Efficiency of methods for Karl Fischer determination of water in oils based on oven evaporation and azeotropic distillation

The efficiency of azeotropic distillation and oven evaporation techniques for trace determination of water in oils has recently been questioned by the National Institute of Standards and Technology (NIST), on the basis of measurements of the residual water found after the extraction step. The results were obtained by volumetric Karl Fischer (KF) titration in a medium containing a large excess of chloroform (> or = 65%), a proposed prerequisite to ensure complete release of water from the oil matrix. In this work, the extent of this residual water was studied by means of a direct zero-current potentiometric technique using a KF medium containing more than 80% chloroform, which is well above the concentration recommended by NIST. A procedure is described that makes it possible to correct the results for dilution errors as well as for chemical interference effects caused by the oil matrix. The corrected values were found to be in the range of 0.6-1.5 ppm, which should be compared with the 12-34 ppm (uncorrected values) reported by NIST for the same oils. From this, it is concluded that the volumetric KF method used by NIST gives results that are much too high.     

Determination of water in NIST reference material for mineral oils

The accuracy of the reference concentrations of moisture in electrical insulating oil RM 8506 and lubricating oil RM 8507 (both of mineral type) and specified by the National Institute of Standards and Technology (NIST) as containing 39.7 and 76.8 ppm (w/w) water, respectively, has recently been the subject of debate in this journal. To shed some further light on this controversy, we report in this correspondence results for these oils obtained by two additional methods, one based on specially designed reagents for diaphragm-free Karl Fischer (KF) coulometry and the other based on the concept of stripping at elevated temperature/continuous KF coulometry. A positive interference effect was shown to take place for RM 8506 when the direct coulometric method was used. If the results are corrected for this, the values including six different procedures varied in the range 13.5-15.6 ppm (w/w). For RM 8507, all values were between 42.5 and 47.2 ppm (w/w), which means that the values recommended by NIST for both reference oils using volumetric titration are about twice as high as those obtained with the other techniques. A possible explanation for this discrepancy is presented.     

Bias assessment of current technologies used for the determination of low levels of moisture in mineral oil samples

The problem in the current debate on the accuracy of Karl Fischer (KF) titrations lies in the fact that coulometry is being compared to volumetry on mineral oil samples for which the true moisture content is unknown. To clarify this point, dehydrated oil samples equilibrated under known temperature and relative humidity conditions and equilibrated oil samples containing known amounts of added moisture were used to assess the accuracy of the determinations. In addition, the measurements were extended to other techniques given that it is unlikely that they would be affected by the same phenomenon causing the KF systematic errors. The samples sent to different laboratories were analyzed by headspace/capillary gas chromatography, gas-phase H2 sensor, oil-phase or gas-phase RH sensors, KF coulometric titration with direct or indirect injection, and KF volumetric titration using a standard or NIST modified procedure. The laboratory comparison showed that with the exception of 4 techniques out of 10 that were tested, the measurements gave results in the expected concentration range. Considering the exceptions, two techniques based on volumetric titration yielded results tainted with an important positive bias for both sample types. This bias, tentatively associated with the high iodine end point concentration used by these systems, was estimated at approximately 22 ppm under the conditions applied by NIST. On the other hand, the two RH sensors showed a marked tendency to underestimate the value of the samples containing high moisture content. In this case, a loss of analyte through wall adsorption during the time required to achieve steady-state conditions in the measuring chamber seems to be at the origin of the negative biases.     

Systematic bias in the measurement of water in oils by tubular oven evaporation and azeotropic distillation.

Water in oil has been measured by tubular oven evaporation and by azeotropic distillation into a coulometric moisture analyzer. The results of these measurements were compared to the results obtained by volumetric titration of water in oil. The volumetric measurements were consistently higher than the measurements made by tubular oven evaporation or azeotropic distillation. A mass balance study was performed by volumetric Karl Fischer titration of the water in the oil that remained in the tubular oven and in the distillation apparatus. This study indicated that measurable amounts of water were not removed after exhaustive evaporation or distillation. The sum of the water removed by distillation from toluene and that remaining in the distillation chamber was equal to the amount of water measured in the oil by the volumetric method. The data are consistent with the existence of an oil-water azeotrope that does not release water upon evaporation at 160 degrees C or upon dissolution in toluene and distillation of the water-toluene azeotrope. These results were obtained for oils varying in viscosity from 8 to 850 m2/s, and the amount of water remaining associated with the oil appears to be dependent upon the composition of the oil and the method of analysis.     

