Cyanide masking

Hydrogen peroxide prevents oxine from reacting with Ti, V, Nb, U, and Ce. Cyanide masks Ni, Co, Cu, Zn, Cd, Ag, and Fe(II). EDTA or tartrate keeps aluminium in solution at higher pH values, at which it normally hydrolyses. The presence of EDTA does not interfere in the extraction of aluminium with oxine when the pH of the solution is above 8. 

Most interfering cations are masked with EDTA. Tartrate masks milligram quantities of Ta, Ti, W, Mo, Sb(V), and Sn(IV) U(VI) and Zr can be masked with phosphate fluoride masks A1 and Th cyanide masks any silver present. The interfering effect of Ce(IV) and V(V) can be eliminated by addition of ascorbic acid which reduces them to Ce(III) and V(IV), respectively. Thus, the BPR method can be regarded as specific, provided that... 

Free cyanide, thiocyanate Human saliva and pralidoxime solutions Chloroform UV—Vis 0.004, 0.007 mg L 1 C-FIA membrane for phase [466] separation formaldehyde addition for cyanide masking... 

Probably the most extensively applied masking agent is cyanide ion. In alkaline solution, cyanide forms strong cyano complexes with the following ions and masks their action toward EDTA Ag, Cd, Co(ll), Cu(ll), Fe(ll), Hg(ll), Ni, Pd(ll), Pt(ll), Tl(lll), and Zn. The alkaline earths, Mn(ll), Pb, and the rare earths are virtually unaffected hence, these latter ions may be titrated with EDTA with the former ions masked by cyanide. Iron(lll) is also masked by cyanide. However, as the hexacy-anoferrate(lll) ion oxidizes many indicators, ascorbic acid is added to form hexacyanoferrate(ll) ion. Moreover, since the addition of cyanide to an acidic solution results in the formation of deadly... 

Another type of demasking involves formation of new complexes or other compounds that are more stable than the masked species. For example, boric acid is used to demask fluoride complexes of tin(IV) and molybdenum(VI). Formaldehyde is often used to remove the masking action of cyanide ions by converting the masking agent to a nonreacting species through the reaction ... 

Cyanide is frequently used as a masking agent for metal ions. The effectiveness of CN as a masking agent is generally better in more basic solutions. Explain the reason for this pH dependency. 

Polyurethanes. These polymers can be considered safe for human use. However, exposure to dust, generated in finishing operations, should be avoided. Ventilation, dust masks, and eye protection are recommended in foam fabrication operations. Polyurethane or polyisocyanurate dust may present an explosion risk under certain conditions. Airborne concentrations of 25—30 g/m are required before an explosion occurs. Inhalation of thermal decomposition products of polyurethanes should be avoided because carbon monoxide and hydrogen cyanide are among the many products present. 

Skin Absorption. Normal skin absorbs HCN slowly. However, 2% HCN in air may cause poisoning in 3 min, 1% is dangerous in 10 min, and 0.05% may produce symptoms after 30 min, even though a gas mask or air mask is worn. Some areas of the body, such as the feet and mucous membranes, are more absorptive than others. Cuts and abrasions absorb cyanide rapidly, and 50 mg of HCN absorbed through the skin can be fatal. 

Laboratory work with hydrogen cyanide should be carried out only in a well-ventilated fume hood. Special safety equipment such as air masks, face masks, plastic aprons, and mbber gloves should be used. A chemical proof suit should be available for emergency. Where hydrogen cyanide is handled inside a building, suitable ventilation must be provided. The people involved should be thoroughly trained in first aid. 

Woodward s strychnine synthesis commences with a Fischer indole synthesis using phenylhydrazine (24) and acetoveratrone (25) as starting materials (see Scheme 2). In the presence of polyphosphor-ic acid, intermediates 24 and 25 combine to afford 2-veratrylindole (23) through the reaction processes illustrated in Scheme 2. With its a position suitably masked, 2-veratrylindole (23) reacts smoothly at the ft position with the Schiff base derived from the action of dimethylamine on formaldehyde to give intermediate 22 in 92% yield. TV-Methylation of the dimethylamino substituent in 22 with methyl iodide, followed by exposure of the resultant quaternary ammonium iodide to sodium cyanide in DMF, provides nitrile 26 in an overall yield of 97%. Condensation of 2-veratryl-tryptamine (20), the product of a lithium aluminum hydride reduction of nitrile 26, with ethyl glyoxylate (21) furnishes Schiff base 19 in a yield of 92%. 

