Hydrochloric acid
is the aqueous solution of hydrogen chloride gas (HCl). It is a strong acid, the major component of gastric acid, and of wide industrial use. Hydrochloric acid must be handled with appropriate safety precautions because it is a highly-corrosive liquid.
Hydrochloric acid, or muriatic acid by its historical but still occasionally-used name, has been an important and frequently-used chemical from early history, and was discovered by the alchemist Jabir ibn Hayyan around the
year 800. It was used throughout the Middle Ages by alchemists in the quest for the philosopher's stone, and later by several European scientists including Glauber, Priestley, and Davy in order to help establish modern chemical
knowledge.
From the Industrial Revolution, it became an important industrial chemical for many applications, including the large-scale production of organic compounds, such as vinyl chloride for PVC plastic, and MDI/TDI for
polyurethane, and smaller-scale applications, such as production of gelatin and other ingredients in food, and leather processing. About 20 million metric tonnes of HCl gas are produced annually.
History
Hydrochloric acid
was first discovered around 800 AD by the alchemist Jabir ibn Hayyan (Geber), by mixing common salt with vitriol (sulfuric acid). Jabir discovered many important chemicals, and recorded his findings in over twenty books, which
carried his chemical knowledge of hydrochloric acid and other basic chemicals for hundreds of years. Jabir's invention of the gold-dissolving aqua regia, consisting of hydrochloric acid and nitric acid, was of great interest to
alchemists searching for the philosopher's stone.
Jabir ibn Hayyan, medieval manuscript drawing
Jabir ibn Hayyan, medieval manuscript drawing
In the Middle Ages, hydrochloric acid was known to European alchemists as
spirit of salt or acidum salis. Gaseous HCl was called marine acid air. The old (pre-systematic) name muriatic acid has the same origin (muriatic means "pertaining to brine or salt"), and this name is still sometimes
used. Notable production was recorded by Basilius Valentinus, the alchemist-canon of the Benedictine priory Sankt Peter in Erfurt, Germany in the fifteenth century. In the seventeenth century, Johann Rudolf Glauber from Karlstadt
am Main, Germany used sodium chloride salt and sulfuric acid for the preparation of sodium sulfate in the Mannheim process, releasing hydrogen chloride gas. Joseph Priestley of Leeds, England prepared pure hydrogen chloride in
1772, and in 1818 Humphry Davy of Penzance, England proved that the chemical composition included hydrogen and chlorine.
During the Industrial Revolution in Europe, demand for alkaline substances such as soda ash increased,
and the new industrial soda process by Nicolas Leblanc (Issoundun, France) enabled cheap large-scale production. In the Leblanc process, salt is converted to soda ash, using sulfuric acid, limestone, and coal, releasing hydrogen
chloride as a by-product. Until the Alkali Act of 1863, excess HCl was vented to the air. After the passage of the act, soda ash producers were obliged to absorb the waste gas in water, producing hydrochloric acid on an industrial
scale.
When early in the twentieth century the Leblanc process was effectively replaced by the Solvay process without the hydrochloric acid by-product, hydrochloric acid was already fully settled as an important chemical in
numerous applications. The commercial interest initiated other production methods which are still used today, as described below. Today, most hydrochloric acid is made by absorbing hydrogen chloride from industrial organic
compounds production.
Hydrochloric acid is listed as a Table II precursor under the 1988 Convention Against Illicit Traffic in Narcotic Drugs and Psychotropic Substances because of its use in the production of heroin,
cocaine, and methamphetamine.
Chemistry
Acid titration
Hydrogen chloride (HCl) is a monoprotic acid, which means it can dissociate (i.e., ionize) only once to give up one H+ ion (a single proton). In aqueous
hydrochloric acid, the H+ joins a water molecule to form a hydronium ion, H3O+:
HCl + H2O ¥ H3O+ + Cl¥
The other ion formed is Cl¥, the chloride ion. Hydrochloric acid can
therefore be used to prepare salts called chlorides, such as sodium chloride. Hydrochloric acid is a strong acid, since it is fully dissociated in water.
