Hydrogen cyanide water

The cycloaddition reaction on the azadiene substrate is usually followed by elimination of nitrogen, hydrogen cyanide, water, amines, or other simple compounds and, as a result of this retrograde process, a new carbo- or heterocyclic system is formed (Scheme 67). The method provides a very convenient route to the synthesis of many not easily accessible compounds. In... 

Methane Ethene Carbon (Ethylene) dioxide Ethyne (Acetylene) Ammonia Nitrous acid Hydrogen cyanide Water Formaldehyde... 

In the recovery section, the effluent vapor from the reactor is scrubbed to recover the organics. Non-condensables may be vented or incinerated depending on local regulations. In the purification section, hydrogen cyanide, water and impurities are separated from the crude acrylonitrile in a series of fractionation steps to produce acrylonitrile product that meets specification. Hydrogen cyanide (HCN) may be recovered as a byproduct or incinerated. 

Half-reaction (i) means that Co(II) in aqueous solution cannot be oxidised to Co(III) by adding ammonia to obtain the complexes in (ii), oxidation is readily achieved by, for example, air. Similarly, by adding cyanide, the hexacyanocobaltate(II) complex becomes a sufficiently strong reducing agent to produce hydrogen from water ... 

Nitrogen and sulphur present. Just acidify 2-3 ml. of the fusion solution with dilute nitric acid, and evaporate to half the original volume in order to expel hydrogen cyanide and/or hydrogen sulphide which may be present. Dilute with an equal volume of water. If only one halogen is present, proceed as in tests (i) or (iii). If one or more halogens may be present, use tests (ii), (iii) or (iv). 

The conversion of primary alcohols and aldehydes into carboxylic acids is generally possible with all strong oxidants. Silver(II) oxide in THF/water is particularly useful as a neutral oxidant (E.J. Corey, 1968 A). The direct conversion of primary alcohols into carboxylic esters is achieved with MnOj in the presence of hydrogen cyanide and alcohols (E.J. Corey, 1968 A,D). The remarkably smooth oxidation of ethers to esters by ruthenium tetroxide has been employed quite often (D.G. Lee, 1973). Dibutyl ether affords butyl butanoate, and tetra-hydrofuran yields butyrolactone almost quantitatively. More complex educts also give acceptable yields (M.E. Wolff, 1963). 

Compounds with active hydrogen add to the carbonyl group of acetone, often followed by the condensation of another molecule of the addend or loss of water. Hydrogen sulfide forms hexamethyl-l,3,5-trithiane probably through the transitory intermediate thioacetone which readily trimerizes. Hydrogen cyanide forms acetone cyanohydrin [75-86-5] (CH2)2C(OH)CN, which is further processed to methacrylates. Ammonia and hydrogen cyanide give (CH2)2C(NH2)CN [19355-69-2] ix.orn. 6<55i the widely used polymerization initiator, azobisisobutyronitrile [78-67-1] is made (4). 

A solution of sodium cyanide [143-33-9] (ca 25%) in water is heated to 65—70°C in a stainless steel reaction vessel. An aqueous solution of sodium chloroacetate [3926-62-3] is then added slowly with stirring. The temperature must not exceed 90°C. Stirring is maintained at this temperature for one hour. Particular care must be taken to ensure that the hydrogen cyanide, which is formed continuously in small amounts, is trapped and neutrali2ed. The solution of sodium cyanoacetate [1071 -36-9] is concentrated by evaporation under vacuum and then transferred to a glass-lined reaction vessel for hydrolysis of the cyano group and esterification. The alcohol and mineral acid (weight ratio 1 2 to 1 3) are introduced in such a manner that the temperature does not rise above 60—80°C. For each mole of ester, ca 1.2 moles of alcohol are added. 

Mercuric Cyanides. Mercuric cyanide7, Hg(CN)2, is a white tetragonal crystalline compound, Httle used except to a small degree as an antiseptic. It is prepared by reaction of an aqueous slurry of yellow mercuric oxide (the red is less reactive) with excess hydrogen cyanide. The mixture is heated to 95°C, filtered, crystallized, isolated, and dried. Its solubihty in water is 10% at 25°C. 

Cobalt(II) oxalate [814-89-1], C0C2O4, is a pink to white crystalline material that absorbs moisture to form the dihydrate. It precipitates as the tetrahydrate on reaction of cobalt salt solutions and oxaUc acid or alkaline oxalates. The material is insoluble in water, but dissolves in acid, ammonium salt solutions, and ammonia solution. It is used in the production of cobalt powders for metallurgy and catalysis, and is a stabilizer for hydrogen cyanide. 

