Assessment and assurance of quality in water measurement by coulometric Karl Fischer titration of petroleum products

The precise and accurate determination of water in petroleum products—gasoline, diesel oil and aromatic hydrocarbons—is of significant importance for their normal functional and operational characteristics for economics as well as in meeting international requirements. The standard method ISO 12937 for the measurement of water by the coulometric Karl Fischer titration method was subject to within-laboratory assessment. Thereby it was established that the analytical procedure could not always be relied upon, especially when low levels of water were determined. The aim of this work is to assess each stage of the test procedure depending on the particular problems defined by the samples, using high-reactive Karl Fischer reagents and coulometric cells with and without a diaphragm, and to indicate the major factors causing the uncertainty. A reduced combined uncertainty was achieved by modifying the sample preparation step, the administration of the moisture in the coulometric cell, and sample injection manipulation. Experiments showed that the cell without the diaphragm ensures lower and uniform uncertainty of the measurements in the range of 0.01 to 10 mg H₂O in comparison to the cell with a diaphragm and therefore is more appropriate for the determination of low water levels in the petroleum products. A procedure that utilized a mixture of the reagent and toluene (10:6) was able to resolve the problem of two phases of formation and reduced conductivity of the reagent in direct titration of diesel oils. The results suggest that the modified procedure ensures relative expanded uncertainty equal to or less than 2.0% (n=5, confidence interval close to 95%) and 99.4% recovery for petroleum products investigated in repeatability conditions.     

Determination of the water content of amphiphilic liquid crystals by coulometric Karl Fischer titration

An apparatus is described, which allows the precise determination of the water content of amphiphilic liquid crystals by means of coulometric Karl Fischer titration. The scope and limitations of this method are described.     

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.     

Comparison of standards in the Karl Fischer method for water determination.

The use of 4-(5-nonyl)pyridine oxide and trioctylamine oxide for the extraction of niobium(V) from different mineral acid solutions is described. The influence of the concentration of the solvents, acids and salting-out agents is discussed. Separations of niobium(V) from tantalum(V) and zirconium(IV) have been achieved.     

Interference-free coulometric titration of water in lithium bis(oxalato)borate using Karl Fischer reagents based on N-methylformamide

A non-alcoholic coulometric reagent based on N-methylformamide (NMF) was shown to eliminate the severe interference effect caused by the alcohol component of the conventional Karl Fischer (KF) reagent on the battery electrolyte lithium bis(oxalato)borate (LiBOB). For sample amounts up to 240 μg of water, the stoichiometry of the KF reaction deviated only slightly from the ideal 1:1 ratio for the best reagent composition. Both solid and dissolved (in acetonitrile, tetrahydrofuran (THF), and ethylene carbonate/ethyl methyl carbonate) LiBOB were titrated successfully using a Metrohm 756 KF Coulometer with a diaphragm cell. The detection limit was estimated to be 0.5-1 μg of water using 100 ml of reagent in this system.     

Prerequisites for attaining 1:1 stoichiometry between water and iodine using dimethylformamide as solvent in coulometric Karl Fischer titrations

Summary Conditions for attaining 1:1 stoichiometry between water and iodine in a non-alcoholic, dimethylformamide-based Karl Fischer reagent have been investigated. It has been made clear that the stoichiometric ratio is determined by the rate of the main KF-reaction consuming iodine, in relation to the rate of the side reaction between water and sulphur trioxide, which is a reaction product of the KF-reaction. The rate constants for these reactions were determined to be 9.8±0.6 M^–2s^–1 and 0.072±0.007 M^–1s^–1, respectively. It is shown theoretically as well as experimentally by means of coulometric titrations that the attainment of a 1:1 stoichiometric ratio requires that the titration is carried out at very high iodine concentrations.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Reaction rates between water and the Karl Fischer reagent

