Sensitizers thiocyanates

A sensitive and selective method based on the use of Arsenazo HI, a moderately sensitive method involving benzoylmethane, and a low-sensitivity thiocyanate method are described below. 

Phosphates, arsenates, oxalates, tartrates, and other organic hydroxyl compounds, fluorides, and many compounds which give stable complex salts with iron III, can, according to the proportion present, so reduce the concentration of ferric ions that the ionic product necessary for the color reaction is not reached. Even considerable amounts of iron may then fail to be detected by the sensitive thiocyanate reaction. The same interference occurs when great amounts of mercury salts are present because they form slightly dissociated mercuric thiocyanate or double thiocyanates, e.g. Ka[Hg(CNS)J, and thus consume the thiocyanate ions. 

The a-thiocyanatoketones are easily obtainable from a-halocarbonyl compounds and metal thiocyanates (sodium, potassium, barium, or lead thiocyanate) (416, 484, 519, 659) in an alcoholic solution. Yields ranged from 80 to 95%. They are very sensitive substances that isomerize when reacted upon by acids, bases, or labile hydrogen and sulfur compounds. 

Lesser amounts of sodium thiocyanate are used in color toning photographic paper, as a stabilizer in rapid film development, and as a sensitizing agent in color negative-film emulsions. It is also used as a brightener in copper electroplating. 

The main chemico-analytical properties of the designed ionoselective electrodes have been determined. The work pH range of the electrodes is 1 to 5. The steepness of the electrode function is close to the idealized one calculated for two-charged ions (26-29 mV/pC). The electrode function have been established in the concentration range from 0.1 to 0.00001 mole/1. The principal advantage of such electrodes is the fact that thiocyanate ions are simultaneously both complexing ligands and the ionic power. The sensitivity (the discovery limits), selectivity (coefficient of selectivity) and the influence of the main temporal factors (drift of a potential, time of the response, lifetime of the membranes) were determined for these electrodes. 

The use of potassium hydrogen carbonate for the cyclization of thiocyan-atohydrin mesylates containing alkali-sensitive groups has been reported, but the selectivity for thiirane formation is reduced. ... 

The pyrotechnic literature does not contain a critical evaluation of the ignition response time. of primary initiators in terms of their compn, temp tolerance and shock sensitivity. In general, primary expls such as Pb Azide or styphnate are selected whenever a brief (microsecond) response is desired, while, for instance, Pb thiocyanate-chlorate mixts are selected when high temps and high radiation environments are encountered, and presumably a longer ignition delay is the price which is paid for the extra margin of safety... 

Figure 14 also demonstrates the principle that sometimes extraction into an organic solvent increases the intensity of the color. This is true, for example, for ferric thiocyanate, where extraction into an organic solvent will increase the sensitivity of iron determination to that obtainable with the phenanthrolines. The advantage of the iron ferric thiocyanate method in organic solvents is the fact that it is insensitive to pH changes, which is not true for the phenanthroline procedures (19). 

The concentration of an oxidative gel breaker can be measured by colorimetric methods, by periodically or continuously sampling the gel [341]. The colorimetric reagent is sensitive to oxidizing agents. It contains iron ions and thiocyanate. Thus the quantity of breaker added to the fracturing fluid can be controlled. 

Cyanide and thiocyanate anions in aqueous solution can be determined as cyanogen bromide after reaction with bromine [686]. The thiocyanate anion can be quantitatively determined in the presence of cyanide by adding an excess of formaldehyde solution to the sample, which converts the cyanide ion to the unreactive cyanohydrin. The detection limits for the cyanide and thiocyanate anions were less than 0.01 ppm with an electron-capture detector. Iodine in acid solution reacts with acetone to form monoiodoacetone, which can be detected at high sensitivity with an electron-capture detector [687]. The reaction is specific for iodine, iodide being determined after oxidation with iodate. The nitrate anion can be determined in aqueous solution after conversion to nitrobenzene by reaction with benzene in the presence of sulfuric acid [688,689]. The detection limit for the nitrate anion was less than 0.1 ppm. The nitrite anion can be determined after oxidation to nitrate with potassium permanganate. Nitrite can be determined directly by alkylation with an alkaline solution of pentafluorobenzyl bromide [690]. The yield of derivative was about 80t.with a detection limit of 0.46 ng in 0.1 ml of aqueous sample. Pentafluorobenzyl p-toluenesulfonate has been used to derivatize carboxylate and phenolate anions and to simultaneously derivatize bromide, iodide, cyanide, thiocyanate, nitrite, nitrate and sulfide in a two-phase system using tetrapentylammonium cWoride as a phase transfer catalyst [691]. Detection limits wer Hi the ppm range. 

