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Sodium hydroxide is a highly caustic base and alkali that decomposes proteins at ordinary ambient temperatures and may cause severe chemical burns. It is highly soluble in water, and readily absorbs moisture and carbon dioxide from the air. It forms a series of hydrates NaOH·nH2O.[11] The monohydrate NaOH·H2O crystallizes from water solutions between 12.3 and 61.8 °C. The commercially available "sodium hydroxide" is often this monohydrate, and published data may refer to it instead of the anhydrous compound.
Sodium hydroxide is used in many industries: in the manufacture of pulp and paper, textiles, drinking water, soaps and detergents, and as a drain cleaner. Worldwide production in 2004 was approximately 60 million tons, while demand was 51 million tons.[13]
Pure sodium hydroxide is a colorless crystalline solid that melts at 318 °C (604 °F) without decomposition, and with a boiling point of 1,388 °C (2,530 °F). It is highly soluble in water, with a lower solubility in polar solvents such as ethanol and methanol.[14] NaOH is insoluble in ether and other non-polar solvents.
Similar to the hydration of sulfuric acid, dissolution of solid sodium hydroxide in water is a highly exothermic reaction[15] where a large amount of heat is liberated, posing a threat to safety through the possibility of splashing. The resulting solution is usually colorless and odorless. As with other alkaline solutions, it feels slippery with skin contact due to the process of saponification that occurs between NaOH and natural skin oils.
Concentrated (50%) aqueous solutions of sodium hydroxide have a characteristic viscosity, 78 mPa·s, that is much greater than that of water (1.0 mPa·s) and near that of olive oil (85 mPa·s) at room temperature. The viscosity of aqueous NaOH, as with any liquid chemical, is inversely related to its service temperature, i.e., its viscosity decreases as temperature increases, and vice versa. The viscosity of sodium hydroxide solutions plays a direct role in its application as well as its storage.[14]
Sodium hydroxide can form several hydrates NaOH·nH2O, which result in a complex solubility diagram that was described in detail by S. U. Pickering in 1893.[16] The known hydrates and the approximate ranges of temperature and concentration (mass percent of NaOH) of their saturated water solutions are:[11]
NaOH and its monohydrate form orthorhombic crystals with the space groups Cmcm (oS8) and Pbca (oP24), respectively. The monohydrate cell dimensions are a = 1.1825, b = 0.6213, c = 0.6069 nm. The atoms are arranged in a hydrargillite-like layer structure, with each sodium atom surrounded by six oxygen atoms, three each from hydroxide ions and three from water molecules. The hydrogen atoms of the hydroxyls form strong bonds with oxygen atoms within each O layer. Adjacent O layers are held together by hydrogen bonds between water molecules.[21]
In 1986, an aluminium road tanker in the UK was mistakenly used to transport 25% sodium hydroxide solution,[23] causing pressurization of the contents and damage to the tanker. The pressurization was due to the hydrogen gas which is produced in the reaction between sodium hydroxide and aluminium:
Unlike sodium hydroxide, which is soluble, the hydroxides of most transition metals are insoluble, and therefore sodium hydroxide can be used to precipitate transition metal hydroxides. The following colours are observed:
Aluminium hydroxide is used as a gelatinous flocculant to filter out particulate matter in water treatment. Aluminium hydroxide is prepared at the treatment plant from aluminium sulfate by reacting it with sodium hydroxide or bicarbonate.
Sodium hydroxide can be used for the base-driven hydrolysis of esters (as in saponification), amides and alkyl halides.[14] However, the limited solubility of sodium hydroxide in organic solvents means that the more soluble potassium hydroxide (KOH) is often preferred. Touching a sodium hydroxide solution with bare hands, while not recommended, produces a slippery feeling. This happens because oils on the skin such as sebum are converted to soap.Despite solubility in propylene glycol it is unlikely to replace water in saponification due to propylene glycol's primary reaction with fat before reaction between sodium hydroxide and fat.
