Iodide detection

As in the earlier examinations, the amount of methyl iodide detected in the purged product was still averaged ca. 0.3 wt.%. However, unlike the earher ran with [MePy]I, we took a close look at the effluent from the operation with l,2-dimethyl-5-ethyl-pyridinium iodide ([DMEpy] ). All the product was distilled overhead leaving a residue that upon examination by NMR contained a ca. 3 1 acetate [DMEpyratio. Closer examination by NMR revealed that only about 3% of [DMEpy]l in the overhead distillate had been dealkylated to 2-methyl-5-ethyl pyridium hydroiodide. 

Wygladacz K, Bakker E (2007) Fluorescent microsphere fiber optic microsensor array for direct iodide detection at low picomolar concentrations. Analyst 132 268-272... 

We have made the interesting observation that most dioxetanes bleach iodine when the latter is used as a spotting agent. Thus, a bright white spot remains where dioxetane is located, while the rest of the TLC plate turns yellowish on exposure to iodine vapors. The combination of potassium iodide detection (brown spot) and iodine detection (white spot) can be quite definitive for the presence of dioxetanes. The lack of such tests, however, does not mean that dioxetanes are not present. 

It has been observed - that a considerable amount of acetone is formed at very high light intensities (lO -lO quanta.P. sec ) under these conditions acetyl radicals are a product of primary process III and not of the secondary reactions. There was no acetyl iodide detectable in the presence of iodine at medium and low light intensities -Primary process III is likely to play only a minor part at these intensities. 

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. 

Noncnzymc-Catalyzcd Reactions The variable-time method has also been used to determine the concentration of nonenzymatic catalysts. Because a trace amount of catalyst can substantially enhance a reaction s rate, a kinetic determination of a catalyst s concentration is capable of providing an excellent detection limit. One of the most commonly used reactions is the reduction of H2O2 by reducing agents, such as thiosulfate, iodide, and hydroquinone. These reactions are catalyzed by trace levels of selected metal ions. Eor example the reduction of H2O2 by U... 

Fluorine in the atmosphere can be detected by chemical methods involving the displacement of halogens from haUdes. Dilute fluorine leaks are easily detected by passing a damp piece of starch iodide paper around the suspected area. The paper should be held with metal tongs or forceps to avoid contact with the gas stream and immediately darkens when fluorine is present. 

The pH must be kept at 7.0—7.2 for this method to be quantitative and to give a stable end poiut. This condition is easily met by addition of soHd sodium bicarbonate to neutralize the HI formed. With starch as iudicator and an appropriate standardized iodine solution, this method is appHcable to both concentrated and dilute (to ca 50 ppm) hydraziue solutious. The iodiue solutiou is best standardized usiug mouohydraziuium sulfate or sodium thiosulfate. Using an iodide-selective electrode, low levels down to the ppb range are detectable (see Electro analytical techniques) (141,142). Potassium iodate (143,144), bromate (145), and permanganate (146) have also been employed as oxidants. 

O ne. Air pollution (qv) levels are commonly estimated by determining ozone through its chemiluminescent reaction with ethylene. A relatively simple photoelectric device is used for rapid routine measurements. The device is caHbrated with ozone from an ozone generator, which in turn is caHbrated by the reaction of ozone with potassium iodide (308). Detection limits are 6—9 ppb with commercially available instmmentation (309). 

The range of uses of mercuric iodide has increased because of its abiUty to detect nuclear particles. Various metals such as Pd, Cu, Al, Tri, Sn, Ag, and Ta affect the photoluminescence of Hgl2, which is of importance in the preparation of high quaUty photodetectors (qv). Hgl2 has also been mentioned as a catalyst in group transfer polymerization of methacrylates or acrylates (8). 

The detection and quantitation of y-emission from is accompHshed by well counting. A thaUium-activated sodium iodide crystal, having a well... 

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). 

Impurities in bromine may be deterrnined quantitatively (54). Weighing the residue after evaporation of a bromine sample yields the total nonvolatile matter. After removing the bromine, chloride ion may be deterrnined by titration with mercuric nitrate, and iodide ion by titration with thiosulfate water and organic compounds may be detected by infrared spectroscopy sulfur may be deterrnined turbidimetricaHy as barium sulfate and heavy metals may be deterrnined colorimetricaHy after conversion to sulfides. 

Detection of Bromine Vapor. Bromine vapor in air can be monitored by using an oxidant monitor instmment that sounds an alarm when a certain level is reached. An oxidant monitor operates on an amperometric principle. The bromine oxidizes potassium iodide in solution, producing an electrical output by depolarizing one sensor electrode. Detector tubes, usefiil for determining the level of respiratory protection required, contain (9-toluidine that produces a yellow-orange stain when reacted with bromine. These tubes and sample pumps are available through safety supply companies (54). The usefiil concentration range is 0.2—30 ppm. 

Analytical Methods. Most of the analytical and testing methods used for ethyl ether are conventional laboratory methods. Ethyl ether that is to be used for anesthetic purposes or in processes that involve heating or distiHation must be peroxide-free, and should pass the USP standard test with potassium iodide. This test detects approximately 0.001% peroxide as hydrogen peroxide. 

Diazirines (3) smoothly add Grignard compounds to the N—N double bond, giving 1-alkyldiaziridines. Reported yields are between 60 and 95% without optimization (B-67MI50800). The reaction is easily carried out on a preparative scale without isolation of the hazardous diazirines and may serve as an easy access to alkylhydrazines. The reaction was also used routinely to detect diazirines in mixtures. The diaziridines formed are easily detected by their reaction with iodide. Phenyllithium or ethylzinc iodide also add to (3) with diaziridine formation. 

Note The reagent can be employed on silica gel and cellulose layers. When derivatization is carried out from the vapor phase the detection limit for morphine is 10 ng and that for papaverine 1 ng per chromatogram zone [5]. In some cases it has been recommended that ammonium sulfate be added to the layer with subsequent heating to 150 —180 °C [1] after derivatization. It is also possible to spray afterwards with an aqueous solution of potassium iodide (1 %) and starch (1%) [2]. 

Nicotine may be detected by the colourless, crystalline mercurichloride obtained when an aqueous solution is added to a solution of mercuric chloride, by the black precipitate formed under similar conditions with potassium platinic iodide and the characteristic crystalline periodide, BI2. HI, m.p. 123°, produced on admixture, under specified conditions, 2 of ethereal solutions of nicotine and iodine (cf Anabasine, p. 43). A polarographic study of nicotine has been made by Kirkpatrick. ... 

Reductive coupling reaction of fluonnated vinyl iodides or bromides has been used as a route to fluorinated dienes [246, 247, 248, 249, 250. Generally, the vinyl iodide is heated with copper metal in DMSO or DMF no 1 ntermediate perfluorovmy I-copper reagent is detected. Typical examples are shown m equations 163-165 [246, 247, 249. The X-ray crystal structure of perfluorotetracyclobutacyclooctatetraene, prepared via coupling of tetrafluoro-l,2-diiodocyclobutene with copper, is planar... 

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