mass fraction of water has been measured in cement, coal, and refined oil samples. The accuracy of this method was established by using SRM 2890, water-saturated 1-octanol that was added to white oil. The samples were analyzed for total reactive Karl Fischer reagent (KFR) material, for interfering materials, and for material that does not react with the aldehyde–ketone KFR. All of the samples yielded volatile material that reacted with the standard KFR. None of the samples contained significant masses of material that reacted with iodine. The cement and coal SRMs contained no material that reacted with methanol and very little material that did not volatilize at 107°C. The refined oils contained some material that was volatile at 107°C and some at 160°C. However, none of this material reacted with the aldehyde–ketone reagent. These results show that the material in the solid samples is water and that the material in the refined oils is a material other than water which reacts with methanol to form water.     

A coulometric method for determining substances that interfere with the measurement of water in oils and other chemicals by the Karl Fischer method

In order to fulfill a need to measure water in crude oils containing materials that interfere with the measurement of water by the Karl Fischer method, by reacting with iodine or iodide, a coulometric method has been developed and validated using 0.1 mol L(-1) Sodium thiosulfate as a calibrant. These interfering substances were measured in water-mass-equivalents, which were expressed as the mass of water that reacts with an equal mass of iodine in the Karl Fischer method. The SO(2)-free reagent that has been modified reacts quantitatively with sodium thiosulfate, cysteine and ascorbic acid but does not react with vinyl acetate. The level of interfering substances was measured in five transformer oils (including Reference Materials RM 8506 and RM 8507), a high and a low sulfur crude oil (Standard Reference Materials SRM 2721 and SRM 2722 respectively), a white oil, a high-vacuum oil and a high-viscosity base-stock oil. One oil contained less than 10 mg kg(-1) (water-mass-equivalents of interfering substances in oil) and two oils (RM 8507 and Drakeol 35) contained no measurable amount of interfering material (<0.2 mg kg(-1)). SRM 2271, a sour crude oil contained 834 mg kg(-1) (standard deviation (SD)=25 mg kg(-1)) (water-mass-equivalents of interfering substances in oil). Approximately 20% of this material was volatile and an additional 20% appeared to undergo some degradation (possibly oxidation) once the oil was exposed to air. These results indicate that this is a general method for measuring substances in oils that react with iodine and that it is capable of measuring in a variety of oils, using commercial instrumentation, interfering substances that inflate water measurements.     

Quantitative moisture measurements in lubricating oils by FTIR spectroscopy combined with solvent extraction approach

Quantitative measurements of moisture in mineral and synthetic polyol ester based lubricating oils using FTIR spectroscopy combined with solvent extraction approach are described. The samples are prepared by mixing dry dimethyl sulfoxide (DMSO) and lubricating oils, and after phase separation, the extracted bottom DMSO layers are analyzed with FTIR. The results from the solvent extraction show that the DMSO is an excellent aprotic solvent for water removal from lubricating oils. The spectroscopic data reveal that near IR region (5400–4800 cm^{− 1}, molecular water) gives the best results for water determination in both mineral and synthetic lubricants, followed by mid-IR region (3800–3200 cm^{− 1}, O―H stretching). However, the water content estimated from the IR region (1800–1550 cm^{− 1}, O―H bending) has the lowest accuracy due to the interference from aminic, phenolic additives and other oxidation products present in the lubricants. The accuracy of the FTIR spectroscopy combined with solvent extraction approach is exemplified by monitoring the water content in mineral oil during oxidation process at 150 °C for 30 days. The quantitative determination of the moisture in the fresh and oxidized oils by the developed approach is shown to be an alternative technique to Karl Fischer titration.     

Preparation of 4-trifluoroethylidene-1,3-dioxolane derivatives via new stable (trifluoromethyl)ethynylation reagent

Perfluoroalkylated 4-trifluoroethylidene-1,3-dioxolane derivatives 2a-q were prepared in excellent yields from the reaction of new stable (trifluoromethyl)ethynylation reagent 1a with 1.3 equiv. of TBAF at −15°C for 10 min, followed by treatment with 2 equiv. of phenyl perfluoroalkylated ketone derivatives at room temperature. The reaction of 1a with 1.3 equiv. of TBAF, followed by treatment with 1 equiv. of aldehyde or ketone at −15°C for 10 min and then with trifluoroacetophenone (1 equiv.) at room temperature afforded perfluoroalkylated 4-trifluoroethylidene-1,3-dioxolane derivatives 2t-u in moderate yields.     