Quantitative determination of moisture in lubricants by Fourier transform infrared spectroscopy

This paper describes the development of a practical Fourier transform infrared (FT-IR) method for the determination of moisture in lubricants through the combined use of signal transduction and differential spectroscopy to circumvent matrix effects. The acid-catalyzed stoichiometric reaction of 2,2-dimethoxypropane (DMP) with moisture to produce acetone was used to provide IR signals proportional to the amount of moisture present in oils. Calibration standards were prepared by spiking polyalphaolefin (PAO) gravimetrically with water using dioxane as a carrier. For FT-IR analysis, standards and samples were diluted with acidified isooctane and then split, with one aliquot treated with DMP and the other with a blank reagent. The spectra of the two aliquots were collected, and a differential spectrum was obtained so as to ratio out the invariant spectral contributions from the sample. Quantitation for moisture was based on measurement of the peak height of the nu(C=O) absorption of acetone at 1717 cm(-1), yielding a standard error of calibration of approximately 40 ppm H2O. The method was validated by standard addition of water in dioxane to PAO containing added base as well as to new and used oils. In all cases the method responded quantitatively to standard addition, the average standard error of prediction being approximately 80 ppm, with the results showing only a minor dependence on the oil formulation. From an analytical perspective, the FT-IR method is both more reproducible and more accurate than Karl Fischer methods and has advantages in terms of environmental considerations, sample size, and speed of analysis as well as the variety of oil types that can be handled. Signal transduction/differential spectroscopy may have broader utility as an alternative means for the determination of low levels of moisture in complex matrices.     

A new Fourier transform infrared method for the determination of moisture in edible oils

A rapid, practical, and accurate Fourier transform infrared (FT-IR) method for the determination of moisture content in edible oils has been developed based on the extraction of water from oil samples into dry acetonitrile. A calibration curve covering a moisture content range of 0-2000 ppm was developed by recording the mid-infrared (MIR) spectra of moisture standards, prepared by gravimetric addition of water to acetonitrile that had been dried over molecular sieves, in a 500 microm ZnSe transmission flow cell and ratioing these spectra against that of the dry acetonitrile. Water was measured in the resulting differential spectra using either the OH stretching (3629 cm(-1) or bending (1631 cm(-1)) bands to produce linear standard curves having standard deviations (SDs) of approximately +/-20 ppm. For moisture analysis in oils, the oil sample was mixed with dry acetonitrile in a 1:1 w/v ratio, and after centrifugation to separate the phases, the spectrum of the upper acetonitrile layer was collected and ratioed against the spectrum of the dry acetonitrile used for extraction. The method was validated by standard addition experiments with samples of various oil types, as well as with oil samples deliberately contaminated with alcohols, hydroperoxides, and free fatty acids to investigate possible interferences from minor constituents that may be present in oils and are potentially extractable into acetonitrile. The results of these experiments confirmed that the moisture content of edible oils can be assessed with high accuracy (on the order of +/-10 ppm) by this method, thus providing an alternative to the conventional, but problematic, Karl Fischer method and facilitating the routine analysis of edible oils for moisture content.     

Performance of a gas flow meter calibration system utilizing critical flow venturi standards

A set of Critical Flow Venturis (CFVs) were manufactured by Flow Systems and calibrated by NIST in Gaithersburg, MD. Subsequently these flow standards along with pressure and temperature standards have been integrated into a gas flow meter calibration (GFC) system. Performance data and an uncertainty analysis is discussed here in this paper. Calibration data on these CFV standards will be used to inter-compare the NIST and CEESI primary facilities.     

