Mercury acetylenic compounds

Mercury Acetylenic compounds, chlorine, fulminic acid, ammonia, ethylene oxide, metals, methyl azide, oxidants, tetracarbonylnickel... 

Acetylenic compounds with replaceable acetylenically bound hydrogen atoms must be kept out of contact with copper, silver, magnesium, mercury or alloys containing them, to avoid formation of explosive metal acetylides. 

See Mercury(II) sulfate, etc., above See Other ACETYLENIC COMPOUNDS... 

The pure diol may be distilled unchanged, but traces of alkali or alkaline earth hydroxides or halides may cause explosive decomposition during distillation. In presence of strong acids, mercury salts may cause violent decomposition of the diol. See other ACETYLENIC COMPOUNDS, CATALYTIC IMPURITY INCIDENTS... 

Acetylenic compounds, especially polyacetylenes, haloacetylenes, and heavy metal salts of acetylenes (copper, silver, and mercury salts are particularly sensitive)... 

DOT CLASSIFICATION 6.1 Label KEEP AWAY FROM FOOD SAFETY PROFILE A poison by ingestion. A skin sensitizer upon long or repeated contact. Moderately explosive. When heated to decomposition it emits acrid smoke and fumes and may explode. Explosive reaction with traces of alkalies, alkali earth hydroxides, halide salts, strong acids, mercury salts + strong acids. See also ACETYLENE COMPOUNDS. 

MERCURY (7439-97-6) Violent reaction with alkali metals, aluminum, acetylenic compounds, azides, boron phosphodiiodide (vapor explodes), bromine, 3-bromopropyne, chlorine, chlorine dioxide, ethylene oxide, lithium, metals, methyl silane (when shaken in air), nitromethane, peroxyformic acid, potassium, propargyl bromide, rubidium, sodium, sodium carbide. Forms sensitive explosive products with acetylene, ammonia (anhydrous), chlorine, picric acid. Increases the explosive sensitivity of methyl azide. Mixtures with hot sulfuric acid can be explosive. Incompatible with calcium, sodium acetylide, nitric acid. Reacts with copper, silver, and many other metals (except iron), forming amalgams. 

The oxydation of acetylenic and related steroid hormones was examined in aqueous MeOH solution by several electrochemical techniques at Hg electrodes The electrochemical behaviour was strongly affected by reactant and product adsorption and a mercury acetylide compound was formed during the controlled potential electrolysis. 

He showed that sodium salts of aliphatic primary and secondary nitrocompounds react with acids to form carbonyl compounds 2R2CHNO2 = 2R2C0+N2O+ H2O. Nef supported the theory of bivalent carbon. In the preparation of the explosive mercuric salt of nitromethane, he found that mercury fulminate is formed and regarded fulminic acid as C N OH, the reaction being Hg(CH2 N0 0)2==Hg(0-N C)2 + 2H20. He prepared the explosive addition compound of fulminic acid and hydrogen chloride, HON CHCl. In researches on acetylene compounds he prepared explosive di-iodoacetylene, IC-CI (he formulated it IgC.-C). He discovered the reaction between sodium acetylene and a ketone, followed by hydrolysis, to form an acetylenic carbinol ... 

Under certain circumstances acetylene combines with the metals copper, silver and mercury to form acetylides. As a dry substance these acetylene compounds are explosive and ignite through impact or friction. Compared to the other acetylides, silver acetylide releases the largest amount of energy in an explosion. Acetylides can originate and precipitate from watery saline solutions of the metals mentioned above under certain conditions regarding temperature, pH value and concentration. These precipitation reactions were previously used in the wet chemical acetylene analytics. 

Meier IK, Marsella JA (1993) Hydration of acetylenic compounds without using mercury. J Mol Cat 78 31 2... 

Mercury(II) nitrate Acetylene, aromatics, ethanol, hypophosphoric acid, phosphine, unsaturated organic compounds... 

Atomic absorption spectroscopy is more suited to samples where the number of metals is small, because it is essentially a single-element technique. The conventional air—acetylene flame is used for most metals however, elements that form refractory compounds, eg, Al, Si, V, etc, require the hotter nitrous oxide—acetylene flame. The use of a graphite furnace provides detection limits much lower than either of the flames. A cold-vapor-generation technique combined with atomic absorption is considered the most suitable method for mercury analysis (34). 

Methyl ketones are important intermediates for the synthesis of methyl alkyl carbinols, annulation reagents, and cyclic compounds. A common synthetic method for the preparation of methyl ketones is the alkylation of acetone derivatives, but the method suffers limitations such as low yields and lack of regioselectivity. Preparation of methyl ketones from olefins and acetylenes using mercury compounds is a better method. For example, hydration of terminal acetylenes using HgSO gives methyl ketones cleanly. Oxymercuration of 1-olefins and subsequent oxidation with chromic oxide is... 

Mercury(II) cyanide Mercury(I) nitrate Mercury(II) nitrate Fluorine, hydrogen cyanide, magnesium, sodium nitrite Phosphorus Acetylene, aromatics, ethanol, hypophosphoric acid, phosphine, unsaturated organic compounds... 

In from eight to ten hours up to 10 1. of acetylene are taken up. The colourless intermediate mercury compound very soon begins to separate. After the passing in of acetylene has ceased the whole of the reaction mixture is transferred to a round-bottomed flask and heated on a conical (Babo) air bath, while steam is passed through to decompose the mercury compound. The acetaldehyde liberated distils with the steam. An apparatus similar to that described under (a) is used one receiver containing ether and cooled in a freezing mixture is sufficient. The aldehyde is precipitated from the ethereal solution as aldehyde-ammonia in the manner described above. Yield of aldehyde-ammonia 5-6 g. 

Catalytic forms of copper, mercury and silver acetylides, supported on alumina, carbon or silica and used for polymerisation of alkanes, are relatively stable [3], In contact with acetylene, silver and mercury salts will also give explosive acetylides, the mercury derivatives being complex [4], Many of the metal acetylides react violently with oxidants. Impact sensitivities of the dry copper derivatives of acetylene, buten-3-yne and l,3-hexadien-5-yne were determined as 2.4, 2.4 and 4.0 kg m, respectively. The copper derivative of a polyacetylene mixture generated by low-temperature polymerisation of acetylene detonated under 1.2 kg m impact. Sensitivities were much lower for the moist compounds [5], Explosive copper and silver derivatives give non-explosive complexes with trimethyl-, tributyl- or triphenyl-phosphine [6], Formation of silver acetylide on silver-containing solders needs higher acetylene and ammonia concentrations than for formation of copper acetylide. Acetylides are always formed on brass and copper or on silver-containing solders in an atmosphere of acetylene derived from calcium carbide (and which contains traces of phosphine). Silver acetylide is a more efficient explosion initiator than copper acetylide [7],... 

It is unlikely that this is due to a simple difference in the solubility of elemental mercury in these cuts it is more likely that there is a chemical interaction between the acetylenic species (ME and PD) with mercury. Elemental mercury and MAPD alone would not form Hg organometaUic compounds at room temperature, but an interaction... 

Again several alkyls add—molybdenum, chromium, iron, cobalt, nickel, the alkali metal alkyls and aluminum alkyls react. A tin alkoxide has recently been studied by Russian workers and found to add to acetylenes. Mercury chloride, of course, adds and two cobalt—cobalt bonded compounds add to acetylene. The second is questionable because it dissociates in solution and the reaction may be a radical reaction, one cobalt adding to each end of the triple bond. 

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