Mixtures of thiocyanates with chlorates (or nitrates) are friction- and heat-sensitive, and explode on rubbing, heating to 400°C, or initiation by spark or flame [1]. A violent explosion occurred when a little chlorate was ground in a mortar contaminated with ammonium thiocyanate. A similar larger-scale explosion involving traces of barium thiocyanate is also described [2],... 

Acrylonitrile metabolites have been measured in blood and urine, but, except for measurement of thiocyanate, these methods have not been developed for routine monitoring of exposed humans. Supercritical fluid extraction/chromatography and immunoassay analysis are two areas of intense current activity from which substantial advances in the determination of acrylonitrile and its metabolites in biological samples can be anticipated. The two techniques are complementary because supercritical fluid extraction is especially promising for the removal of analytes from sample material and immunoassay is very analyte-selective and sensitive (Vanderlaan et al. 1988). 

In a method described by Kiriyama and Kuroda [500], molybdenum is sorbed strongly on Amberlite CG 400 (Cl form) at pH 3 from seawater containing ascorbic acid, and is easily eluted with 6 M nitric acid. Molybdenum in the effluent can be determined spectrophotometrically with potassium thiocyanate and stannous chloride. The combined method allows selective and sensitive determination of traces of molybdenum in seawater. The precision of the method is 2% at a molybdenum level of 10 xg/l. To evaluate the feasibility of this method, Kiriyama and Kuroda [500] spiked a known amount of molybdenum and analysed it by this procedure. The recoveries for 4 to 8 xg molybdenum added to 500 or 1000 ml samples were between 90 and 100%. 

The ability of vanadium(II) chloride to facilitate sulfoxide deoxygenation has been discussed (Section IV,C), and it appears that vana-dium(III) sulfoxide complexes may be prepared by air oxidation of van-adium(II) salts in the presence of the sulfoxide. In this manner, [V(Me2S0)6][C104]3 was prepared from vanadium(II) perchlorate (119) and the kinetics of substitution with thiocyanate ion detailed. Care is necessary in handling the pure compound, as it is reported to be sensitive to detonation. A large number of oxovanadium(IV) species have... 

The nervous system is the most sensitive target for cyanide toxicity, partly because of its high metabolic demands. High doses of cyanide can result in death via central nervous system effects, which can cause respiratory arrest. In humans, chronic low-level cyanide exposure through cassava consumption (and possibly through tobacco smoke inhalation) has been associated with tropical neuropathy, tobacco amblyopia, and Leber s hereditary optic atrophy. It has been suggested that defects in the metabolic conversion of cyanide to thiocyanate, as well as nutritional deficiencies of protein and vitamin B12 and other vitamins and minerals may play a role in the development of these disorders (Wilson 1965). 

Methods for Determining Biomarkers of Exposure and Effect. Besides environmental exposure, exposure to cyanide can also occur from consumption of cyanide-containing food, metabolism of certain drugs, and smoking cigarettes. Since so many factors can influence cyanide exposure, the exact correlation between cyanide concentrations in the body and its level in the environment has not been made. Therefore, measuring cyanide and/or thiocyanate levels in blood and urine cannot be used as a biomarker for exposure to low cyanide concentrations. Analytical methods of required sensitivity and reliability to detect cyanide and thiocyanate in blood, plasma, and urine of both unexposed and exposed persons are available (see Table 6-1 and Table 6-3). Further studies determining biomarkers for exposure to low cyanide concentrations would be useful. 

Photoindnced electron transfer in the presence of a sensitizer (9,10-diphenylanthracene) also generates the same anion-radical. However, its disintegration proceeds within the solvent (acetonitrile) cage. Inside the cage, the 4-nitrobenzyl radical and thiocyanate ion unite anew, but in this case, by their soft-to-soft ends. This nucleophilic reaction takes place faster than the back electron transfer does. The final, stable product of the whole process is 4-nitrobenzyl- o-thiocyanate (Wakamatsu et al. 2000) ... 

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