Electrophilic amination of diorganozinc reagents by oxaziridines

Electrophilic amination of organozinc reagents by oxaziridines has been studied. Diorganozinc reagents R₂Zn (R = alkyl or aryl) react with N-Boc oxaziridine to afford N-Boc protected primary amines BocNHR in moderate to good yields. No additives are needed in this reaction, which proceeds at 0 °C. We suggest that the presence of two heteroatoms in oxaziridine allows Lewis base activation of the diorganozinc reagent.     

The use of thin-layer chromatography in the analysis of lubricating oils

Summary A report is given on the application of thin-layer chromatography to the analysis of additives in lubricating oils. The separation and identification of antioxidants, phenates, sulphonates, zinc dialkyl dithiophosphates and polymeric additives is described. A measurement of additive depletion in used oils is possible by comparison of corresponding chromatograms.

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Zusammenfassung Es wird über die Verwendung der Dünnschicht-Chromatographie bei der Analyse der Additive von Schmierölen berichtet. Die Abtrennung und Identifizierung von Antioxydantien, Phenolaten, Sulfonaten, Zinkdialkyldithiophosphaten und polymeren Additiven wird beschrieben. Eine Messung der Abnahme der Additivkonzentration in gebrauchten Ölen ist durch Vergleich entsprechender Chromatogramme möglich.

     

Characteristics of bicyclic sesquiterpanes in crude oils and petroleum products

This study presents a quantitative gas chromatography–mass spectrometry analysis of bicyclic sesquiterpanes (BSs) in numerous crude oils and refined petroleum products including light and mid-range distillate fuels, residual fuels, and lubricating oils collected from various sources. Ten commonly recognized bicyclic sesquiterpanes were determined in all the studied crude oils and diesel range fuels with principal dominance of BS3 (C₁₅H₂₈), BS5 (C₁₅H₂₈) and BS10 (C₁₆H₃₀), while they were generally not detected or in trace in light fuel oils like gasoline and kerosene and most lubricating oils. Laboratory distillation of crude oils demonstrated that sesquiterpanes were highly enriched in the medium distillation fractions of ∼180 to 481 °C and were generally absent or very low in the light distillation fraction (boiling point to ∼180 °C) and the heavy residual fraction (>481 °C). The effect of evaporative weathering on a series of diagnostic ratios of sesquiterpanes, n-alkanes, and biomarkers was evaluated with two suites of weathered oil samples. The change of abundance of sesquiterpanes was used to determine the extent of weathering of artificially evaporated crude oils and diesel. In addition to the pentacyclic biomarker C₂₉ and C₃₀ αβ-hopane, C₁₅ and C₁₆ sesquiterpanes might be alternative internal marker compounds to provide a direct way to estimate the depletion of oils, particularly diesels, in oil spill investigations. These findings may offer potential applications for both oil identification and oil-source correlation in cases where the tri- to pentacyclic biomarkers are absent due to refining or environmental weathering of oils.     

Determination of aluminum by electrothermal atomic absorption spectroscopy in lubricating oils emulsified in a sequential injection analysis system

The sequential injection (SIA) technique was applied for the on-line preparation of an “oil in water” microemulsion and for the determination of aluminum in new and used lubricating oils by electrothermal atomic absorption spectrometry (ET AAS) with Zeeman-effect background correction. Respectively, 1.0, 0.5 and 1.0 ml of surfactants mixture, sample and co-surfactant (sec-butanol) solutions were sequentially aspirated to a holding coil. The sonication and repetitive change of the flowing direction improved the stability of the different emulsion types (oil in water, water in oil and microemulsion). The emulsified zone was pumped to fill the sampling arm of the spectrometer with a sub-sample of 200 μl. Then, 10 μl of this sample solution were introduced by means of air displacement in the graphite tube atomizer. This sequence was timed to synchronize with the previous introduction of 15 μg of Mg(NO₃)₂ (in a 10 μl) by the spectrometer autosampler. The entire SIA system was controlled by a computer, independent of the spectrometer. The furnace program was carried out by employing a heating cycle in four steps: drying (two steps at 110 and 130 °C), pyrolisis (at 1500 °C), atomization (at 2400 °C) and cleaning (at 2400 °C). The calibration graph was linear from 7.7 to 120 μg Al l⁻¹. The characteristic mass (mo) was 33.2 pg/0.0044 s and the detection limit was 2.3 μg Al l⁻¹. The relative standard (RSD) of the method, evaluated by replicate analyses of different lubricating oil samples varied in all cases between 1.5 and 1.7%, and the recovery values found in the analysis of spiked samples ranged from 97.2 to 100.4%. The agreement between the observed and reference values obtained from two NIST Standard Certified Materials was good. The method was simple and satisfactory for determining aluminum in new and used lubricating oils.     

