Determination of the analytical performance of a headspace capillary gas chromatographic technique and karl Fischer coulometric titration by system calibration using oil samples containing known amounts of moisture

Over the past few years, concerns have been raised in the literature about the accuracy of the Karl Fischer (KF) method for assessing moisture in transformer mineral oils. To better understand this issue, the performance of a static headspace capillary gas chromatographic (HS-CGC) technique was compared to that of KF coulometric titration by analyzing moisture in samples containing known amounts of water and various samples obtained from the National Institute of Standards and Technology (NIST). Two modes of adding samples into the KF vessel were used: direct injection and indirect injection via an azeotropic distillation of the moisture with toluene. Under the conditions used for direct injection, the oil matrix was totally dissolved in the anolyte, which allowed the moisture to be titrated in a single-phase solution rather than in a suspension. The results have shown that when HS-CGC and combined azeotropic distillation/KF titration are calibrated with moisture-in-oil standards, a linear relation is observed over 0-60 ppm H(2)O with a correlation coefficient better than 0.9994 (95% confidence), with the regression line crossing through zero. A similar relation can also be observed when calibration is achieved by direct KF addition of standards prepared with octanol-1, but in this case an intercept of 4-5 ppm is noted. The amount of moisture determined by curve interpolation in NIST reference materials by the three calibrated systems ranges from 13.0 to 14.8 ppm for RM 8506 and 42.5 to 46.4 ppm for RM 8507, and in any case, the results were as high as those reported in the literature with volumetric KF titration. However, titration of various dehydrated oil and solvent samples showed that direct KF titration is affected by a small bias when samples contain very little moisture. The source of error after correction for the large sample volume used for the determination (8 mL) is about 6 ppm for Voltesso naphthenic oil and 4 ppm for toluene, revealing a matrix effect on the measurement. Finally, the results revealed that HS-CGC is a good technique for measuring moisture in oil samples and that the use of azeotropic vapors for introducing moisture into the titrator almost completely eliminates the matrix effect observed with the oil components. Direct KF injection could also be used provided the system is calibrated with moisture-in-oil standards prepared in the same matrix which is to be used for the determination.     

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.     

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.     

Source of the Difference between the Measurement of Water in Hydrocarbons As Determined by the Volumetric and Coulometric Karl Fischer Methods

The disparity between the volumetric and coulometric Karl Fischer methods for the measurement of water in hydrocarbons and hydrocarbon mixtures (oils) has been resolved. The amount of water detected by the volumetric method when the titration vessel solution is homogeneous is higher than that measured coulometrically or volumetrically when the titration vessel solution is heterogeneous. Water in oil that is not measured by the coulometric method when the oil is incompletely dissolved has been shown to reside in the oil phase of the heterogeneous (multiphasic) coulometric vessel suspension. Water that is not measured volumetrically under relatively low chloroform concentrations after the point of transition to a heterogeneous titration vessel solution is reached also appears to reside in the nonaqueous phase of the titration vessel solution. It appears that this water is retained in the hydrocarbon phase in a manner such that it is completely inaccessible to the volumetric or coulometric Karl Fischer reagents.     

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.     

Silicon lattice comparisons related to the Avogadro project:uniformity of new material and surface preparation effects

New high-quality silicon has been produced by Wacker Siltronics as potential starting material for a precision determination of the Avogadro constant, N_A. An assessment of the uniformity of this material is an essential first step in determining whether this material is of sufficient quality to be used in this project. We have made extensive measurements to determine lattice parameter uniformity of several regions of this new material using the NIST lattice comparator. Measurements from this comparator have been shown to have a relative internal consistency near 1×10^-8. In the course of these measurements we noted a significant dependence of lattice parameter values on surface preparation of the samples. Samples prepared by grinding followed by chemical-mechanical (C-M) polishing show a wider distribution than samples prepared by grinding followed by etching. Surface preparation procedures were altered to include etching after C-M polishing. This unexpected dependence on surface preparation raises the possibility that some of the NIST lattice comparison results presented at CPEM96 may be biased by surface preparation effects. To test this possibility, some of the samples included in our CPEM96 contribution have been etched and remeasured. Preliminary estimates of corrections to some NIST CPEM96 lattice comparison results appear to confirm that bias     

