Sulfur analytical determination

Analytical Methods Whole rock and LA-ICPMS analyses were carried our at Universite du Quebec a Chicoutimi (UQAC). Sulfur was determined by combustion and IR analysis. Ni and Cu were determined by atomic absorption spectrophotometry after aqua regia digestion. Gold and PGE were determined by Ni-sulfide fire assay followed by Te co-precipitation followed by ICPMS. 

Originally the FeMoco was reported to contain iron, molybdenum and sulfide in a 8 1 6 atomic ratio (2). Subsequent analytical determinations gave Fe/Mo ratios of 7 1 (3) and 8.2 0.4 1 (4). The most recent analytical data on functional FeMoco, isolated by a mild procedure, indicates (5) a Fe/Mo ratio of 5 0.5 1. A similar fluctuation in analytical results is also apparent in several determinations of sulfur content, and ratios of S/Mo as low as 4 1 (3) and as high as 9 or 8.T (4) have been reported. 

Even prior to Pasteur, alcohol content determination was important as a basis for local, import, and export taxes. Other important applications of accurate wine analysis have been to detect and to accurately determine food additives now there are legal reasons for analyzing wines for sulfur dioxide, organic chloride or bromide, sodium, cyanide, diglucoside pigments, various insecticides, fungicides, etc. Winery control calls for analytical determination of iron, copper, protein, total acidity, pH, tartaric, malic and lactic acids, etc. Finally, quality control... 

NIOBIC ACID. Any hydrated form of Nb Os. It forms as a white, insoluble precipitate when a potassium hydrogen sulfate fusion of a niobium compound is leached with hot water or when niobium fluoride solutions are treated widi ammonium hydroxide. Soluble in concentrated sulfuric acid, concentrated hydrochloric acid, hydrogen fluoride, and bases. Important in analytical determination of niobium. See also Niobium. 

Sulfur is determined as the further loss of weight on extraction with carbon disulfide in a Wilcv extractor or other suitable apparatus. After the extraction, the crucible ought to be allowed to dry in the air away from flames until all the inflammable carbon disulfide has escaped. It is then dried in the oven to constancy of weight, and the residue is taken as charcoal. Ash is determined by igniting the residue in the crucible until all carbon has burned away. A high result for ash may indicate that the water extraction during the determination of potassium nitrate was not complete. The analytical results may be calculated on a moisture-free basis for a closer approximation to the formula by which the manufacturer prepared the powder. 

Experiments were carried out with elec-tropolished Ti in sulfuric acid solution [2]. The current transients yield the overall current density i and the total charge flux at the electrode interface. Analytic determination of the corroded Ti by atomic absorbance spectroscopy (AAS) measurements yielded icon- As long as ioj can be neglected. 

A two-step approach was used for the determination of method detection and quantification limits for the sulfur analytes, as described in Lee Aizawa (2003). The two step approach takes into consideration several factors that affect the analyte signal, including instrumental noise, variability in instrumental sensitivity, and variability in method efficiency, matrix effects and interference, and is simple to follow. Other methods, such as the Hubaux-Vos approach for the calculation of the detection limit can also be used, as reported in Fedrizzi et al. (2007). However, this later approach is complicated, time consuming and does not take either the variabiUty in method efficiency or the matrix effects into consideration (Lee Aizawa, 2003). A brief discussion on how to conduct the method vahdation using the two steps approach is mentioned in this section. 

The amount or presence of sulfite in each of these states (freely, reversibly or irreversibly bound) depends on a number of factors such as the level of addition, the type and composition of the food or beverage, and the processing and storage conditions. For example, reversibly bound sulfite may dissociate into free sulfite when a food is treated with acidic solutions and heated to boiling (Fazio and Warner, 1990 Liick and Jager, 1997). On the other hand, the free sulfite fraction is rapidly converted to molecular sulfur dioxide when the sulfited food is acidified (Wedzicha, 1992). Analytical determination of sulfite does not therefore reflect the preservatives that were initially added. 

When a suitable reaction involving the analyte does not exist it may be possible to generate a species that is easily titrated. Eor example, the sulfur content of coal can be determined by using a combustion reaction to convert sulfur to sulfur dioxide. 

Another important example of a redox titration for inorganic analytes, which is important in industrial labs, is the determination of water in nonaqueous solvents. The titrant for this analysis is known as the Karl Fischer reagent and consists of a mixture of iodine, sulfur dioxide, pyridine, and methanol. The concentration of pyridine is sufficiently large so that b and SO2 are complexed with the pyridine (py) as py b and py SO2. When added to a sample containing water, b is reduced to U, and SO2 is oxidized to SO3. 

Analytical and Test Methods. o-Nitrotoluene can be analyzed for purity and isomer content by infrared spectroscopy with an accuracy of about 1%. -Nitrotoluene content can be estimated by the decomposition of the isomeric toluene diazonium chlorides because the ortho and meta isomers decompose more readily than the para isomer. A colorimetric method for determining the content of the various isomers is based on the color which forms when the mononitrotoluenes are dissolved in sulfuric acid (45). From the absorption of the sulfuric acid solution at 436 and 305 nm, the ortho and para isomer content can be deterrnined, and the meta isomer can be obtained by difference. However, this and other colorimetric methods are subject to possible interferences from other aromatic nitro compounds. A titrimetric method, based on the reduction of the nitro group with titanium(III) sulfate or chloride, can be used to determine mononitrotoluenes (32). Chromatographic methods, eg, gas chromatography or high pressure Hquid chromatography, are well suited for the deterrnination of mononitrotoluenes as well as its individual isomers. Freezing points are used commonly as indicators of purity of the various isomers. 