Characterization of zinc dialkyl dithiophosphate lubricating oil additives by high-voltage zone electrophoresis

A method is described for the rapid qualitative characterization of zinc dialkyl dithiophosphate oil additives by high-voltage zone electrophoresis, on a silica gel substrate. Samples of lubricating oils and lubricating oil additive packages can be analysed directly, as solutions in light petroleum (b.p. 80–100°).     

Effect of solute polarity on the performance of porapak type porous polymers

Summary The breakthrough volume of ådsorbent traps made with porous polymer beads Porapak N, P. Q, R, S was evaluated by analysis of polarity reference substances proposed by Rohrschneider (ethanol, methyl ethyl ketone, nitrometane, benzene, pyridine) by McReynolds (butanol, methyl propyl ketone) and of the first term of some homologous series: alcohols, aldehides, carboxilic acids, nitrocompounds, iodoalkanes and nitriles.Adjusted retention times of the compounds were measured at 200°C and correlated with the physical properties and with polarity class according to Ewell.Trapping efficiency of the various Porapak types was evaluated and the theoretical breakthrough volumes at 25°C was calculated for the used test substances.Dedicated to Prof. Dr. A. Liberti on the occasion of his 70th birthday.     

Synthesis and properties of aminomethoxy derivatives of 1-(ethylsulfanyl)alkanes

Mannich condensation of 1-(ethylsulfanyl)alkan-2-ols, formaldehyde, and secondary amines taken in equimolar amounts was used to obtain new amino derivatives of 1-(ethylsulfanyl)alkanes. The structure of the thus synthesized compounds was confirmed by elemental analysis, IR and ¹H NMR spectroscopies, and mass spectrometry. It is shown that the obtained compounds can be used as antimicrobial additives to lubricating oils and antiseptic substances against bacteria and fungi.     

Interlaboratory comparisons and improvements of methods for acid number determination in used motor oils

The results of two interlaboratory comparisons of acid number determinations in used motor oils are discussed. It is shown that the comparability of the measurement results is not as good as that required by known standards for petroleum products. The problem is motor oil contaminants which accumulated during use, and which are the source of a matrix effect in the acid number determination. The standard methods’ drawbacks are analyzed and some improvements are proposed. Repeatability and accuracy of the improved methods are evaluated. Received: 11 December 2001 Accepted: 15 February 2002     

Conductance of potassium lodide in mixed solvents

The conductance of potassium iodide has been measured in the solvents ethylene carbonate, water, methyl ethyl ketone, and pairwise mixtures of these solvents at 40°C; and ethylene carbonate-water, tetramethylene sulfone-water, dimethyl sulfoxide-water, tetrahydrofuran-water, ethylene carbonate-tetramethylene sulfone-water, ethylene carbonate-tetramethylene sulfone, and tetrahydrofuran-dimethyl sulfoxide at 25°C. For dielectric constants greater than about 60, the pairing constants K_A are in the range 0.3–2.0; no correlation between K_A and solvent properties could be established. For lower dielectric constants, K_A increases exponentially with decreasing dielectric constant. Addition of a proton, acceptor to water initially decreases K_A regardless of whether the dielectric constant of the mixture is higher or lower than that of water, suggesting that ion pairs in water may be stabilized by cage structures. The Walden product A_o is also decreased by the addition of proton acceptors.     

