Of cyanide

These water streams contain mainly dissolved salts ammonium chloride and sulfide, sodium chloride, traces of cyanide, phenols for water coming from catalytic and thermal cracking operations. 

The complexes of manganese(III) include [Mn(CN)g] (formed when manganesefll) salts are oxidised in presence of cyanide ions), and [Mnp5(H20)] , formed when a manganese(II) salt is oxidised by a manganate(VII) in presence of hydrofluoric acid ... 

Here, effectively, the Co " (aq) is being oxidised by the nitrite ion and the latter (in excess) is simultaneously acting as a ligand to form the hexanitrocobaltate(III) anion. In presence of cyanide ion CN. cobalt(II) salts actually reduce water to hydrogen since... 

Furfural undergoes condensation to furoin under the catal3rtic influence of cyanide ions in aqueous alcohol solution (compare Benzoin, Section IV,125) ... 

A is common to all the routes we are considering but it is obviously cheaper to use a mole of cyanide or nitromethane rather than another mole of rnalonate. In fact, though, these contribute relatively httle to the cost, the main part being p-chlorobenzaldehyde. So, use whichever route you hke ... 

The most general methods for the syntheses of 1,2-difunctional molecules are based on the oxidation of carbon-carbon multiple bonds (p. 117) and the opening of oxiranes by hetero atoms (p. 123fl.). There exist, however, also a few useful reactions in which an a - and a d -synthon or two r -synthons are combined. The classical polar reaction is the addition of cyanide anion to carbonyl groups, which leads to a-hydroxynitriles (cyanohydrins). It is used, for example, in Strecker s synthesis of amino acids and in the homologization of monosaccharides. The ff-hydroxy group of a nitrile can be easily substituted by various nucleophiles, the nitrile can be solvolyzed or reduced. Therefore a large variety of terminal difunctional molecules with one additional carbon atom can be made. Equally versatile are a-methylsulfinyl ketones (H.G. Hauthal, 1971 T. Durst, 1979 O. DeLucchi, 1991), which are available from acid chlorides or esters and the dimsyl anion. Carbanions of these compounds can also be used for the synthesis of 1,4-dicarbonyl compounds (p. 65f.). 

Cyanide ion ( C = N ) The negatively charged carbon atom of cyanide ion IS usually the site of its nucleophilic character Use of cyanide ion as a nucleophile permits the extension of a carbon chain by carbon-carbon bond formation The product is an alkyl cyanide or nitrile... 

Step 1 Nucleophilic attack by the negatively charged carbon of cyanide ion at the... 

In the Strecker synthesis an aldehyde is converted to an a ammo acid with one more carbon atom by a two stage procedure m which an a ammo nitrile is an mterme diate The a ammo nitrile is formed by reaction of the aldehyde with ammonia or an ammonium salt and a source of cyanide ion Hydrolysis of the nitrile group to a car boxylic acid function completes the synthesis... 

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 ... 

The concentration of cyanide, CN, in a copper electroplating bath can be determined by a complexometric titration with Ag+, forming the soluble Ag(CN)2 complex. In a typical analysis a 5.00-mL sample from an electroplating bath is transferred to a 250-mL Erlenmeyer flask, and treated with 100 mL of H2O, 5 mL of 20% w/v NaOH, and 5 mL of 10% w/v Kl. The sample is titrated with 0.1012 M AgN03, requiring 27.36 mL to reach the end point as signaled by the formation of a yellow precipitate of Agl. Report the concentration of cyanide as parts per million of NaCN. 

Formation of cyanide by degradation of hydantoia derivatives used as antiseptics for water treatment has been described (84), and this fact might have toxicological relevance. 

L. J. BoUyky, O ne Treatment of Cyanide-Bearing Wastes, EPA Report 600/2-77-104, U.S. Environmental Protection Agency, Research Triangle Park,... 

Silver Chloride. Silver chloride, AgCl, is a white precipitate that forms when chloride ion is added to a silver nitrate solution. The order of solubility of the three silver halides is Cl" > Br" > I. Because of the formation of complexes, silver chloride is soluble in solutions containing excess chloride and in solutions of cyanide, thiosulfate, and ammonia. Silver chloride is insoluble in nitric and dilute sulfuric acid. Treatment with concentrated sulfuric acid gives silver sulfate. 

