Formamide (FA), N-methylformamide (NMF), and dimethylformamide (DMF), were evaluated as solvents for coulometric Karl Fischer (KF) reagents in combination with several amine bases. Except for the effect of the iodine species (iodine or triiodide), the pH of the reagent and the position of the sulfur dioxide/hydrogen sulfite equilibrium were found to be the main factors explaining the large difference in the observed reaction rates between water and the KF reagent in these solvents. Acid–base titrations showed that hydrogen sulfite is the main sulfur reactant in these media. The results will be of great importance in finding suitable combinations of base and solvent with respect to stoichiometry, side reactions caused by active carbonyl compounds, and reagent stability.

ABSTRACT This study examined older adults' (≥ 55 years of age) perceived social health benefits associated with participating in a county-wide chair volleyball program. Of the 300 individuals who had participated in the program, 222 completed a 22-item survey on their perceived social health benefits (74% response rate). Results indicated that the largest benefits were that the program provides them with a challenging activity, makes them feel like they are part of a group, and helps them make new friends. Females and those very/extremely competitive felt program participation was significantly more beneficial to their social health than did males and those somewhat/not competitive. Findings illustrate the positive effects that participation in a chair volleyball program can have on the social health of older adults.

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.

Factors influencing the accuracy and precision for diaphragm-free Karl Fischer coulometric determinations of low mug-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 100-400mA) 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 100mA 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.

The efficiency of azeotropic 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 (greater than or equal to65%), 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.

Different designs of a semiopen, drainable cathode compartment of a medium-sized coulometric Karl Fischer (KF) cell for the determination of water in the range 0.1-500 microg were evaluated. The main criterion for the design was to keep the resistance between the anolyte and catholyte low enough to permit the generation of currents larger than 20 mA (for an output voltage of 28 V). It was found that a good compromise between the size of this current and a minimal influence from diffusing/migrating oxidizable reduction products from the catholyte was achieved by means of an interface having a channel length and diameter of 8 and 2.1 mm, respectively (catholyte volume, approximately 1 mL). To show the general applicability of the concept, the following different types of coulometric reagents suitable for nonpolar and polar samples, as well as for samples containing active carbonyl compounds, were investigated: Hydranal Coulomat A, AD, AK, AG-H (modified with chloroform, Merck), and two homemade methanolic reagents modified with 40% (v/v) chloroform and 50% (v/v) formamide, respectively. Except for Hydranal Coulomat A, the mean value of five consecutive titrations of 50 microg water did not deviate by more than 0.2% from the expected value for all reagents. Draining after every titration was sufficient to obtain accurate results, even for Coulomat A which, when used in the commercial diaphragm-free system of Metrohm, gave values which were about 10% too high. As compared to earlier reported results for diaphragm-free coulometry, the descibed modified cell represents a significant improvement, mainly because of the high accuracy achieved for all types of reagents.

Factors influencing the accuracy of water determinations using diaphragm-free, pulsed current Karl Fischer (KF) coulometry were investigated with the new Metrohm 756 instrument. Results obtained with commercially available reagents from Riedel-deHaën and Merck were compared with home-made ones that were especially designed to minimize the formation of iodine-consuming reduction products generated in the cathode reaction. Positive errors in the range 2–5% were found for the commercial reagents as compared to 0.2–1% for the home-made ones which were buffered at about pH 10 containing modifiers like chloroform, hexanol or ethylene glycol. Except for the composition of the KF-reagent, the cathode current density and the titration rate were found to be critical parameters for the accuracy of the determinations. For all reagents investigated, the best results were obtained for the maximum generator current 400 mA (corresponding to a current density of 1400 mA cm–2) in combination with a maximum titration rate of 2000 μg min–1. Surprisingly, the errors found under optimum conditions for the pulse technique were always somewhat larger than the corresponding values obtained with continuous coulometry.

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.

A flexible instrument was designed in order to investigate the influence of current magnitude, current duration and the frequency of the pulse generation on the error obtained in coulometric Karl Fischer titrations carried out in diaphragm-free cells. For a given current magnitude the lowest errors were obtained for current durations more than 60% of the total time for the pulse cycle. No significant influence of the pulse frequency (5–1000 Hz) was found independently of the pulse current duration for three different types of reagents intended for diaphragm-free coulometry. For all reagents, the errors obtained with the home-built instrument were significantly smaller than those obtained with an optimized commercial titrator based on pulsed current generation. Using optimum conditions for the former instrument, in combination with an imidazole-buffered reagent at pH 10 containing chloroform as modifier, the accuracy was close to 100%. Thus, it is now possible to achieve the same high accuracy with diaphragm-free coulometry as with the conventional diaphragm based technique. The precision of the water determinations was affected by the size of the background.