Round Robin for Optical Fiber Bragg Grating Metrology

NIST has administered the first round robin of measurements for optical fiber Bragg gratings. We compared the measurement of center wavelength, bandwidth, isolation, minimum relative transmittance, and relative group delay among several grating types in two industry groups, telecommunications and sensors. We found that the state of fiber Bragg grating metrology needs improvement in most areas. Specifically, when tunable lasers are used a filter is needed to remove broadband emissions from the laser. The linear slope of relative group delay measurements is sensitive to drift and systematic bias in the rf-modulation technique. The center wavelength measurement had a range of about 27 pm in the sensors group and is not adequate to support long-term structural monitoring applications.     

A Summary of Heat-Flux Sensor Calibration Data

This paper presents a statistical evaluation of the responsivity data on a number of heat-flux sensors, calibrated using an electrical substitution radiometer as a transfer standard up to 5 W·cm⁻². The sensors, furnished by the customers, were of circular-foil or thermopile type. Comparison of the NIST and the customer measured responsivity values showed that the measurements agree within 3 % for more than half the number of sensors tested, so far. Considering the variation in the customer calibration techniques and the wide measuring range of the sensors used in the calibration, the agreement is encouraging.     

Moisture content estimation in paper pulp using fringing field impedance spectroscopy

Currently used methods for estimation of moisture content in paper pulp are restricted to levels of moisture concentration below 90%. Some of the existing methods require less practical double-sided contact measurements. A few other methods make restrictive assumptions, such as the constituents of the pulp that determine its conductance. This paper presents a technique that uses fringing field interdigital sensors to measure moisture concentration in paper pulp at levels as high as 96%. The method proposed in this paper uses single-sided measurements, offers high sensitivity, and does not require special operating conditions. The accuracy of the proposed method is also demonstrated. The repeatability and reproducibility of the sensor measurements are also shown.     

Scene-based nonuniformity correction for focal plane arrays by the method of the inverse covariance form

What is to our knowledge a new scene-based algorithm for nonuniformity correction in infrared focal-plane array sensors has been developed. The technique is based on the inverse covariance form of the Kalman filter (KF), which has been reported previously and used in estimating the gain and bias of each detector in the array from scene data. The gain and the bias of each detector in the focal-plane array are assumed constant within a given sequence of frames, corresponding to a certain time and operational conditions, but they are allowed to randomly drift from one sequence to another following a discrete-time Gauss-Markov process. The inverse covariance form filter estimates the gain and the bias of each detector in the focal-plane array and optimally updates them as they drift in time. The estimation is performed with considerably higher computational efficiency than the equivalent KF. The ability of the algorithm in compensating for fixed-pattern noise in infrared imagery and in reducing the computational complexity is demonstrated by use of both simulated and real data.     

Determination of serum uric acid by isotope dilution mass spectrometry as a new candidate definitive method

A new isotope dilution mass spectrometric method for uric acid is described. A known weight of [1,3-15N2]uric acid is added to a known weight of serum, and the mixture is allowed to equillibrate. The serum is put through an anion-exchange resin, and the isolated uric acid is converted to the tetrakis-(tert-butyldlmethylsilyl) derivative of uric acid. For measurement, the derivative is injected into a gas chromatograph interfaced with a low-resolution, magnetic sector mass spectrometer. Isotope ratio measurements are made from the abundances of the [M - tert-butyl]+ ions at m/z 567 and 569. Bias is investigated by measuring the uric acid level in the same samples under different chromatographic conditions and with different ionization techniques. If these confirmatory measurements agree with the principal measurements, we have strong evidence for the absence of measurement bias. Uric acid was determined in three lyophilized human serum pools by this method. For Standard Reference Material (SRM) 909, four sets of six samples each were prepared. For Candidate SRM 909a, which consisted of two pools, each with a different level of uric acid, six sets of two samples of each level were prepared. The coefficient of variation for a single measurement ranged from 0.34% to 0.42%, while the relative standard error of the mean ranged from 0.08% to 0.14%. The results from the confirmatory measurements demonstrated that there was no significant bias in the measurements. The combination of high precision and absence of significant bias in the results qualifies this method as a candidate definitive method as defined by the National Committee for Clinical Laboratory Standards.     