Sodium hydroxide is industrially produced as a 50% solution by variations of the electrolytic chloralkali process.[24] Chlorine gas is also produced in this process.[24] Solid sodium hydroxide is obtained from this solution by the evaporation of water. Solid sodium hydroxide is most commonly sold as flakes, prills, and cast blocks.[13]
In 2004, world production was estimated at 60 million dry tonnes of sodium hydroxide, and demand was estimated at 51 million tonnes.[13] In 1998, total world production was around 45 million tonnes. North America and Asia each contributed around 14 million tonnes, while Europe produced around 10 million tonnes. In the United States, the major producer of sodium hydroxide is Olin, which has annual production around 5.7 million tonnes from sites at Freeport, Texas, and Plaquemine, Louisiana, St Gabriel, Louisiana, McIntosh, Alabama, Charleston, Tennessee, Niagara Falls, New York, and Becancour, Canada. Other major US producers include Oxychem, Westlake, Shintek and Formosa. All of these companies use the chloralkali process.[25]
Historically, sodium hydroxide was produced by treating sodium carbonate with calcium hydroxide in a metathesis reaction which takes advantage of the fact that sodium hydroxide is soluble, while calcium carbonate is not. This process was called causticizing.[26]
This reaction is commonly used for demonstrating the reactivity of alkali metals in academic environments; however, it is not commercially viable, as the isolation of sodium metal is typically performed by reduction or electrolysis of sodium compounds including sodium hydroxide.
Sodium hydroxide is a popular strong base used in industry. Sodium hydroxide is used in the manufacture of sodium salts and detergents, pH regulation, and organic synthesis. In bulk, it is most often handled as an aqueous solution,[27] since solutions are cheaper and easier to handle.
For example, in the petroleum industry, sodium hydroxide is used as an additive in drilling mud to increase alkalinity in bentonite mud systems, to increase the mud viscosity, and to neutralize any acid gas (such as hydrogen sulfide and carbon dioxide) which may be encountered in the geological formation as drilling progresses.
Poor quality crude oil can be treated with sodium hydroxide to remove sulfurous impurities in a process known as caustic washing. As above, sodium hydroxide reacts with weak acids such as hydrogen sulfide and mercaptans to yield non-volatile sodium salts, which can be removed. The waste which is formed is toxic and difficult to deal with, and the process is banned in many countries because of this. In 2006, Trafigura used the process and then dumped the waste in Ivory Coast.[28][29]
Sodium hydroxide is also widely used in pulping of wood for making paper or regenerated fibers. Along with sodium sulfide, sodium hydroxide is a key component of the white liquor solution used to separate lignin from cellulose fibers in the kraft process. It also plays a key role in several later stages of the process of bleaching the brown pulp resulting from the pulping process. These stages include oxygen delignification, oxidative extraction, and simple extraction, all of which require a strong alkaline environment with a pH > 10.5 at the end of the stages.
In a similar fashion, sodium hydroxide is used to digest tissues, as in a process that was used with farm animals at one time. This process involved placing a carcass into a sealed chamber, then adding a mixture of sodium hydroxide and water (which breaks the chemical bonds that keep the flesh intact). This eventually turns the body into a liquid with a dark brown color,[32][33] and the only solids that remain are bone hulls, which can be crushed between one's fingertips.[34]
Sodium hydroxide is a dangerous chemical due to its ability to hydrolyze protein. If a dilute solution is spilled on the skin, burns may result if the area is not washed thoroughly and for several minutes with running water. Splashes in the eye can be more serious and can lead to blindness.[37]
Strong bases attack aluminium. Sodium hydroxide reacts with aluminium and water to release hydrogen gas. The aluminium takes the oxygen atom from sodium hydroxide, which in turn takes the oxygen atom from the water, and releases the two hydrogen atoms. The reaction thus produces hydrogen gas and sodium aluminate. In this reaction, sodium hydroxide acts as an agent to make the solution alkaline, which aluminium can dissolve in.
Sodium aluminate is an inorganic chemical that is used as an effective source of aluminium hydroxide for many industrial and technical applications. Pure sodium aluminate (anhydrous) is a white crystalline solid having a formula variously given as NaAlO2, Na3AlO3, Na[Al(OH)4], Na2O·Al2O3 or Na2Al2O4. Formation of sodium tetrahydroxoaluminate(III) or hydrated sodium aluminate is given by:[38]
In the Bayer process, sodium hydroxide is used in the refining of alumina containing ores (bauxite) to produce alumina (aluminium oxide) which is the raw material used to produce aluminium metal via the electrolytic Hall-Héroult process. Since the alumina is amphoteric, it dissolves in the sodium hydroxide, leaving impurities less soluble at high pH such as iron oxides behind in the form of a highly alkaline red mud.
For the manufacture of biodiesel, sodium hydroxide is used as a catalyst for the transesterification of methanol and triglycerides. This only works with anhydrous sodium hydroxide, because combined with water the fat would turn into soap, which would be tainted with methanol. NaOH is used more often than potassium hydroxide because it is cheaper and a smaller quantity is needed. Due to production costs, NaOH, which is produced using common salt is cheaper than potassium hydroxide.[40] 2b1af7f3a8
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