Lithium, Elemental

CAS RN: 7439-93-2

Reactivities / Incompatibilities

Reacts with water forming lithium hydroxide and hydrogen. Keep under mineral oil or other liquid free from oxygen or water.
Water. Powdered metal reacts explosively; shavings react violently with hot water, ... vigorously with cold water.
Platinum and molten lithium react violently at 540 deg C plus or minus 20 deg C. An intermetallic cmpd is formed.
In electric battery systems, lithium is inert to the electrolyte components in absence of carbon, but in presence of over 10% of carbon (pre-mixed by grinding with the metal), contact with the electrolyte mixture leads to ignition or explosion ... Pregrinding lithium with carbon leads to ignition on contact with sulfinyl chloride in electric battery systems.
Reduction of tetralin to octalin with lithium and ethylenediamine proceeds slowly, but if heated to 85 deg C it becomes violent, with rapid evolution of hydrogen.
Finely divided metal may ignite in air at ambient temperature and massive metal above the m.p., 180 deg C, especially if oxide or nitride is present. ... Lithium will burn in oxygen, nitrogen or carbon dioxide, and when alight it will remove the combined oxygen in sand, sodium carbonate, etc., it is difficult to extinguish once alight. Molten lithium is extremely reactive and will attack concrete and refractory materials ... A well-tried and usually uneventful demonstration of atmospheric oxidation of molten lithium led to an explosion. A high degree of correlation of incidence of explosions with high atmospheric humidity was demonstrated, with the intensity of explosion apparently directly related to the purity of the sample of metal ... While cleaning lithium wire by washing with hexane, the wire must be dried carefully with a paper towel. Too-vigorous rubbing will cause a fire.
... Mixtures of carbon disulfide with ... lithium are capable of detonation by shock, though not by heating.
Accidental contamination of lithium strip with anhydrous chromium trichloride or zirconium tetrachloride caused it to ignite and burn vigorously in the nitrogen atmosphere of a glove box.
When 15 mL of nitric acid were poured onto 15 g of lithium in an attempt to dissolve the metal, a small fire started in the flask. In less than a minute, the reaction was so vigorous that burning lithium was thrown upward in the lab hood.
Vigorous stirring of finely powdered lithium in bromobenzene resulted in an explosion.
In a modified prepn of phenyllithium, bromobenzene was added to finely powdered lithium (rather than coarse particles) in ether. The reaction appeared to be proceeding normally, but after about 30 min it became very vigorous and accelerated to explosion. It was thought that the powdered metal may have been partially coated with oxide or nitride which abraded during stirring, exposing a lot of fresh metal surface on the powdered metal.
Halogens. Mixtures with bromine explode only on heavy impact; mixtures with iodine are highly exothermic above 200 deg C.
Lithium burns in gaseous hydrogen.
The reaction of lithium is violent with both strongly heated arsenic and phosphorus.
Lithium will burn in air, oxygen, nitrogen, and carbon dioxide. The susceptibility of molten lithium surfaces to spontaneous ignition is increased by the presence of lithium oxides or nitrides. These reactions and the reaction with water are extremely violent at higher temperatures. Contact with halogenated hydrocarbons can produce extremely violent reactions, especially on impact ... The reaction of lithium and nitrogen incr greatly as the metal melts.
Evolves hydrogen and ignites on contact with water.
The product of the reaction between lithium and carbon monoxide, lithium carbonyl, detonates violently with water, igniting gaseous products.
Chlorine vapors and cesium, lithium, or rubidium react with luminous flame.
Diborane reacts spontaneously with aluminum and lithium to form hydrides that ignite in air.
Maleic anhydride decomp explosively in the presence of alkali metals /eg, lithium/.
Sodium chloride extinguishant should not be used on lithium fires since the reaction releases sodium and results in a more violent fire.
Lithium reacts with sodium nitrite to form lithium sodium hydronitrite, a cmpd which decomp violently around 100 to 130 deg C.
Interaction /of lithium and sulfur/ when either is molten is very violent and, even in presence of inert diluent, the reaction begins explosively. Reaction of sulfur with lithium dissolved in liq ammonia at -33 deg C is also very vigorous.
Interaction to form lithium amalgam is violently exothermic and may be explosive if large pieces of lithium are used.
Lithium blocks containing traces of nitride but which had been supplied under argon in sealed tins were cut into 1 cm strips and stored under air in closed tins overnight until used. Lithium containing some nitride reacts slowly with nitrogen at ambient temp to form more nitride, which autocatalyses the reaction which progressively accelerates and becomes exothermic. The strips of lithium reacted with the nitrogen of the air in the closed tins, causing a partial vacuum and an oxygen-enriched atmosphere. When the tins collapsed, the impact and/or compression of the oxygen-enriched atmosphere caused ignition and fierce burning of the lithium, which was very difficult to extinguish inside the crushed tins.