Hydroxyquinoline, having both a phenolic hydroxyl group and a basic nitrogen atom, is amphoteric in aqueous solution it is completely extracted from aqueous solution by chloroform at pH < 5 and pH > 9 the distribution coefficient of the neutral compound between chloroform and water is 720 at 18 °C. The usefulness of this sensitive reagent has been extended by the use of masking agents (cyanide, EDTA, citrate, tartrate, etc.) and by control of pH. 

Determination. To an aliquot of the silver(I) solution containing between 10 and 50 pg of silver, add sufficient EDTA to complex all those cations present which form an EDTA complex. If gold is present (>250 xg) it is masked by adding sufficient bromide ion to form the AuBr4 complex. Cyanide, thiocyanate or iodide ions are masked by adding sufficient mercury(II) ions to complex these anions followed by sufficient EDTA to complex any excess mercury(II). Add 1 mL of 20 per cent ammonium acetate solution, etc., and proceed as described under Calibration. 

By the use of masking agents, some of the cations in a mixture can often be masked so that they can no longer react with EDTA or with the indicator. An effective masking agent is the cyanide ion this forms stable cyanide complexes with the cations of Cd, Zn, Hg(II), Cu, Co, Ni, Ag, and the platinum metals, but not with the alkaline earths, manganese, and lead ... 

It is therefore possible to determine cations such as Ca2+, Mg2+, Pb2+, and Mn2+ in the presence of the above-mentioned metals by masking with an excess of potassium or sodium cyanide. A small amount of iron may be masked by cyanide if it is first reduced to the iron(II) state by the addition of ascorbic acid. Titanium(IV), iron(III), and aluminium can be masked with triethanolamine mercury with iodide ions and aluminium, iron(III), titanium(lV), and tin(II) with ammonium fluoride (the cations of the alkaline-earth metals yield slightly soluble fluorides). 

Cu, Ni, Co, Cr, Fe, or Al, even in traces, must be absent when conducting a direct titration of the other metals listed above if the metal ion to be titrated does not react with the cyanide ion or with triethanolamine, these substances can be used as masking reagents. It has been stated that the addition of 0.5-1 mL of 0.001 M o-phenanthroline prior to the EDTA titration eliminates the blocking effect of these metals with solochrome black and also with xylenol orange (see below). 

Traces of many metals interfere in the determination of calcium and magnesium using solochrome black indicator, e.g. Co, Ni, Cu, Zn, Hg, and Mn. Their interference can be overcome by the addition of a little hydroxylammonium chloride (which reduces some of the metals to their lower oxidation states), or also of sodium cyanide or potassium cyanide which form very stable cyanide complexes ( masking ). Iron may be rendered harmless by the addition of a little sodium sulphide. 

Many other examples of synthetic equivalent groups have been developed. For example, in Chapter 6 we discussed the use of diene and dienophiles with masked functionality in the Diels-Alder reaction. It should be recognized that there is no absolute difference between what is termed a reagent and a synthetic equivalent group. For example, we think of potassium cyanide as a reagent, but the cyanide ion is a nucleophilic equivalent of a carboxy group. This reactivity is evident in the classical preparation of carboxylic acids from alkyl halides via nitrile intermediates. 

Unfortunately, most fatalities in fires occur by inhalation of toxic vapours. These can be carbon monoxide (which arises from incomplete combustion), cyanides (from nitrogen-containing polymers) and chlorides (from chloropoly-mers). These are the adverse consequences of flammable polymer combustion. They can be overcome by using breathing apparatus, face masks, etc. 

Dissolve the sample in nitric acid. Separate Pb by extraction with CHC solution of sodium diethyl dithiocarbonate using alkaline cyanide solution to mask interferences. Titrate Pb in an ammonia-ammonium chloride medium at pH =10 using eriochrome black T. 

Cyanide wastes, ozone oxidation of, 2 7 808 Cyan indophenol dye developer, 29 287 Cyanine dyes, 7 373t 29 236-237 20 520 Cyanine dyes, 9 503, 504, 505-506 Cyan masking coupler, 29 256-257 l-Cyano-2-methoxy-l,2-dihydroquinoline, 22 184... 

It should be noted that HCN can be absorbed through the skin. For this reason, ACGIH (1996) and NIOSH (1997) guidelines carry a skin notation. Drinker (1931) cites the case of three men protected with gas masks in an atmosphere of 2% (20,000 ppm) HCN. After 8 or 10 min the men felt symptoms of marked dizziness, weakness, and throbbing pulse. They left the chamber just before collapse. For several hours after the exposure they experienced weakness, high pulse rate, and headache. They were incapacitated for several days, followed by complete recovery. Based on exposure to several cyanide salts, the dermal LD50 in rabbits was calculated to be 6.7 mg CN/kg (Ballantyne 1983). 

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