电位滴定法标定余氯标准物质

应用自动电位滴定仪,建立了电位滴定法标定余氯标准物质的方法。根据电位滴定法的基本原理分析该法的影响因素,分别从滴定液预加体积、加液步长以及加水量等滴定条件进行方法优化,确定电位滴定法的滴定参数。采用建立的方法对余氯标准物质进行标定,验证方法的精密度和准确度。结果表明该法的相对标准偏差为0.09%,与手工滴定法标定值的相对误差为-0.08%。证明建立的电位滴定法能够准确标定余氯标准物质,同时操作简便、重复性好并且具有可行性和实用性。     

Uncertainty in NIST Force Measurements

This paper focuses upon the uncertainty of force calibration measurements at the National Institute of Standards and Technology (NIST). The uncertainty of the realization of force for the national deadweight force standards at NIST is discussed, as well as the uncertainties associated with NIST’s voltage-ratio measuring instruments and with the characteristics of transducers being calibrated. The combined uncertainty is related to the uncertainty of dissemination for force transfer standards sent to NIST for calibration.     

Calibration of a liquid scintillation counter to assess tritium levels in various samples

An LKB-Wallac 1217 Liquid Scintillation Counter (LSC) was calibrated with a newly adopted cocktail. The LSC was then used to measure tritium levels in various samples to assess the compliance of tritium levels with the recommended international levels. The counter was calibrated to measure both biological and operational samples for personnel and for an accelerator facility at KFUPM. The biological samples include the bioassay (urine), saliva, and nasal tests. The operational samples of the light ion linear accelerator include target cooling water, organic oil, fomblin oil, and smear samples. Sets of standards, which simulate various samples, were fabricated using traceable certified tritium standards. The efficiency of the counter was obtained for each sample. The typical range of the efficiencies varied from 33% for smear samples down to 1.5% for organic oil samples. A quenching curve for each sample is presented. The minimum detectable activity for each sample was established. Typical tritium levels in biological and operational values are presented. All measured values are far below the recommended international limits.     

Standards for bullets and casings

The National Institute of Standards and Technology is developing reference standards through its Office of Law Enforcement Standards with funding provided by the National Institute of Justice. The standard reference materials are used by crime laboratories to verify that results obtained when using their protocols and methodologies meet legal requirements and that equipment is operating properly. The NIST Reference Materials 8240/8250 standard bullets and casings is an example of materials that will assist laboratories in calibrating their instruments and ensuring quality control.The Office of Law Enforcement Standards (OLES) at the National Institute of Standards and Technology (NIST) manages research in many different disciplines of forensic science. One of these projects supports the National Integrated Ballistics Information Network (NIBIN). NIST digitized six bullet signatures from samples provided by the Bureau of Alcohol, Tobacco, and Firearms (ATF) and the Federal Bureau of Investigation (FBI). Using these signatures as a virtual standard, NIST’s Instrument Shop manufactured 20 reference materials (RM) 8240 standard bullets using a numerically-controlled diamond turning machine. Test results show high reproducibility of the bullet signatures on standard bullets. NIST has also developed a new parameter for bullet signature comparisons, using autocorrelation functions, and proposed a diagram for tracing local ballistics measurements to the National Laboratory Center of the ATF and to the FBI. Using an electro-forming process, NIST has manufactured prototype standard casings and test results show high reproducibility for the casing signatures.     

Intramural Comparison of NIST Laser and Optical Fiber Power Calibrations

The responsivity of two optical detectors was determined by the method of direct substitution in four different NIST measurement facilities. The measurements were intended to demonstrate the determination of absolute responsivity as provided by NIST calibration services at laser and optical-communication wavelengths; nominally 633 nm, 850 nm, 1060 nm, 1310 nm, and 1550 nm. The optical detectors have been designated as checks standards for the purpose of routine intramural comparison of our calibration services and to meet requirements of the NIST quality system, based on ISO 17025. The check standards are two optical-trap detectors, one based on silicon and the other on indium gallium arsenide photodiodes. The four measurement services are based on: (1) the laser optimized cryogenic radiometer (LOCR) and free field collimated laser light; (2) the C-series isoperibol calorimeter and free-field collimated laser light; (3) the electrically calibrated pyroelectric radiometer and fiber-coupled laser light; (4) the pyroelectric wedge trap detector, which measures light from a lamp source and monochromator. The results indicate that the responsivity of the check standards, as determined independently using the four services, agree to within the published expanded uncertainty ranging from approximately 0.02 % to 1.24 %.     

Supercritical carbon dioxide extraction of 2,4-dichlorophenol from food crop tissues.