Fluoro-ketones. II Reactions of fluorocarbon grignards and copper compounds with perfluoroalkylacid fluorides

The reactions between C₆F₅MgBr (I), p-BrC₆F₄MgBr (X), C₆F₅Cu (XXI), p-HC₆F₄Cu (XXII) and p-BrC₆F₄Cu (XV) with primary and secondary perfluoroalkylether acid fluorides were studied. The Grignard compounds react very slowly with the secondary acid halides (R_fCF(CF₃C(O)F) whereby competing reactions cause undesirable by-products and reduction of ketone yields. Primary acid halides (R_fCF₂C(O)F) react much faster with C₆F₅MgBr to give the ketone in improved yields. The organocopper compound react with either primary or secondary acid halides to give the ketone in excellent yields with no by-product formation from competing secondary reactions. Solvent, type of organometallic reagent and primary versus secondary acid fluoride are variables that influence product yield and product distribution.     

Measurement of critical heat flux conditions under vacuum

Determination of optimum conditions for waste oil (used motor oils, transformer oils) regeneration using vacuum distillation was attempted including the search for the optimum temperature difference between the heating surface and the boiling point of the liquid. Optimum temperature allowed the distillation equipment to operate at maximum performance. Equipment suitable for the measurement of boiling curves under atmospheric pressure and vacuum conditions was assembled. These curves were used to determine the optimum temperature difference of various substances including waste oils. Properties of pure substances, for example water, ethanol, hexane, heptane, isooctane, decane, or dodecane, were measured with this equipment under atmospheric pressure. Results of various liquids measurements under vacuum and atmospheric pressure are presented.     

Ene-type reaction of trisubstituted monoterpene alkenes with methyl sulfite and thionyl chloride

Trisubstituted methylalkenes react with methyl sulfite at 25°C in the presence of BF₃ · Et₂O in the ene-type fashion to give the corresponding methallyl sulfinates. Such compounds can also be prepared under considerably milder conditions by the Et₂AlCl-catalyzed reaction of thionyl chloride with mono- and dienes followed by methanolysis of intermediate alkyl sulfinyl chlorides. These reactions represent a new method for terminal functionalization of linear isoprenoids.Deceased Nov.1, 1992.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 105–107, January, 1993.     

Modelling relation between oxidation resistance and tribological properties of non-toxic lubricants with the use of artificial neural networks

The lubricants based on vegetable oils, as environmental friendly, are urgently sought. However, in addition to ecological characteristics, the lubricating properties have to be met. To meet these requirements the active additives influencing the lubricating properties and oxidation resistance are used. The useful lifetime of lubricants is determined largely by their abilities to resist oxidation. The article presented the results of new, ecological lubricants development. The oxidation performances of different developed lubricants have been tested. The experimentally determined oxidation stability of the compositions based on vegetable oils are presented. Analysed oxidation onset temperature was obtained from the differential scanning calorimetry (DSC) curves, which provides the rapid prediction of the oxidative stability of lubricants. Besides the lubricating composition based on vegetable oils, the developed greases-based mineral, or synthetic oil were investigated. The properties of these greases were evaluated using the measurement of parameters describing structure (penetration) and resistance to high temperature (dropping point). The lubricating properties of both the greases and vegetable oil compositions were tested on four-ball testing machine. In the results of the modelling of the lubricating properties the neural network models for the both types of the lubricants were developed. A discussion of the research results and analysis of models validity is given below. The experimental results are compared with the calculated using the neural models. An acceptable agreement was achieved.     

Use of temperature dependent Raman spectra to improve accuracy for analysis of complex oil-based samples: Lube base oils and adulterated olive oils

A simple and effective strategy to improve accuracy for Raman spectroscopic analysis of complex mixture samples by probing a measurement temperature yielding enhanced spectral selectivity has been demonstrated. For the evaluation, the determination of Kinematic Viscosity at 40 °C (KV@40) of lube base oil (LBO) samples was initially attempted. Partial least squares (PLS) was used to determine the KV@40 using Raman spectra of the samples collected at 8 different temperatures from 20 to 90 °C with 10 °C increments. Interestingly, the distinct temperature-induced spectral variation among the samples occurred at 50 °C, thereby resulting in the improved accuracy for determination of KV@40. Two-dimensional (2D) correlation analysis was also performed to find an additional supportive rationale for the improved accuracy. The strategy was further evaluated for the identification of soybean oil-adulterated olive oils using linear discriminant analysis (LDA). Similarly, the discrimination accuracy was improved around 80–90 °C due to the enhanced spectral selectivity between olive and soybean oils. In overall, these two results successfully demonstrate analytical effectiveness of the strategy.