Monoprotic acids have one acid dissociation constant, Ka, which
indicates the level of dissociation in water. For a strong acid like HCl, the Ka is large. Theoretical attempts to assign a Ka to HCl have been made. When chloride salts such as NaCl are added to aqueous HCl they have practically
no effect on pH, indicating that Cl¥ is an exceedingly weak conjugate base and that HCl is fully dissociated in aqueous solution. For intermediate to strong solutions of hydrochloric acid, the assumption that H+ molarity (a unit of
concentration) equals HCl molarity is excellent, agreeing to four significant digits.
Of the seven common strong acids in chemistry, all of them inorganic, hydrochloric acid is the monoprotic acid least likely to undergo an
interfering oxidation-reduction reaction. It is one of the least hazardous strong acids to handle; despite its acidity, it produces the less reactive and non-toxic chloride ion. Intermediate strength hydrochloric acid solutions are
quite stable, maintaining their concentrations over time. These attributes, plus the fact that it is available as a pure reagent, mean that hydrochloric acid makes an excellent acidifying reagent and acid titrant (for determining
the amount of an unknown quantity of base in titration). Strong acid titrants are useful because they give more distinct endpoints in a titration, making the titration more precise. Hydrochloric acid is frequently used in chemical
analysis and to digest samples for analysis. Concentrated hydrochloric acid will dissolve some metals to form oxidized metal chlorides and hydrogen gas. It will produce metal chlorides from basic compounds such as calcium carbonate
or copper(II) oxide. It is also used as a simple acid catalyst for some chemical reactions.
Physical properties
The physical properties of hydrochloric acid, such as boiling and melting points, density, and pH depend on the
concentration or molarity of HCl in the acid solution. They can range from those of water at 0% HCl to values for fuming hydrochloric acid at over 40% HCl.
Hydrochloric acid as the binary (two-component) mixture of HCl and
H2O has a constant-boiling azeotrope at 20.2% HCl and 108.6 °C (227 °F). There are four constant-crystallization eutectic points for hydrochloric acid, between the crystal form of HCl·H2O (68% HCl), HCl·2H2O (51% HCl), HCl·3H2O
(41% HCl), HCl·6H2O (25% HCl), and ice (0% HCl). There is also a metastable eutectic point at 24.8% between ice and the HCl·3H2O crystallization
Production
Main article: hydrogen chloride
Hydrochloric acid is
prepared by dissolving hydrogen chloride in water. Hydrogen chloride can be generated in many ways, and thus several different precursors to hydrochloric acid exist. The large-scale production of hydrochloric acid is almost always
integrated with other industrial scale chemicals production.
Industrial market
Hydrochloric acid is produced in solutions up to 38% HCl (concentrated grade). Higher concentrations up to just over 40% are chemically possible, but the evaporation rate is
then so high that storage and handling need extra precautions, such as pressure and low temperature. Bulk industrial-grade is therefore 30% to 34%, optimized for effective transport and limited product loss by HCl vapors. Solutions
for household purposes, mostly cleaning, are typically 10% to 12%, with strong recommendations to dilute before use.
Major producers worldwide include Dow Chemical at 2 million metric tonnes annually (2 Mt/year), calculated
as HCl gas, and FMC, Georgia Gulf Corporation, Tosoh Corporation, Akzo Nobel, and Tessenderlo at 0.5 to 1.5 Mt/year each. Total world production, for comparison purposes expressed as HCl, is estimated at 20 Mt/year, with 3 Mt/year
from direct synthesis, and the rest as secondary product from organic and similar syntheses. By far, most of all hydrochloric acid is consumed captively by the producer. The open world market size is estimated at 5 Mt/year.
Applications
Hydrochloric acid is a common laboratory reagent.
Hydrochloric acid is a strong inorganic acid that is used in many industrial processes. The application often determines the required product quality.
Regeneration of ion exchangers
An important application of high-quality hydrochloric acid is the regeneration of ion exchange resins. Cation exchange is widely used to remove ions such as Na+ and Ca2+ from aqueous solutions, producing demineralized water.
