Iodides, acid detection

The impurities of potassium bromide.—Judging from the analyses of potassium bromide by H. Adrian,4 the older commercial varieties were very much more contaminated with impurities than modern samples. For example, H. Adrian found 10 to 15 per cent, of impurities in 10 commercial samples to-day, the German Pharmacopoeia permits 2 per cent, of potassium chloride, and about 0T per cent, of the carbonate. There has been reported 0T3 per cent, of KC1 in English bromide, 4 52 to 5 92 per cent, in American and in both, 0 35 to 1 29 per cent, of moisture. The bromide from Stassfurt is free from iodides. To detect iodides, the soln. is first treated with a little fuming nitric acid, and then shaken with chloroform, if but little iodine is present, the chloroform will not be coloured, but if the bromide be treated with an excess of ferric chloride the iodine will colour the chloroform... 

Stainton [31] has described an automated method for the determination of sulphate and chloride in non saline waters. An ion exchange resin is used to convert the sulphates and chlorides to their free acids. Detection is achieved by electrical conductance. The use of silver-saturated cation exchange resin to precipitate chloride permits distinction between chloride and sulphate. High levels of nitrate, orthophosphate and fluoride give positive interference for sulphate bromide and iodide similarly interfere with chloride estimates. 

Absolute diethyl ether. The chief impurities in commercial ether (sp. gr. 0- 720) are water, ethyl alcohol, and, in samples which have been exposed to the air and light for some time, ethyl peroxide. The presence of peroxides may be detected either by the liberation of iodine (brown colouration or blue colouration with starch solution) when a small sample is shaken with an equal volume of 2 per cent, potassium iodide solution and a few drops of dilute hydrochloric acid, or by carrying out the perchromio acid test of inorganic analysis with potassium dichromate solution acidified with dilute sulphuric acid. The peroxides may be removed by shaking with a concentrated solution of a ferrous salt, say, 6-10 g. of ferrous salt (s 10-20 ml. of the prepared concentrated solution) to 1 litre of ether. The concentrated solution of ferrous salt is prepared either from 60 g. of crystallised ferrous sulphate, 6 ml. of concentrated sulphuric acid and 110 ml. of water or from 100 g. of crystallised ferrous chloride, 42 ml. of concentrated hydiochloric acid and 85 ml. of water. Peroxides may also be removed by shaking with an aqueous solution of sodium sulphite (for the removal with stannous chloride, see Section VI,12). 

CAUTION. Ethers that have been stored for long periods, particularly in partly-filled bottles, frequently contain small quantities of highly explosive peroxides. The presence of peroxides may be detected either by the per-chromic acid test of qualitative inorganic analysis (addition of an acidified solution of potassium dichromate) or by the liberation of iodine from acidified potassium iodide solution (compare Section 11,47,7). The peroxides are nonvolatile and may accumulate in the flask during the distillation of the ether the residue is explosive and may detonate, when distilled, with sufficient violence to shatter the apparatus and cause serious personal injury. If peroxides are found, they must first be removed by treatment with acidified ferrous sulphate solution (Section 11,47,7) or with sodium sulphite solution or with stannous chloride solution (Section VI, 12). The common extraction solvents diethyl ether and di-tso-propyl ether are particularly prone to the formation of peroxides. 

Before coupling, excess nitrous acid must be destroyed. Nitrite can react with coupling components to form nitroso compounds causiag deHterious effects on the final dyestuff. The presence of nitrite can be detected by 4,4 -diamiQO-diphenyHnethane-2,2 -sulfone [10215-25-5] (Green reagent) or starch—iodide. Removal of nitrite is achieved by addition of sulfamic acid or urea [57-13-6], however, sulfamic acid [5329-14-6] has been more effective ia kinetic studies of nine nitrous acid scavangers (18). 

To detect nitrous acid, a drop of the mixture is diluted with water and tested with starch iodide paper. 

The amount of reddish-purple acid-chloranilate ion liberated is proportional to the chloride ion concentration. Methyl cellosolve (2-methoxyethanol) is added to lower the solubility of mercury(II) chloranilate and to suppress the dissociation of the mercury(II) chloride nitric acid is added (concentration 0.05M) to give the maximum absorption. Measurements are made at 530nm in the visible or 305 nm in the ultraviolet region. Bromide, iodide, iodate, thiocyanate, fluoride, and phosphate interfere, but sulphate, acetate, oxalate, and citrate have little effect at the 25 mg L 1 level. The limit of detection is 0.2 mg L 1 of chloride ion the upper limit is about 120 mg L . Most cations, but not ammonium ion, interfere and must be removed. 

A number of methods have been proposed for the detection of rancidity. The determination of active oxygen consists of dissolving the fat in a suitable medium such as chloroform and acetic acid, adding potassium iodide, and titrating the liberated iodine with a standard thiosulfate solution (16, 20). This is perhaps the most widely used method at the present time. Another procedure which has been proposed for the detection of peroxides employs ferrous ammonium sulfate and ammonium thiocyanate in acetone. The resulting red color of ferric thiocyanate is measured spectrophotometrically, and is said by the authors to yield more reproducible results than do the usual titration methods (21). 