Electroplating. Most silver-plating baths employ alkaline solutions of silver cyanide. The silver cyanide complexes that are obtained in a very low concentration of free silver ion in solution produce a much firmer deposit of silver during electroplating than solutions that contain higher concentrations. An excess of cyanide beyond that needed to form the Ag(CN)2 complex is employed to control the concentration. The silver is added to the solution either directly as silver cyanide or by oxidation of a silver-rod electrode. Plating baths frequently contain 40—140 g/L of silver cyanide... 

Manufacture. An extensive technology was developed initially ia the 1930s for isolation of ammonium thiocyanate from coke-oven gases, but this technology is no longer practiced ia the United States (372). However, such thiocyanate recovery processes are used iadustrially ia Europe. Likewise, the direct sulfurization of cyanides to thiocyanates is not practiced commercially ia the United States. The principal route used ia the United States is the reaction of carbon disulfide with aqueous ammonia, which proceeds by way of ammonium dithiocarbamate [513-74-6]. Upon heatiag, the ammonium dithiocarbamate decomposes to ammonium thiocyanate and hydrogen sulfide. 

A new cyanide dye for derivatizing thiols has been reported (65). This thiol label can be used with a visible diode laser and provide a detection limit of 8 X 10 M of the tested thiol. A highly sensitive laser-induced fluorescence detector for analysis of biogenic amines has been developed that employs a He—Cd laser (66). The amines are derivatized by naphthalenedicarboxaldehyde in the presence of cyanide ion to produce a cyanobenz[ isoindole which absorbs radiation at the output of He—Cd laser (441.6 nm). Optimization of the detection system yielded a detection limit of 2 x 10 M. 

Spectrophotometric deterrnination at 550 nm is relatively insensitive and is useful for the deterrnination of vitamin B 2 in high potency products such as premixes. Thin-layer chromatography and open-column chromatography have been appHed to both the direct assay of cobalamins and to the fractionation and removal of interfering substances from sample extracts prior to microbiological or radioassay. Atomic absorption spectrophotometry of cobalt has been proposed for the deterrnination of vitamin B 2 in dry feeds. Chemical methods based on the estimation of cyanide or the presence of 5,6-dimethylben2irnida2ole in the vitamin B 2 molecule have not been widely used. 

Cyanide. Industrial processes frequently discharge significant concentrations of cyanide, which can be extremely toxic at very low levels. 

Ethyl carbamate, C2HyN02, is developed naturally during the fermentation of alcohoHc beverages. It also appears in foods such as bread and yogurt. Since ethyl carbamate is not easily distilled, its formation most likely involves a distillable precursor. The mechanism of ethyl carbamate formation probably involves cyanate produced from the oxidation of cyanide or from urea-based compounds in the beer. Cyanate reacts with alcohol to form ethyl carbamate as follows ... 

Dehalogenation of monochlorotoluenes can be readily effected with hydrogen and noble metal catalysts (34). Conversion of -chlorotoluene to Ncyanotoluene is accompHshed by reaction with tetraethyl ammonium cyanide and zero-valent Group (VIII) metal complexes, such as those of nickel or palladium (35). The reaction proceeds by initial oxidative addition of the aryl haHde to the zerovalent metal complex, followed by attack of cyanide ion on the metal and reductive elimination of the aryl cyanide. Methylstyrene is prepared from -chlorotoluene by a vinylation reaction using ethylene as the reagent and a catalyst derived from zinc, a triarylphosphine, and a nickel salt (36). 

Recovery of hydrogen cyanide from coke-oven gases has been dormant in the early 1990s, but new methods involving environmental control of off-gas pollutants may be lea ding the way for a modest return to the recovery of cyanide from coke-oven gases (see Coal conversion process, carbonization). 

Inhalation. The threshold limit value of HCN is 4.7 ppm. This is defined as the maximum average safe exposure limit for a 15-min period by the Occupational Safety and Health Administration. Exposure to 20 ppm of HCN in air causes slight warning symptoms after several hours 50 ppm causes disturbances within an hour 100 ppm is dangerous for exposures of 30 to 60 min and 300 ppm can be rapidly fatal unless prompt, effective first aid is adininistered. There is always a small concentration of cyanide (0.02 to 0.04 mg/L) in the blood, and the body has a mechanism for continuous removal of small amounts, such as from smoking, by converting it to thiocyanate, which is discharged in the urine. 

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