Reaction rates between water and the Karl Fischer reagent have been determined by potentiometric measurement for various compositions of the Karl Fischer reagent. The study has been made with an iodine complex concentration of 0.3-1.2 mM and sulphur dioxide complex at 0.01-0.5M. The concentration of excess of pyridine had no measurable effect on the rate of the main reaction. The reaction was found to be first-order with respect to iodine complex, to sulphur dioxide complex, and to water. The rate constant was (1.2+/-0.2) x 10(3) 1(2). mole(-2). sec(-1). In an ordinary titration it is therefore essential to keep the sulphur dioxide concentration high for the reaction to go to completion within a reasonable time. The extent of side-reactions was found to be independent of the iodine concentration at low concentrations. The side-reactions increased somewhat with increasing sulphur dioxide pyridine concentrations and decreased to about 60% when the temperature was lowered from 24 degrees to 7 degrees.     

Coulometric trace determination of water by using Karl Fischer reagent and potentiometric end-point detection

A new approach to the determination of water via the Karl Fischer reaction is described. Iodine is coulometrically generated and the end-point corresponding to a slight excess of iodine, is detected potentiometrically with a non-polarized platinum electrode. Samples of 1-500 mul containing 0.05-200 mug of water were analysed with a standard deviation of 0.015 mug in the range 0.05-20 mug of H(2)O. A specially constructed electrolysis cell was used in combination with an LKB 16300 Coulometric Analyzer and the time for a complete analysis was 1-4 min, depending on sample size. The reagent composition has been optimized in order to enhance the rate of the main reaction and to minimize the extent of side-reactions. Decreasing the temperature reduced the extent of side-reactions. The displacement of end-point potential on dilution was studied and a correction is discussed.     

Comparison between amperometric and true potentiometric end-point detection in the determination of water by the Karl Fischer method

A rapid and sensitive method using true potentiometric end-point detection has been developed and compared with the conventional amperometric method for Karl Fischer determination of water. The effect of the sulphur dioxide concentration on the shape of the titration curve is shown. By using kinetic data it was possible to calculate the course of titrations and make comparisons with those found experimentally. The results prove that the main reaction is the slow step, both in the amperometric and the potentiometric method. Results obtained in the standardization of the Karl Fischer reagent showed that the potentiometric method, including titration to a preselected potential, gave a standard deviation of 0.001(1) mg of water per ml, the amperometric method using extrapolation 0.002(4) mg of water per ml and the amperometric titration to a pre-selected diffusion current 0.004(7) mg of water per ml. Theories and results dealing with dilution effects are presented. The time of analysis was 1-1.5 min for the potentiometric and 4-5 min for the amperometric method using extrapolation.     

Determination of water in thiols by Karl Fischer titration

Water in thiol-containing samples may be determined by titration with Karl Fischer reagent after conversion of the thiol into a thioether. Both acrylonitrile and N-ethylmaleimide have been found to be suitable reagents.     

Certification by the Karl Fischer method of the water content in SRM 2890, Water Saturated 1-Octanol, and the analysis of associated interlaboratory bias in the measurement process

The calibration of Karl Fischer instruments and reagents and the compensation for instrumental bias are essential to the accurate measurement of trace levels of water in organic and inorganic chemicals. A stable, non-hygroscopic standard, Water Saturated Octanol, which is compatible with the Karl Fischer reagents, has been prepared. This material, Standard Reference Material (SRM) 2890, is homogeneous and is certified to contain 39.24 ± 0.85 mg water/mL (expanded uncertainty) of solution (47.3 ± 1.0 mg water/g solution, expanded uncertainty) at 21.5?°C. The solubility of water in 1-octanol has been shown to be nearly constant between 10?°C and 30?°C (i.e., within 1% of the value at 21.5?°C). The results of an interlaboratory comparison exercise illustrate the utility of SRM 2890 in assessing the accuracy and bias of Karl Fischer instruments and measurements.     