Effects of Sample Handling and Transportation on the Moisture Content of Biomass Samples

Using biomass in energy production has a significant role in the progress toward carbon neutrality in Finland. In the biomass combustion process, moisture content is an important factor. To enhance efforts for well-quantified uncertainty estimations in reference moisture measurements for biomass, errors related to handling and transporting samples were studied in this work. At the Centre for metrology of VTT Technical Research Centre of Finland, experiments and simulations were carried out on effects of water mass gain and loss when forest biomass samples are transported to a laboratory and prepared for moisture analysis. Results suggest that opening the sample bag may change bulk moisture content considerably and homogenization of the sample with varying moisture contents inside sample bags typically takes weeks. Results with varying thermal conditions show that the moisture content changes in the tested samples were insignificant. Monitoring the masses of samples and sample containers separately is recommended when aiming at high accuracy in the analysis of hygroscopic samples.     

Tracer monitored titrations: measurement of total alkalinity

We introduce a new titration methodology, tracer monitored titration (TMT), in which analyses are free of volumetric and gravimetric measurements and insensitive to pump precision and reproducibility. Spectrophotometric monitoring of titrant dilution, rather than volume increment, lays the burden of analytical performance solely on the spectrophotometer. In the method described here, the titrant is a standardized mixture of acid-base indicator and strong acid. Dilution of a pulse of titrant in a titration vessel is tracked using the total indicator concentration measured spectrophotometrically. The concentrations of reacted and unreacted indicator species, derived from Beer's law, are used to calculate the relative proportions of titrant and sample in addition to the equilibrium position (pH) of the titration mixture. Because the method does not require volumetric or gravimetric additions of titrant, simple low-precision pumps can be used. Here, we demonstrate application of TMT for analysis of total alkalinity (A(T)). High-precision, high-accuracy seawater A(T) measurements are crucial for understanding, for example, the marine CaCO3 budget and saturation state, anthropogenic CO2 penetration into the oceans, calcareous phytoplankton blooms, and coral reef dynamics. We present data from 286 titrations on three types of total alkalinity standards: Na2CO3 in 0.7 mol kg x soln(-1) NaCl, NaOH in 0.7 mol kg x soln(-1) NaCl, and a seawater Certified Reference Material (CRM). Based on Na2CO3 standards, the accuracy and precision are +/-0.2 and +/-0.1% (4 and 2 micromol kg x soln(-1) for A(T) approximately 2100-2500 micromol kg x soln(-1), n = 242), using low-precision solenoid pumps to introduce sample and titrant. Similar accuracy and precision were found for analyses run 42 days after the initial experiments. Excellent performance is achieved by optimizing the spectrophotometric detection system and relying upon basic chemical thermodynamics for calculating the equivalence point. Although applied to acid-base titrations in this paper, the approach should be generally applicable to other types of titrations.     

Simulating moisture distribution within concrete pavement slabs: model development and sensitivity study

This study simulates internal relative humidity (RH) distributions for in-service jointed plain concrete pavement slabs. A one-dimensional isothermal mass transport model is used to predict the concrete slab’s RH distribution through its depth. At the top of the slab, a new statistical algorithm is applied to estimate the occurrences of drying and wetting cycles. During drying cycles, both local wind speed and ambient RH govern the slab surface’s moisture convection. During the wetting cycle, the moisture at the surface is treated as a fixed saturated condition. The feasibility of this model is verified through laboratory observations of internal RH in concrete prisms as well as through field measurements of internal RH for an in-service concrete pavement. Using the developed model, predictions of internal RH distributions of in-service slabs are centered on their sensitivity to local weather conditions, including factors such as the ambient RH, wind speed, and rainfall, especially for slabs in arid regions.     