Factors influencing the extent of formation of oxidizable reduction products in coulometric cells used for Karl Fischer (KF) determination of water were investigated. For methanolic KF reagents buffered with imidazole (Im) or diethanolamine (DEA) (separately or in combination), three parameters were found to be of outmost importance: the cathodic current density, the pH, and the concentration of protonated base (ImH+ or DEAH+). For reagents buffered with only Im, the relative formation of oxidizable reduction products varied in the range 2-40%; i.e., 51-70 micrograms of water was found for a 50 micrograms water sample, depending on the above-mentioned parameters. The lowest values were observed for reagents having a pH around 10 in combination with cathodic current densities in the range 2000-5000 mA cm-2. For all the Imbuffered reagents investigated, the addition of modifiers such as chloroform, hexanol, and carbon tetrachloride was found to decrease the formation of oxidizable reduction products significantly. For example, a reagent buffered at pH 10 containing 1 M hexanol gave less than 0.3% formation in the current density interval from 200 to 4000 mA cm-2. The best reagents based on the above-mentioned modifiers were tested in the continuous coulometric mode with errors typically in the interval 0-0.5% using optimum conditions. One prerequisite for obtaining such small errors with diaphragm-free continuous coulometry is to use a cathode area no larger than 0.002 cm2. For some of the reagents based on both Im and DEA, the formation of oxidizable reduction products was close to zero at certain current densities, although the analytical performance was not as good as for the reagents buffered solely by Im due to longer conditioning and titration times.

A new approach to the use of the Karl Fischer (KF) reagent is presented. The method is based on direct potentiometry (zero current) using spent KF reagents and a platinum wire as indicating electrode. A large number of imidazole-buffered methanolic reagents were investigated; the most promising one was based on a 3:1 mixture of chloroform: methanol containing 2 M imidazole/0.2 M sulfur dioxide/0.1-0.2 M iodide/0.5 M trichloroacetic acid. For this reagent, the slope of the calibration curve, -log [H2O] versus the redox potential, was found to be strictly linear in the interval 10(-3)-1 M water, with a typical regression coefficient of 0.9999. For calibrations carried out in the interval 10(-3)-1 M, the standard deviation of the slope values, for three additions of water for each calibration curve, obtained at eight different occasions (i.e., n = 24), using two different types of cells, was 1.5 mV, with a mean slope value of 37.5 mV, A lower working range, 10(-4)-10(-3) M water, could also be used for analytical purposes, although the slope of the calibration curve in this interval was only about 30 mV/decade, The response time, i.e., the time required to reach the drift level, was, for this reagent, relatively short (2-20 s), The most rapid response was obtained for larger concentrations of water. The drift in the potential readings was typically about 0.1 mV min(-1) for the reagent mixture described above. Since the method operates at extremely low iodine concentrations, 10(-8)-10(-13) M, the possibilities of achieving discrimination between the water reaction and some iodine-consuming interferences such as sodium tetraborate, cyclohexanone and a penicillin were investigated. A procedure is described which shows that the large positive error caused by sodium tetraborate under normal KF-conditions could be almost completely eliminated by means of a simple graphic evaluation of the potentiometric response curve obtained in the interval 10(-3) M to 10(-2) M of water.

A flexible computer-controlled coulometric Karl Fischer system based on zero-current potentiometry is described. A negligible influence of the generating current on the potentiometric signal is indicated by the low noise level of the system. For example, the noise in the background observed at an iodine end-point concentration of 5 x 10(-5) M using a current amplification factor of 181 mu A (generating current)/mV (deviation between measured and preset potential) was about 5 mu A(peak-to-peak). For a 1-min titration, this corresponds to a maximum error in the evaluation of the current/time integral of about +/-0.01 mu g calculated as water. The accuracy of the system was tested using a standard water-in-methanol solution, and no significant difference was found between the predicted and experimentally found values, Trace determination of water in a mineral oil was used to illustrate the high sensitivity of the described system.