Supercritical fluid extraction with carbon dioxide has been found to be effective for the isolation of residue levels (0.1-1 ppm) of 2,4-dichlorophenol from selected plant tissues. The 2,4-dichlorophenol residues were incompletely extracted with supercritical CO2 alone, since a substantial fraction of the 2,4-dichlorophenol was covalently attached to the plant matrix. An acid pretreatment procedure was developed to partially hydrolyze the plant tissue prior to extraction, releasing the bound 2,4-dichlorophenol residues. Steam distillation showed higher residue levels for field-treated straw samples. This is attributed to the greater degree of hydrolysis inherent in the steam distillation procedure. Supercritical CO2 extraction of field-treated seed samples showed higher levels of 2,4-dichlorophenol residues than did steam distillation. The supercritical fluid extractant was able to solvate 2,4-dichlorophenol residues in the interior of the seed and transport them to the surface for collection. The aqueous medium used in steam distillation was unable to penetrate the hydrophobic seed matrix to the same degree. While the actual extraction time experienced in supercritical fluid extraction was far less than that of steam distillation (45 min vs 6 h, respectively), the total sample preparation time was similar in both methods.     

Microwave-assisted steam distillation for simple determination of polychlorinated biphenyls and organochlorine pesticides in sediments

A novel sample extraction technique for polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) analysis using microwave-heating device is developed. In this study, microwave-assisted extraction (MAE) and steam distillation techniques were combined. Desorption of the anatytes from solid matrixes was accelerated with water vapor which was generated by microwave irradiation. A sample holder in a commercial microwave extraction cell kept the sample from direct contact with the organic solvent for analytes trapping during the treatment process. Therefore, relatively clean extracts were obtained with small amount of solvents. Without any cleanup steps, the obtained extract could be analyzed with gas chromatograph/mass spectrometers (GC/MS). Six PCB congeners (PCB15, 28, 70, 101, 180, 194, 209) and three OCPs (gamma-HCH, 4,4'-DDE, 4,4'-DDD) in two marine sediment samples (a sediment collected from a bay of Kyusyu Island, Japan, and a certified reference material NIST SRM1944) were analyzed by using this microwave-assisted steam distillation (MASD) technique and another extraction method (exhaustive steam distillation, MAE, and Soxhlet extraction); and comparisons of the results are shown in this report. Although recovery yields of highly chlorinated biphenyls (PCB180, 194, 209) and relatively polar OCPs (gamma-HCH, 4,4'-DDD) were low (30-60%) compared with other analytes (PCB15, 28, 70, 101, 4,4'-DDE; recovery, 80-100%), use of isotope labeled internal standards for the MASD technique gave comparable results with the values obtained by other extraction methods and the certified values in the samples.     

Holmium Oxide Glass Wavelength Standards

Holmium oxide glass has been used as a wavelength standard for over four decades. These standards have shown insignificant spectral variation from batch to batch and from one manufacturer to another. The National Institute of Standards and Technology (NIST) has certified and recertified holmium oxide glass samples for over four decades. Over this period of time there has been no recorded instance of a spectral shift of the certified bands for any of the samples measured. Moreover, these samples are known to be robust and relatively insensitive to a normal range of temperature and humidity. Based on the extensive experience that NIST has with this material and its long-term stability, NIST will no longer recommend the recertification of these standards. Furthermore, traceability may be established either through the supplier or by the end user without the need for NIST involvement.     

Elemental analysis of organic species with electron ionization high-resolution mass spectrometry

We present a new elemental analysis (EA) technique for organic species (CHNO) that allows fast on-line analysis (10 s) and reduces the required sample size to approximately 1 ng, approximately 6 orders of magnitude less than standard techniques. The composition of the analyzed samples is approximated by the average elemental composition of the ions from high-resolution electron ionization (EI) mass spectra. EA of organic species can be performed on organic/inorganic mixtures. Elemental ratios for the total organic mass, such as oxygen/carbon (O/C), hydrogen/carbon (H/C), and nitrogen/carbon (N/C), in addition to the organic mass to organic carbon ratio (OM/OC), can be determined. As deviations between the molecular and the ionic composition can appear due to chemical influences on the ion fragmentation processes, the method was evaluated and calibrated using spectra from 20 compounds from the NIST database and from 35 laboratory standards sampled with the high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). The analysis of AMS (NIST) spectra indicates that quantification of O/C is possible with an error (average absolute value of the relative error) of 30% (17%) for individual species. Precision is much better than accuracy at +/-5% in the absence of air for AMS data. AMS OM/OC has an average error of 5%. Additional calibration is recommended for types of species very different from those analyzed here. EA was applied to organic mixtures and ambient aerosols (sampled at 20 s from aircraft). The technique is also applicable to other EI-HRMS measurements such as direct injection MS.     