Na+ is replaced by H3O+
Ca2+ is replaced by 2 H3O+
Ion exchangers and demineralized water are used in all chemical industries, drinking water production, and many food industries.
pH Control and neutralization
A very common application of hydrochloric acid is to regulate the basicity (pH) of solutions.
OH¥ + HCl ¥ H2O + Cl¥
In industry demanding purity (food, pharmaceutical,
drinking water), high-quality hydrochloric acid is used to control the pH of process water streams. In less-demanding industry, technical-quality hydrochloric acid suffices for neutralizing waste streams and swimming pool treatment.
Pickling of steel
Pickling is an essential step in metal surface treatment, to remove rust or iron oxide scale from iron or steel before subsequent processing, such as extrusion, rolling, galvanizing, and other techniques. Technical-quality HCl
at typically 18% concentration is the most commonly-used pickling agent for the pickling of carbon steel grades.
Fe2O3 + Fe + 6 HCl ¥ 3 FeCl2 + 3 H2O
The spent acid has long
been re-used as ferrous chloride solutions, but high heavy-metal levels in the pickling liquor has decreased this practice.
In recent years, the steel pickling industry has, however, developed hydrochloric acid regeneration
processes, such as the spray roaster or the fluidized bed HCl regeneration process, which allow the recovery of HCl from spent pickling liquor. The most common regeneration process is the pyrohydrolysis process, applying the
following formula:
4 FeCl2 + 4 H2O + O2 ¥ 8 HCl+ 2 Fe2O3
By recuperation of the spent acid, a closed acid loop is established. The ferric oxide by product of the regeneration
process is a valuable by-product, used in a variety of secondary industries.
HCl is not a common pickling agent for stainless steel grades.
Production of inorganic compounds
Numerous products can be produced with hydrochloric
acid in normal acid-base reactions, resulting in inorganic compounds. These include water treatment chemicals such as iron(III) chloride and polyaluminium chloride (PAC).
Fe2O3 + 6 HCl ¥ 2 FeCl3 + 3 H2O
Both iron(III) chloride and PAC are used as flocculation and coagulation agents in wastewater treatment, drinking water production, and paper
production.
Other inorganic compounds produced with hydrochloric acid include road application salt calcium chloride, nickel(II) chloride for electroplating, and zinc chloride for the galvanizing industry and battery
production.
Production of organic compounds
The largest hydrochloric acid consumption is in the production of organic compounds such as vinyl chloride for PVC, and MDI and TDI for polyurethane. This is often captive use,
consuming locally-produced hydrochloric acid that never actually reaches the open market. Other organic compounds produced with hydrochloric acid include bisphenol A for polycarbonate, activated carbon, and ascorbic acid, as well
as numerous pharmaceutical products.
Other applications
Hydrochloric acid is a fundamental chemical, and as such it is used for a large number of small-scale applications, such as leather processing, household cleaning, and building
construction. In addition, a way of stimulating oil production is by injecting hydrochloric acid into the rock formation of an oil well, dissolving a portion of the rock, and creating a large-pore structure. Oil-well acidizing is a
common process in the North Sea oil production industry.
Many chemical reactions involving hydrochloric acid are applied in the production of food, food ingredients, and food additives. Typical products include aspartame,
fructose, citric acid, lysine, hydrolyzed (vegetable) protein as food enhancer, and in gelatin production. Food-grade (extra-pure) hydrochloric acid can be applied when needed for the final product.
Safety
Dangerous goods labels
Dangerous goods label for hydrochloric acid: corrosive Dangerous goods label for hydrochloric acid: corrosive
Hydrochloric acid in high concentrations forms acidic mists. Both the mist and
the solution have a corrosive effect on human tissue, with the potential to damage respiratory organs, eyes, skin, and intestines. Upon mixing hydrochloric acid with common oxidizing chemicals, such as bleach (NaClO) or
permanganate (KMnO4), the toxic gas chlorine is produced. To minimize the risks while working with hydrochloric acid, appropriate precautions should be taken, including wearing rubber or PVC gloves, protective eye goggles, and
chemical-resistant clothing.
The hazards of solutions of hydrochloric acid depend on the concentration. The following table lists the EU classification of hydrochloric acid solutions: |
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