A. o-Bromobenzenediazonium hexafluorophosphate. A solution of 95 ml. of 12N hydrocMoric acid in 650 ml. of water is added with stirring to 60 g. of o-bromoaniline (0.35 mole Note 1) in a 2-1. three-necked flask equipped with stirrer and thermometer. Solution is effected by heating the mixture on a steam bath (Note 2). A solution of 29 g. (0.42 mole) of sodium nitrite in 75 ml. of water is added with stirring while the mixture is maintained at — 5° to —10° by means of a bath of ice and salt or of dry ice and acetone. At the end of the addition there is an excess of nitrous acid, which can be detected with starch iodide paper. Seventy-four milliliters (134 g., 0.60 mole) of 65% hexafluorophosphoric acid (Note 3) is added in one portion, with vigorous stirring, to the cold solution of the diazonium salt. Cooling and slow stirring are continued for an additional 30 minutes, and the precipitated diazonium hexafluorophosphate is then collected on a Bilchner funnel. The diazonium salt is washed on the funnel with 300 ml. of cold water and with a solution of 80 ml. of methanol in 320 ml. 

Note Tertiary amines and quaternary ammonium compounds yield stronger colors than primary amines [25]. The dipping solution can also be used as spray solution [44]. Other reagent compositions have also been reported in the literature (1, 3, 6, 12, 13, 15, 18, 21, 23, 41] In some cases the reagents have been made up in acetone [38, 39], methanol [14] or ethanol [37] and/or acidified with hydrochloric acid [3, 33, 37-40]. The concentrations of hexachloroplatinic(IV) acid have been in the range of 0.05 -0.4 those of potassium iodide between 0.5 and 24spray solution containing 2% potassium iodide and 0.23170 hexachloroplatinic(IV) acid hexahydrate in N-hydro-chloric acid is reported to yield the best coloration results with respect to detection sensitivity and color differentiation in the detection of morphine, codeine, quinine, methadone and cocaine [46]. Acidic reagent solutions have been recommended for benzodiazepines [10, 11]. Sulfones do not react [39]. 

It appeared that, we needed to limit or omit the ethyl iodide if we were going to operate the ethylene carbonylation in ionic liquids. Unfortunately, the previous literature indicated that EtI or HI (which are interconvertible) represented a critical catalyst component. Therefore, it was surprising when we found that, in iodide based ionic liquids, the Rh catalyzed carbonylation of ethylene to propionic acid was still operable at acceptable rates in the absence of ethyl iodide, as shown in Table 37.2. Further, we not only achieved acceptable rates when omitting the ethyl iodide, we also achieved the desired reduction in the levels of ethyl propionate. More importantly, when the reaction products were analyzed, there was no detectable ethyl iodide formed in situ. However, we should note that we now observed traces of ethanol which were normally undetectable in the earlier Ed containing experiments. 

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. 

POOH + 31 + 2H+ I3 + H20 + POH The method does not usually detect dialkylperoxides, POOP [16]. In applying the method, a known weight of sample will be refluxed in a mixture of isopropanol and acetic acid in the presence of sodium iodide. The reaction time is usually about 30 min. A detection limit of ca. 30 ppm of hydroperoxide has been reported [1]. 

C. On Fe-Beta-300 the dimethyl ether selectivity was maximum at 240 °C and the hydrocarbons (mostly LC4) selectivities increased in addition to some constant amount of formaldehyde between 240-360 °C (Fig. la). This result confirms the presence of light Bronsted and Lewis acid sites (Fig. 2a) in accordance with FTIR results by pyridine [6], The methyl iodide started to convert to hydrocarbon (C1-C4) at 240 °C but dimethyl ether was not detected. 

To date, a few methods have been proposed for direct determination of trace iodide in seawater. The first involved the use of neutron activation analysis (NAA) [86], where iodide in seawater was concentrated by strongly basic anion-exchange column, eluted by sodium nitrate, and precipitated as palladium iodide. The second involved the use of automated electrochemical procedures [90] iodide was electrochemically oxidised to iodine and was concentrated on a carbon wool electrode. After removal of interference ions, the iodine was eluted with ascorbic acid and was determined by a polished Ag3SI electrode. The third method involved the use of cathodic stripping square wave voltammetry [92] (See Sect. 2.16.3). Iodine reacts with mercury in a one-electron process, and the sensitivity is increased remarkably by the addition of Triton X. The three methods have detection limits of 0.7 (250 ml seawater), 0.1 (50 ml), and 0.02 pg/l (10 ml), respectively, and could be applied to almost all the samples. However, NAA is not generally employed. The second electrochemical method uses an automated system but is a special apparatus just for determination of iodide. The first and third methods are time-consuming. 

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