油页岩灰渣提取纳米α-Al_2O_3的方法研究

以油页岩为原料合成纳米α-Al2O3,采用表面活性剂超声辅助分散制备氢氧化铝前躯体,再用共沸蒸馏干燥的综合处理制备超细纳米氧化铝,并以共沸蒸馏法干燥,用XRD、TEM、BET进行分析,用热重/差热、红外、XPS进行表征,实验结果表明,所得的纳米氧化铝分散均匀,粒径为50-80nm,表面活性剂超声结合共沸蒸馏的方法对防止前躯体硬团聚很有效。     

Comparison of spectral irradiance standards used to calibrate shortwave radiometers and spectroradiometers

Absolute calibration of spectral shortwave radiometers is usually performed with National Institute of Standards and Technology (NIST) or NIST-traceable incandescent lamps. We compare 18 irradiance standards from NIST and three commercial vendors using the same spectrometer to assess their agreement with our working standard. The NIST procedure is followed for the 1000-W FEL lamps from NIST, Optronics, and EG&G. A modified calibration procedure developed by Li-Cor is followed for their 200-W tungsten-halogen lamps. Results are reproducible from one day to the next to approximately 0.1% using the same spectrometer. Measurements taken four months apart using two similar but different spectrometers were reproducible to 0.5%. The comparisons suggest that even NIST standards may disagree with each other beyond their stated accuracy. Some of the 1000-W commercial lamps agreed with the NIST lamps to within their stated accuracy, but not all. Surprisingly, the lowest-cost lamps from Li-Cor agreed much better with the NIST lamps than their stated accuracy of 4%, typically within 2%. An analysis of errors leads us to conclude that we can transfer the calibration from a standard lamp to a secondary standard lamp with approximately 1% added uncertainty. A field spectrometer was calibrated with a secondary standard, producing a responsivity for the spectrometer that was within 5% of the responsivity obtained by Langley calibration using routine field measurements.     

Determination of aniline derivatives in oils related to the toxic oil syndrome by atmospheric pressure ionization-tandem mass spectrometry

In 1981, an unknown disease appeared in Spain, the Spanish Toxic Oil Syndrome. Nowadays and despite all efforts, the etiological agent is still unknown. Early studies showed a link between this illness and the consumption of denatured rapeseed oil fraudulently processed and marketed as edible oil. Two families of aniline derivatives present in these oils (fatty acid anilides and acylated phenyl amino propanediol derivatives or PAPs) were found to be good chemical markers of toxic oils. In this work, a new method has been developed to analyze these aniline derivatives in oil samples by HPLC-MS and HPLC-MS/MS with an API source. For their quantification, three different internal standards were used, one for anilides and two for PAPs. Quantification limits were 8 ppm for anilides and 0.2 ppm for PAPs. Anilides and PAPs were found in marker-positive samples at levels up to 50,000 and 330 ppm, respectively. The relative abundance of the different fatty acid anilides and PAPs correlates with the fatty acid composition of the oils. More than 2,600 different samples were analyzed by this method in the most exhaustive screening of suspected toxic oils carried out to date.     

Water determination in drugs containing ascorbic acid.

A new rapid analytical method was applied for water determination in tablets of vitamin C, Ce De Calcium Veterinary, and C-Tamin-500 containing ascorbic acid and therefore is not amenable for direct Karl Fischer (KF) titration. The method is based on the consecutive titration first of ascorbic acid by a novel reagent and then of water by a conventional KF reagent (KFR) in the same sample and cell with the electrometric "dead-stop" location of the end point in both titrations. The new reagent consists of iodine, potassium iodide, and sodium acetate in nonaqueous medium. Estimated repeatability and accuracy of both water and ascorbic acid determination are satisfactory.