Certification by the Karl Fischer method of the water content in SRM 2890, Water Saturated 1-Octanol, and the analysis of associated interlaboratory bias in the measurement process

The calibration of Karl Fischer instruments and reagents and the compensation for instrumental bias are essential to the accurate measurement of trace levels of water in organic and inorganic chemicals. A stable, nonhygroscopic standard, Water Saturated Octanol, which is compatible with the Karl Fischer reagents, has been prepared. This material, Standard Reference Material (SRM) 2890, is homogeneous and is certified to contain 39.24 +/- 0.85 mg water/mL (expanded uncertainty) of solution (47.3 +/- 1.0 mg water/g solution, expanded uncertainty) at 21.5 degrees C. The solubility of water in -octanol has been shown to be nearly constant between 10 degrees C and 30 degrees C (i.e., within 1% of the value at 21.5 degrees C). The results of an interlaboratory comparison exercise illustrate the utility of SRM 2890 in assessing the accuracy and bias of Karl Fischer instruments and measurements.     

Coulometric Karl Fischer titration of trace water in diaphragm-free cells

Factors influencing the accuracy and precision for diaphragm-free Karl Fischer coulometric determinations of low μg-amounts of water have been studied using the Metrohm 756 (pulsed current) coulometer and eight different types of commercial coulometric reagents and some modifications of these. As in the case of diaphragm-free coulometric titration of large amounts of water, the positive errors, due to the formation of oxidizable reduction products (of sulfur dioxide) in the cathode reaction (besides hydrogen), were found to be minimized by the use of highest possible pulse current (in the range 100–400 mA) in combination with the fastest possible titration rate. Most accurate (102–103%) and precise results (typical relative standard deviation 1.8%) were obtained for reagents containing very large concentrations of imidazole in combination with the presence of modifiers like hexanol, chloroform and propylene glycol (i.e. the HYDRA-POINT reagents). Similar results were obtained when this type of reagent was mixed 60/40 with xylene according to the ASTM recommendation for water determinations in petroleum products like crude and lubricating oils. Addition of decanol to this type of reagent mixture was found to reduce the influence from the oxidative reduction products significantly. A reduction of the error from 3.6% relative to 1.6% was achieved by addition of 9% (v/v) of decanol to a 60/40 reagent mixture of HYDRA-POINT Coulometric Gen (containing hexanol as modifier) and xylene. For larger concentrations of decanol the pulse current had to be lowered to 100 mA and this might explain why no further improvement was observed. An additional attempt to minimize the interference by lowering the concentration of sulfur dioxide in the reagents gave no significant effect. However, by means of a home-built computer-controlled coulometric instrumentation based on continuous instead of pulsed current (including a large cathodic current density) it was possible to achieve recovery rates close to 100% for the best reagents investigated. The reason for this improvement is discussed.     

Reaction rates between water and some modified rapidly-reacting Karl Fischer reagents

Rate constants were determined for the reaction between water and various modified Karl Fischer reagents containing formamide, dimethylformamide or N-methylformamide. It was shown that the reaction rate can be increased by a factor of 100 by using a reagent containing 40% v/v formamide in pyridine compared to that obtained by use of the conventional methanolic reagent.     

Determination of total water content in inulin using the volumetric Karl Fischer titration

A new sample preparation method for the water content determination of inulin by volumetric Karl Fischer (KF) titration was developed and compared to the usual method of introducing the sample directly in the methanol-based working medium, modified or not by formamide (1:3, v/v) in order to increase sample solubility. In the proposed method, inulins were externally prepared by dissolving them in pure formamide (2.5:7.5, w/w). The time of analysis of the liquid/liquid reaction of the new method between the dissolved sample and the reaction medium is about 1–2 min, while the usual KF method is stopped after the 10 min delay time. The developed method permits the determination of water included in the crystals of the sample, confirmed by analysing both crystalline and amorphous inulin samples. Another advantage of this new method is its applicability for the water content determination of other polysaccharides that are not readily soluble in the working medium. Moreover, water content determination can be done by any type of volumetric KF titrator, as this proposed technique is not dependent on any additional tools such as a built-in homogeniser or a heatable titration beaker.     