Moisture content of polyethylene coated solid fibreboard after industrial lamination

Solid fibreboard is used mainly in highly demanding packaging applications. One solid fibreboard quality having six paper and paperboard layers, a thickness of 1.7 mm and polyethylene coating was studied. Several material tests on liquid water and water vapour penetration were done to assess the environmental moisture sources that change the material moisture content after the lamination process. The in‐plane diffusion coefficient of the combined board was determined based on an integrated unsteady state moisture transport equation and moisture sorption measurements. The transverse diffusion coefficient of the polyethylene coated kraft paper and the solid fibreboard medium were based on water vapour transmission rate measurements. The original moisture content of the solid fibreboard sheet was measured gravimetrically 2 days after the lamination at the mill. The results show that high relative humidity (RH) conditions during the transportation (4°C/90% RH) change the moisture content of the transportation box made from a solid fibreboard sheet very little in 8 days. Local moister (or drier) areas are created near the sheet edges due to in‐plane moisture transport through open material edges. The in‐plane diffusivity for the solid fibreboard grade in question was 5.87 × 10^?10 m²/s. Copyright © 2011 John Wiley & Sons, Ltd.     

Accurate determination of the mean relative humidity in controlled climates at high humidities (new method)

The measurement of the relative humidity (RH) at high levels to the desired accuracy is still a problem, especially for levels above 90% RH. The reasons for this are:

• i The accuracy of the standard apparatus is lower at high RH than at moderate and low RH;
• ii The need for accurate measurement of the RH in moisture controlled rooms is greater at high RH than at lower RH, because for moisture sensitive products, such as fibreboard boxes and certain horticultural products, the influence of a minor deviation in RH on the properties of these products is considerably greater at high RH than at moderate and low RH.

     

Effects of laboratory procedures on soil electrical propertymeasurements

Laboratory measurements of electrical properties of soils were conducted using coaxial, waveguide, and free-space techniques. Results demonstrate that sample preparation can be a significant factor, and that extrapolation of data collected over a limited frequency range should be undertaken cautiously. The importance of both volumetric moisture and soil density in determining soil electrical properties is discussed. Further research is indicated to ascertain the mechanisms relating soil density and its electromagnetic response     

Effect of humidity on nanoparticle-based chemiresistors: a comparison between synthetic and real-world samples

Chemiresistors based on metal monolayer-capped nanoparticles (MCNPs) are promising candidates for fast, inexpensive, and portable tracing of (bio)chemical species in the gas phase. However, the sensitivity of such sensors to humidity is problematic, limiting their reliable and reproducible application in real-world environmental conditions. In this work, we employed a compensation method to explore the effect of humidity on a single MCNP chemiresistor as well as on an array of MCNP sensors used to analyze either synthetic or real-world samples. We show that an array of MCNP chemiresistors is able to precisely detect and estimate subtle concentrations of (mixtures of) volatile organic compounds (VOCs) under variable backgrounds of 2-83% relative humidity (RH) only after humidity compensation. Humidity effects were also tested in two clinical trials aimed at detecting prostate cancer and breast cancer through exhaled breath analysis. Analysis of the results showed improved cancer detection capabilities as a result of RH compensation, though less substantial than the impact of RH compensation on synthetic samples. This outcome is attributed to one - or a combination - of the following effects: (i) the RH variance was smaller in the breath samples than that in the synthetic samples; (ii) the VOC composition in the breath samples is less controlled than the synthetic samples; and (iii) the responses to small polar VOCs and water are not necessarily additive in breath samples. Ultimately, the results presented here could assist the development of a cost-effective, low-power method for widespread detection of VOCs in real-world applications, such as breath analysis, as well as for environmental, security, and food applications.     

Fourier Analysis of Time-Stamped Signals Using a Small Number of Samples

This paper concerns the Fourier analysis of measurements taken at times that are not at all uniformly spaced yet are accurately known. Such can be the case when measurements are obtained by networked sensors with accurate or synchronized clocks using common Internet Protocol networks or other networks that do not guarantee timely data delivery. Such can also be the case when the object being measured is only sporadically available for measurement. A method for computing a complex spectrum from a minimal number of samples taken at nonuniform time intervals is described. The novelty of this paper lies in the method's ability to minimize the number of samples required to ensure a desired accuracy. A practical application of the method lies in doing spectral analysis of signals obtained from networked sensors where acquiring each sample is expensive in time, power, or money, and so, the number of samples taken is to be minimized. The method has been tested on two rather different sets of actual measurements: one taken via smart sensors connected to the Internet and the other taken by a number of observational astronomers using a variety of apparatus over decades.