Air, iodine

Schardt, B.C., Yau. Shneh-Lin, and F. Rinaldi Atomic Resolution Imaging of Adsorbates on Metal Surfaces in Air Iodine Adsorption on Pt(III), Science, 1050... 

Platinic iodide is a blackish brown, amorphous powder, which evolves iodine vapour when placed in vacuo even at ordinary temperatures.6 When warmed to 130° C. in air, iodine is evolved.2... 

The oxidation of aporphines with air, iodine, or mercuric acetate has been shown to be dependent on the presence and position of hydroxy-groups, and isothebaine has been shown to give the salt (67). ... 

When 1 part of sulphur and 8 of iodine are mixed and gently heated, they immediately combine and liquefy. On cooling, the liquid, which is dark brown, consolidates into a black ciystSline solid, which is the iodide of sulphur. It must be kept in well-closed bottles, as it is destroyed by the access of air, iodine being given oft Its composition is probably SI. It is used in medicine as a remedy in various cutaneous diseases. 

In the air, iodine exists as particles associated, inorganic gaseous iodine (I2, HIO) and organic iodine (CH3I, CH2I2, etc.). The different species of iodine in the air can be separated and collected in a series filter and then measured. 

Iodine is a dark-coloured solid which has a glittering crystalline appearance. It is easily sublimed to form a bluish vapour in vacuo. but in air, the vapour is brownish-violet. Since it has a small vapour pressure at ordinary temperatures, iodine slowly sublimes if left in an open vessel for the same reason, iodine is best weighed in a stoppered bottle containing some potassium iodide solution, in which the iodine dissolves to form potassium tri-iodide. The vapour of iodine is composed of I2 molecules up to about 1000 K above this temperature, dissociation into iodine atoms becomes appreciable. 

Iodine has the lowest standard electrode potential of any of the common halogens (E = +0.54 V) and is consequently the least powerful oxidising agent. Indeed, the iodide ion can be oxidised to iodine by many reagents including air which will oxidise an acidified solution of iodide ions. However, iodine will oxidise arsenate(lll) to arsenate(V) in alkaline solution (the presence of sodium carbonate makes the solution sufficiently alkaline) but the reaction is reversible, for example by removal of iodine. 

Hence hydrogen iodide cannot be produced by the reaction of sulphuric acid with an iodide. Hydriodic acid is slowly oxidised by air (more rapidly in light) liberating iodine ... 

About 0.5 g of iodine is placed in a small flask fitted with a long reflux air condenser and 15 cm of fuming nitric acid (b.p. 380 K) are added. The mixture is then heated on a water bath at 385-390 K in a fume cupboard until the reaction seems to be complete. This takes about an hour. The solution is then transferred to an evaporating basin and evaporated to dryness on a steam bath. The iodic acid... 

This should be free from sulphur, and obtained in small containers so that a specimen is rapidly used it should be in dark bottles and stored in the dark. When withdrawing a specimen, the acid should be exposed to the air for as short a time as possible, as both air and light promote its decomposition to iodine. 

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). 

Fit a 750 ml. round-bottomed flask with a fractionating column attached to a condenser set for downward distillation. Place 500 g. of diacetone alcohol (the crude product is quite satisfactory), 01 g. of iodine and a few fragments of porous porcelain in the flask. Distil slowly. with a small free flame (best in an air bath) and collect the following fractions (a) 56-80° (acetone and a little mesityl oxide) (6) 80-126° (two layers, water and mesityl oxide) and (c) 126-131° (mesityl oxide). Whilst fraction (c) is distilling, separate the water from fraction (6), dry with anhydrous potassium carbonate or anhydrous magnesium sulphate, and fractionate from a small flask collect the mesityl oxide at 126-131°. The yield is about 400 g. 