/Bromine pentafluoride/ contacts with ... /lithium powder/ at ambient or slightly elevated temp is violent, ignition often occurring ...
Interaction of lithium or calcium with chlorine tri- or penta-fluorides is hypergolic and particularly energetic.
The preparation of 1-lithio-3-dimethylaminopropane ... involved reaction of the chloro cmpd with a mineral oil dispersion of lithium (30%) in hexane at 0 deg. It had previously been found that lithium with a sodium content of some 0.3% reacted slowly, even at temp above 15 deg C. When a new batch of lithium (later found to contain 1.9% of sodium) was used, a vigorous reaction which set in at between 0 and -35 deg C led to ignition of the reaction mixture. Although it was known that the presence of sodium incr the reactivity of lithium towards organohalides up to a sodium content of 2%, it had not been appreciated that such wide variations in reactivity were likely, or that a hazardous situation could develop. However, a more likely cause proposed for the runaway exothermic reaction was the fact that all the reagents were mixed at 0 deg C, rather than the more usual course of adding the halide slowly to the lithium dispersion in a hydrocarbon solvent lower-boiling than hexane, so as to maintain gentle reflux at 35 to 50 deg C ...
Contact of diazomethane with alkali metals causes explosions
Mixtures of lithium shavings and several halocarbon derivatives are impact-sensitive and will explode, sometime violently. Such materials include: bromoform, carbon tetrabromide, carbon tetrachloride, carbon tetraiodide, chloroform, dichloromethane, diiodomethane, fluorotrichloromethane, tetrachloroethylene, trichloroethylene and 1,1,2-trichlorotrifluoroethane. In an operational incident shearing samples off a lithium billet immersed in carbon tetrachloride caused an explosion and continuing combustion of the immersed metal. Lithium which had been washed in carbon tetrachloride to remove traces of oil exploded when cut with a knife. Hexane is recommended as a suitable washing solvent. A few drops of carbon tetrachloride on burning lithium was without effect, but a 25 cc portion caused a violent explosion.
Interaction /of lithium and mercury/ to form lithium amalgam is violently exothermic and may be explosive if large pieces of lithium are used. An improved technique, using p-cymene as inerting diluent, is described ...
Lithium is used to reduce metallic oxides in metallurgical operations, and the reactions, after initiation at moderate temp, are violently exothermic and rapid. Chromium(III) oxide reacts at 185 deg C, reaching 965 deg; similarly molybdenum trioxide (180 to 1400 deg), niobium pentoxide (320 to 490 deg), titanium dioxide (200 to 400 to 1400 deg), tungsten trioxide (200 to 1030 deg), vanadium pentoxide (394 to 768 deg); also iron(II) sulfide (260 to 945 deg), and manganese telluride (230 to 600 deg). Residual mixtures from lithium production cells containing lithium and rust sometime ignite when left as thin layers exposed to air.
Formation of various intermetallic cmpd of lithium by melting with aluminium, bismuth, calcium, lead, mercury, silicon, strontium, thallium or tin may be very vigorous and dangerous to effect. Ignition and combustion hazards of alloys of lithium with aluminium or magnesium have been studied. the latter being more reactive than the former. Use of nitrogen as a protective medium for alloy powders is ineffective, mixed nitrides being formed.
Mixtures of finely divided metal and shredded polymer /of poly(1,1-difluoroethylene-hexafluoropropylene) (Viton)/ ignited in air on contact with water, or on heating to 369 deg C, or at 354 deg C under argon.
An experimental investigation of explosion hazards in lithium-sulfinyl chloride cells on forced discharge showed cathode limited cells are safe, but anode limited cells may explode without warning signs. Extended reversal at -40 deg C caused explosion on warming to ambient temp, owing to thermal runaway caused by accelerated corrosion of lithium. The violent explosion of a large prismatic cell of a battery is described.
Two reports cover safety studies on lithium-sulfur dioxide batteries. The cause of violent venting of discharged lithium-sulfur dioxide cells was ascribed to corrosion in a glass to metal seal and formation of lithium-aluminium alloys and other cathode reaction product(s) which are both shock-sensitive. The pyrophoric charged anodes of lithium-sulfur dioxide batteries are covered with smooth crystalline platelets, but partially discharged anodes are covered with a rough, non-adherent layer of lithium dithionite. The explosions which may occur during charging are attributed to thermal runaway reactions of lithium and sulfur dioxide to form lithium dithionite, LiOSO.SO.OLi.
Interaction /between trifluoromethyl hypofluorite and lithium/ set in at about 170 deg C with a sufficient exotherm to melt the glass container.
... Prolonged contact with steam forms a thermally insulating layer which promotes overheating of the metal and may lead to a subsequent explosion as the insulating layer breaks up.
Gallium ... undergoes violent reaction on contact with ... lithium ...
Phosphorus reacts vigorously below 250 deg C with ... lithium ...
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