Under certain conditions hydrogen cyanide can polymerize to black soHd compounds, eg, hydrogen cyanide homopolymer [26746-21-4] (1) and hydrogen cyanide tetramer [27027-02-2], C H N (2). There is usually an incubation period before rapid onset of polymer formation. Temperature has an inverse logarithmic effect on the incubation time. Acid stabilizers such as sulfuric and phosphoric acids prevent polymerization. The presence of water reduces the incubation period. 

Although hydrogen cyanide is a weak acid and is normally not corrosive, it has a corrosive effect under two special conditions (/) water solutions of hydrogen cyanide cause transcrystalline stress cracking of carbon steels under stress even at room temperature and in dilute solution and (2) water solutions of hydrogen cyanide containing sulfuric acid as a stabilizer severely corrode steel (qv) above 40°C and stainless steels above 80°C. 

In one patent (31), a filtered, heated mixture of air, methane, and ammonia ia a volume ratio of 5 1 1 was passed over a 90% platinum—10% rhodium gauze catalyst at 200 kPa (2 atm). The unreacted ammonia was absorbed from the off-gas ia a phosphate solution that was subsequently stripped and refined to 90% ammonia—10% water and recycled to the converter. The yield of hydrogen cyanide from ammonia was about 80%. On the basis of these data, the converter off-gas mol % composition can be estimated nitrogen, 49.9% water, 21.7% hydrogen, 13.5% hydrogen cyanide, 8.1% carbon monoxide, 3.7% carbon dioxide, 0.2% methane, 0.6% and ammonia, 2.3%. 

Specifications are 99.5 wt % hydrogen cyanide (min), 0.5 wt % water (max), 0.06—0.10% acidity, and color not darker than APHA 20. A combination of H2SO4 (or H PO and SO2 acts as a stabilizer to prevent polymerization H2SO4 stabilizes the Hquid phase and SO2 stabilizes the vapor phase. 

A German process produces a high (99%) sodium cyanide assay by absorbing the gases from a BMA-type hydrogen cyanide reactor direcdy in sodium hydroxide solution (56). The resulting sodium cyanide solution is heated in a crystallizer to remove water, and form sodium cyanide crystals. 

These cyanides are all soluble in water. The cyanide ion is weaMy held so that water solutions have a much stronger odor of hydrogen cyanide above them than sodium and potassium cyanide solution. 

Ammonium cyanide may be prepared in solution by passing hydrogen cyanide into aqueous ammonia at low temperatures. It may also be prepared from barium cyanide and ammonium sulfate, or calcium cyanide with ammonium carbonate. It may be prepared in the dry state by gentiy heating a mixture of potassium cyanide or ferrocyanide and ammonium chloride, and condensing the vapor in a cooled receiver. Ammonium cyanide is soluble in water or alcohol. The vapor above soHd NH CN contains free NH and HCN, a very toxic mixture. 

Formaldehyde Cyanohydrin. This cyanohydrin, also known as glycolonitrile [107-16-4], is a colorless Hquid with a cyanide odor. It is soluble in water, alcohol, and diethyl ether. Equimolar amounts of 37% formaldehyde and aqueous hydrogen cyanide mixed with a sodium hydroxide catalyst at 2°C for one hour give formaldehyde cyanohydrin in 79.5% yield (22). 

Acetaldehyde Cyanohydrin. This cyanohydrin, commonly known as lactonitnle, is soluble in water and alcohol, but insoluble in diethyl ether and carbon disulfide. Lactonitnle is used chiefly to manufacture lactic acid and its derivatives, primarily ethyl lactate. Lactonitnle [78-97-7] is manufactured from equimolar amounts of acetaldehyde and hydrogen cyanide containing 1.5% of 20% NaOH at —10 20 ° C. The product is stabili2ed with sulfuric acid (28). Sulfuric acid hydroly2es the nitrile to give a mixture of lactic acid [598-82-3] and ammonium bisulfate. 

Ethylene Cyanohydrin. This cyanohydrin, also known as hydracrylonitnle or glycocyanohydrin [109-78-4] is a straw-colored Hquid miscible with water, acetone, methyl ethyl ketone, and ethanol, and is insoluble in benzene, carbon disulfide, and carbon tetrachloride. Ethylene cyanohydrin differs from the other cyanohydrins discussed here in that it is a P-cyanohydrin. It is formed by the reaction of ethylene oxide with hydrogen cyanide. 

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