Into a 1-litre beaker, provided with a mechanical stirrer, place 36 - 8 g. (36 ml.) of aniline, 50 g. of sodium bicarbonate and 350 ml. of water cool to 12-15° by the addition of a little crushed ice. Stir the mixture, and introduce 85 g. of powdered, resublimed iodine in portions of 5-6 g, at intervals of 2-3 minutes so that all the iodine is added during 30 minutes. Continue stirring for 20-30 minutes, by which time the colour of the free iodine in the solution has practically disappeared and the reaction is complete. Filter the crude p-iodoaniline with suction on a Buchner funnel, drain as completely as possible, and dry it in the air. Save the filtrate for the recovery of the iodine (1). Place the crude product in a 750 ml. round-bottomed flask fitted with a reflux double surface condenser add 325 ml. of light petroleum, b.p. 60-80°, and heat in a water bath maintained at 75-80°. Shake the flask frequently and after about 15 minutes, slowly decant the clear hot solution into a beaker set in a freezing mixture of ice and salt, and stir constantly. The p-iodoaniline crystallises almost immediately in almost colourless needles filter and dry the crystals in the air. Return the filtrate to the flask for use in a second extraction as before (2). The yield of p-iodoaniline, m.p. 62-63°, is 60 g. 

Place 125 ml. of glacial acetic acid, 7 -5 g. of purifled red phosphorus (Section II,50,d) and 2 5 g. of iodine in a 500 ml, round-bottomed flask fitted with a reflux condenser. Allow the mixture to stand for 15-20 minutes with occasional shaking until aU the iodine has reacted, then add 2 5 ml. of water and 50 g, of benzilic acid (Section IV,127). Boil the mixture under reflux for 3 hours, and filter the hot mixture at the pump through a sintered glass funnel to remove the excess of red phosphorus. Pour the hot filtrate into a cold, weU-stirred solution of 12 g. of sodium bisulphite in 500 ml, of water the latter should be acid to litmus, pro duced, if necessary, by passing sulphur dioxide through the solution. This procedure removes the excess of iodine and precipitates the diphenyl-acetic acid as a fine white or pale yellow powder. Filter the solid with suction and dry in the air upon filter paper. The yield is 45 g., m.p. 

Amino-3 5-diiodobenzoic acid. In a 2 litre beaker, provided with a mechanical stirrer, dissolve 10 g. of pure p-aminobenzoic acid, m.p. 192° (Section IX,5) in 450 ml. of warm (75°) 12 -5 per cent, hydrochloric acid. Add a solution of 48 g. of iodine monochloride (1) in 40 ml. of 25 per cent, hydrochloric acid and stir the mixture for one minute during this time a yellow precipitate commences to appear. Dilute the reaction mixtiue with 1 litre of water whereupon a copious precipitate is deposited. Raise the temperature of the well-stirred mixture gradually and maintain it at 90° for 15 minutes. Allow to cool to room tempera-tiue, filter, wash thoroughly with water and dry in the air the yield of crude acid is 24 g. Purify the product by dissolving it in dilute sodium hydroxide solution and precipitate with dilute hydrochloric acid the yield of air-dried 4-amino-3 5-diiodobenzoic acid, m.p. >350°, is 23 g. 

Care should be taken in handling and using iodine, as contact with the skin can cause lesions iodine vapor is intensely irritating to the eyes and mucus membranes. The maximum allowable concentration of iodine in air should not exceed 1 mg/nu (8-hour time-weighted average -40-hour). 

THF into the sep funnel. It is recommended that an iodine crystal is placed in the reaction flask and before the condenser is attached, nitrogen should be blown Into the receiving flask to remove any air. As / didn t have any nitrogen available I skipped this step but I did place one small crystal of iodine into the reaction flask. When the iodine is added the solvent will begin to turn brown. Although this looks like the iodine is just dissolving it would appear from what I have read that this is also caused by the reaction. 

United States production of iodine pentafluoride is several hundred metric tons per year. The two U.S. producers are Air Products and Chemicals, Inc. and AUiedSignal, Inc. The 1992 price was ca 50/kg. 

Although not abundant in quantity, iodine is distributed in rocks, soils, waters, plants, animal tissues, and foodstuffs (3,4). Excepting the possible occurrence of elemental iodine vapor in the air near certain iodine-rich springs, iodine never occurs free in nature. It is always found combined with other elements. 

Iodine vapor is characterized by the familiar violet color and by its unusually high specific gravity, approximately nine times that of air. The vapor is made up of diatomic molecules at low temperatures at moderately elevated temperatures, dissociation becomes appreciable. The concentration of monoatomic molecules, for example, is 1.4% at 600°C and 101.3 kPa (1 atm) total pressure. Iodine is fluorescent at low pressures and rotates the plane of polarized light when placed in a magnetic field. It is also thermoluminescent, emitting visible light when heated at 500°C or higher. 