Kinetics and stoichiometry in the Karl Fischer solution

The mechanisms of the Karl Fischer (K.F.) reaction are reviewed and further investigated. Both kinetic measurements of the iodine concentration and chromatographic determinations of the reaction products were performed. In alcoholic solutions mainly alkyl sulfite is oxidized, and a reaction via partial formation of sulfur trioxide is proposed. In methanol an exact 1:1 stoichiometry (H2O:I2) has been verified. In the aprotic, dipolar solvents acetonitrile, DMF and propylene carbonate HSO3- is oxidized by iodine. Based on formation and subsequent hydrolysis of base - SO3 adducts the stoichiometric factor for water is determined by type and concentration of the base, by the concentration of water and by the solvent itself. - In K.F. reagents the oxidation of SO2 by aerial oxygen to sulfate and alkyl sulfate takes place as a side reaction.     

Interlaboratory comparison study for the determination of halogenated hydrocarbons in water

Sixty laboratories of five different countries participated in a large-scale interlaboratory comparison test for the determination of halogenated hydrocarbons in water. Participants used their in-house method with 44 laboratories applying head space GC ECD analysis and 5 using liquid/liquid extraction. A set of two artificially produced samples was prepared; the halogenated hydrocarbons investigated were trichloroethylene, tetrachloroethylene, 1,1,1-trichloroethane, trichloromethane, tetrachloromethane, 1,1-dichloroethylene, dichloromethane, dibromochloromethane, bromodichloromethane, 1,2-dichloroethane and tribromomethane. The procedure of sample preparation, storage and distribution was monitored by an extensive quality assurance system including homogeneity tests, stability tests, and trend analysis of the submitted data. The analytical results submitted by the participants exhibited RSD values of up to 35% and outlier rates of up to 19%. The percentage of false positive and false negative results was at the highest 12% for selected substances. Recovery rates varying from 86% to 106% proved the correctness of the analytical results submitted by the participants and showed that the procedure developed in this study for sample preparation and distribution is well suited for the performance of large-scale interlaboratory comparison tests of halogenated hydrocarbons in water. Received: 7 December 1998 / Revised: 23 March 1999 / Accepted: 24 March 1999     

Interlaboratory comparison study for the determination of halogenated hydrocarbons in water

Sixty laboratories of five different countries participated in a large-scale interlaboratory comparison test for the determination of halogenated hydrocarbons in water. Participants used their in-house method with 44 laboratories applying head space GC ECD analysis and 5 using liquid/liquid extraction. A set of two artificially produced samples was prepared; the halogenated hydrocarbons investigated were trichloroethylene, tetrachloroethylene, 1,1,1-trichloroethane, trichloromethane, tetrachloromethane, 1,1-dichloroethylene, dichloromethane, dibromochloromethane, bromodichloromethane, 1,2-dichloroethane and tribromomethane. The procedure of sample preparation, storage and distribution was monitored by an extensive quality assurance system including homogeneity tests, stability tests, and trend analysis of the submitted data. The analytical results submitted by the participants exhibited RSD values of up to 35% and outlier rates of up to 19%. The percentage of false positive and false negative results was at the highest 12% for selected substances. Recovery rates varying from 86% to 106% proved the correctness of the analytical results submitted by the participants and showed that the procedure developed in this study for sample preparation and distribution is well suited for the performance of large-scale interlaboratory comparison tests of halogenated hydrocarbons in water.     

Application of the Karl Fischer method to the determination of the moisture content in insulating papers

Summary A modified extraction method has been developed for the determination of the moisture content of insulating papers used in condensers and transformers. The water is extracted from the paper sample with methanol continuously titrated with Karl Fischer reagent by means of the special apparatus devised. The method can advantageously be used to measure the adsorption isotherms of paper samples containing 0.05–2 % water.

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Zusammenfassung Eine modifizierte Extraktionsmethode für die Feuchtigkeitsbestimmung in Isolierpapier, wie es für Kondensatoren und Transformatoren verwendet wird, wurde ausgearbeitet. Das Wasser wird aus der Papierprobe mit Methanol extrahiert, das kontinuierlich mit Karl Fischer-Reagens in einer speziellen Apparatur titriert wird. Das Verfahren kann vorteilhaft zur Messung der Adsorptionsisothermen von Papierproben mit einem Wassergehalt von 0,05–2% verwendet werden.