Analytical and Laboratory Operations. Sulfamic acid has been recommended as a reference standard in acidimetry (55). It can be purified by recrystaUization to give a stable product that is 99.95 wt % pure. The reaction with nitrite as used in the sulfamic acid analytical method has also been adapted for determination of nitrites with the acid as the reagent. This reaction is used commercially in other systems for removal of nitrous acid impurities, eg, in sulfuric and hydrochloric acid purification operations. 

Analytical Methods. Detection of carbonyl sulfide ia air can be done by gas chromatography or by combustion to sulfur dioxide and determination of the latter. Where hydrogen sulfide and carbonyl sulfide occur together, the carbonyl sulfide can be determined by combustion after hydrogen sulfide is absorbed by lead acetate, which does not absorb carbonyl sulfide (35). 

Analytical Methods. A method has been described for gas chromatographic analysis of trichloromethanesulfenyl chloride as well as of other volatile sulfur compounds (62). A method has been recommended for determining small amounts of trichloromethanesulfenyl chloride in air or water on the basis of a color-forming reaction with resorcinol (63). 

Analytical Methods. The official NIOSH recommended method for determining sulfur dioxide in air consists of drawing a known prefiltered volume of air through a bubbler containing hydrogen peroxide, thus oxidising the sulfur dioxide to sulfuric acid. Isopropyl alcohol is then added to the contents in the bubbler and the pH of the sample is adjusted with dilute perchloric acid. The resultant solution is then titrated for sulfate with 0.005 M. barium perchlorate, and Thorin is used as the indicator. 

Descriptions of sulfuric acid analytical procedures not specified by ASTM are available (32,152). Federal specifications also describe the requited method of analysis. Concentrations of 78 wt % and 93 wt % H2SO4 are commonly measured indirectly by determining specific gravity. Higher acid concentrations are normally determined by titration with a base, or by sonic velocity or other physical property for plant control. Sonic velocity has been found to be quite accurate for strength analysis of both filming and nonfuming acid. 

Bromine is used as an analytical reagent to determine the amount of unsaturation in organic compounds because carbon—carbon double bonds add bromine quantitatively, and for phenols which add bromine in the ortho and para positions. Standard bromine is added in excess and the amount unreacted is deterrnined by an indirect iodine titration. Bromine is also used to oxidize several elements, such as T1(I) to T1(III). Excess bromine is removed by adding phenol. Bromine plus an acid, such as nitric and/or hydrochloric, provides an oxidizing acid mixture usefiil in dissolving metal or mineral samples prior to analysis for sulfur. 

The ionization eonstant should be a function of the intrinsic heterolytic ability (e.g., intrinsic acidity if the solute is an acid HX) and the ionizing power of the solvents, whereas the dissoeiation constant should be primarily determined by the dissociating power of the solvent. Therefore, Ad is expeeted to be under the eontrol of e, the dieleetrie eonstant. As a consequenee, ion pairs are not deteetable in high-e solvents like water, which is why the terms ionization constant and dissociation constant are often used interchangeably. In low-e solvents, however, dissociation constants are very small and ion pairs (and higher aggregates) become important species. For example, in ethylene chloride (e = 10.23), the dissociation constants of substituted phenyltrimethylammonium perchlorate salts are of the order 10 . Overall dissociation constants, expressed as pArx = — log Arx, for some substanees in aeetie acid (e = 6.19) are perchloric acid, 4.87 sulfuric acid, 7.24 sodium acetate, 6.68 sodium perchlorate, 5.48. Aeid-base equilibria in aeetie acid have been earefully studied beeause of the analytical importance of this solvent in titrimetry. 

The ease of N determination in PVN samples appears to be a function of the degree of polymerization. The nitrometer method gives consistent results, but are about 0.6% lower than the true values (Ref 6). Difficulty is experienced with high viscosity PVN. These products dissolve slowly in sulfuric acid, and give scattered results. Analytical methods based on titanous chloride,... 

The analysis of phosphates and phosphonates is a considerably complex task due to the great variety of possible molecular structures. Phosphorus-containing anionics are nearly always available as mixtures dependent on the kind of synthesis carried out. For analytical separation the total amount of phosphorus in the molecule has to be ascertained. Thus, the organic and inorganic phosphorus is transformed to orthophosphoric acid by oxidation. The fusion of the substance is performed by the addition of 2 ml of concentrated sulfuric acid to — 100 mg of the substance. The black residue is then oxidized by a mixture of nitric acid and perchloric acid. The resulting orthophosphate can be determined at 8000 K by atom emission spectroscopy. The thermally excited phosphorus atoms emit a characteristic line at a wavelength of 178.23 nm. The extensity of the radiation is used for quantitative determination of the phosphorus content. 

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