Seaweeds. The eadiest successful manufacture of iodine started in 1817 using certain varieties of seaweeds. The seaweed was dried, burned, and the ash lixiviated to obtain iodine and potassium and sodium salts. The first process used was known as the kelp, or native, process. The name kelp, initially apphed to the ash of the seaweed, has been extended to include the seaweed itself. About 20 t of fresh seaweed was used to produce 5 t of air-dried product containing a mean of 0.38 wt % iodine in the form of iodides of alkah metals. The ash obtained after burning the dried seaweed contains about 1.5 wt % iodine. Chemical separation of the iodine was performed by lixiviation of the burned kelp, followed by soHd-Hquid separation and water evaporation. After separating sodium and potassium chloride, and sodium carbonate, the mother Hquor containing iodine as iodide was treated with sulfuric acid and manganese dioxide to oxidize the iodide to free iodine, which was sublimed and condensed in earthenware pipes (57). 

Brines. About 65% of the iodine consumed in the world comes from brines processed in Japan, the United States, and the former Soviet Union (see Chemicals frombrine). The predorninant production process for iodine from brines is the blow-out process, which was first used in Japan. Iodine is present in brines as iodide, and its concentration varies from about 10 to 150 ppm. As shown in Figure 3, the recovery process can be divided into brine clean-up, iodide oxidation to iodine followed by air blowing out and recovery, and iodine finishing. 

The I2 formed stays in solution, exerting a certain vapor pressure, and is extracted from the brine in a countercurrent air blow-out process. The extracted brine leaves the extraction tower and is discarded or reinjected into the wells to avoid sinking of the soil. The iodine-loaded air is then submitted to a cocurrent desorption process by means of an acidic iodide solution to which SO2 is added. By this solution the iodine is reduced to iodide by the following reaction ... 

The quantitative conversion of thiosulfate to tetrathionate is unique with iodine. Other oxidant agents tend to carry the oxidation further to sulfate ion or to a mixture of tetrathionate and sulfate ions. Thiosulfate titration of iodine is best performed in neutral or slightly acidic solutions. If strongly acidic solutions must be titrated, air oxidation of the excess of iodide must be prevented by blanketing the solution with an inert gas, such as carbon dioxide or... 

The U.S. Occupational Safety and Health Administration (OSHA) has set a ceiling level for iodine of 0.1 ppm in air. The American Conference of Government and Industrial Hygienists (ACGIH) estabUshed 0.1 ppm as the TLV (TWA) for iodine. The maximum allowable concentration in air (MAK value) is also 0.1 ppm (104—106). 

The iodides of the alkaU metals and those of the heavier alkaline earths are resistant to oxygen on heating, but most others can be roasted to oxide in air and oxygen. The vapors of the most volatile iodides, such as those of aluminum and titanium(II) actually bum in air. The iodides resemble the sulfides in this respect, with the important difference that the iodine is volatilized, not as an oxide, but as the free element, which can be recovered as such. Chlorine and bromine readily displace iodine from the iodides, converting them to the corresponding chlorides and bromides. 

Methylene iodide [75-11-6], CH2I2, also known as diio dome thane, mol wt 267.87, 94.76% I, mp 6.0°C, and bp 181°C, is a very heavy colorless Hquid. It has a density of 3.325 g/mL at 20°C and a refractive index of 1.7538 at 4°C. It darkens in contact with air, moisture, and light. Its solubiHty in water is 1.42 g/100 g H2O at 20°C it is soluble in alcohol, chloroform, ben2ene, and ether. Methylene iodide is prepared by reaction of sodium arsenite and iodoform with sodium hydroxide reaction of iodine, sodium ethoxide, and hydroiodic acid on iodoform the oxidation of iodoacetic acid with potassium persulfate and by reaction of potassium iodide and methylene chloride (124,125). Diiodoform is used for determining the density and refractive index of minerals. It is also used as a starting material in the manufacture of x-ray contrast media and other synthetic pharmaceuticals (qv). 

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