Hydrogen chloride

The compound hydrogen chloride has the chemical formula HCl. At room temperature, it is a colorless gas, which forms white fumes of hydrochloric acid upon contact with atmospheric humidity. Hydrogen chloride gas and hydrochloric acid are important in technology and industry. Hydrochloric acid, the aqueous solution of hydrogen chloride, is also commonly given the formula HCl.

Chemistry

Hydrochloric acid fumes turning pH paper red showing that the fumes are acidic

Hydrogen chloride is a diatomic molecule, consisting of a hydrogen atom H and a chlorine atom Cl connected by a covalent single bond. Since the chlorine atom is much more electronegative than the hydrogen atom, the covalent bond between the two atoms is quite polar. Consequently, the molecule has a large dipole moment with a negative partial charge (δ−) at the chlorine atom and a positive partial charge (δ+) at the hydrogen atom. In part because of its high polarity, HCl is very soluble in water (and in other polar solvents).

Upon contact, H₂O and HCl combine to form hydronium cations H₃O⁺ and chloride anions Cl⁻ through a reversible chemical reaction:

HCl + H₂O → H₃O⁺ + Cl⁻

The resulting solution is called hydrochloric acid and is a strong acid. The acid dissociation or ionization constant, K_a, is large, which means HCl dissociates or ionizes practically completely in water. Even in the absence of water, hydrogen chloride can still act as an acid. For example, hydrogen chloride can dissolve in certain other solvents such as methanol, protonate molecules or ions, and serve as an acid-catalyst for chemical reactions where anhydrous (water-free) conditions are desired.

HCl + CH₃OH → CH₃O⁺H₂ + Cl⁻

Because of its acidic nature, hydrogen chloride is corrosive, particularly in the presence of moisture.

Structure and properties

The structure of solid DCl, as determined by neutron diffraction of DCl powder at 77 K. DCl was used instead of HCl because the deuterium nucleus is easier to detect than the hydrogen nucleus. The "infinite" chains of DCl are indicated by the dashed lines.

Frozen HCl undergoes phase transition at 98.4 K. X-ray powder diffraction of the frozen material shows that the material changes from an orthorhombic structure to a cubic one during this transition. In both structures the chlorine atoms are in a face-centered array. However, the hydrogen atoms could not be located.^[7] Analysis of spectroscopic and dielectric data, and determination of the structure of DCl (deuterium chloride) indicates that HCl forms zigzag chains in the solid, as does HF (see figure on right).^[8]

Solubility of HCl (g/L) in common solvents^[9]
Temperature (°C)	0	20	30	50
Water	823	720	673	596
Methanol	513	470	430
Ethanol	454	410	381
Ether	356	249	195

Infrared (IR) absorption spectrum

One doublet in the IR spectrum resulting from the isotopic composition of chlorine

The infrared spectrum of gaseous hydrogen chloride, shown om the left, consists of a number of sharp absorption lines grouped around 2886 cm⁻¹ (wavelength ~3.47 µm). At room temperature, almost all molecules are in the ground vibrational state v = 0. Including anharmonicity the vibrational energy can be written as.

E_\mathrm{vib}= h\nu_e\cdot\left(v + \tfrac{1}{2}\right)+ hx_e\nu_e\cdot\left(v+\tfrac{1}{2}\right)^2

To promote an HCl molecule from the v = 0 to the v = 1 state, we would expect to see an infrared absorption about ν_o = ν_e + 2x_eν_e = 2880 cm⁻¹. However, this absorption corresponding to the Q-branch is not observed due to it being forbidden by symmetry. Instead, two sets of signals (P- and R-branches) are seen owing to a simultaneous change in the rotational state of the molecules. Because of quantum mechanical selection rules, only certain rotational transitions are permitted. The states are characterized by the rotational quantum number J = 0, 1, 2, 3, ... selection rules state that ΔJ is only able to take values of ±1.

E(J)_\mathrm{rot} = h \cdot B \cdot J(J+1)

The value of the rotational constant B is much smaller than the vibrational one ν_o, such that a much smaller amount of energy is required to rotate the molecule; for a typical molecule, this lies within the microwave region. However, the vibrational energy of HCl molecule places its absorptions within the infrared region, allowing a spectrum showing the rovibrational transitions of this molecule to be easily collected using an infrared spectrometer with a gas cell. The latter can even be made of quartz as the HCl absorption lies in a window of transparency for this material.

Naturally abundant chlorine consists of two isotopes, ³⁵Cl and ³⁷Cl, in a ratio of approximately 3:1. While the spring constants are identical within experimental error, the reduced masses are different causing measurable differences in the rotational energy, thus doublets are observed on close inspection of each absorption line, weighted in the same ratio of 3:1.

Production

Most hydrogen chloride produced on an industrial scale is used for hydrochloric acid production.

Direct synthesis

Flame inside HCl oven

In the chlor-alkali industry, brine (mixture of sodium chloride and water) solution is electrolyzed producing chlorine (Cl₂), sodium hydroxide, and hydrogen (H₂):

2 NaCl + 2 H₂O → Cl₂ + 2 NaOH + H₂

The pure chlorine gas can be combined with hydrogen to produce hydrogen chloride in the presence of UV light:

Cl₂(g) + H₂(g) → 2 HCl(g)

As the reaction is exothermic, the installation is called an HCl oven or HCl burner. The resulting hydrogen chloride gas is absorbed in deionized water, resulting in chemically pure hydrochloric acid. This reaction can give a very pure product, e.g. for use in the food industry.

Organic synthesis

The largest production of hydrochloric acid is integrated with the formation of chlorinated and fluorinated organic compounds, e.g., Teflon, Freon, and other CFCs, as well as chloroacetic acid and PVC. Often this production of hydrochloric acid is integrated with captive use of it on-site. In the chemical reactions, hydrogen atoms on the hydrocarbon are replaced by chlorine atoms, whereupon the released hydrogen atom recombines with the spare atom from the chlorine molecule, forming hydrogen chloride. Fluorination is a subsequent chlorine-replacement reaction, producing again hydrogen chloride:

R−H + Cl₂ → R−Cl + HCl

R−Cl + HF → R−F + HCl

The resulting hydrogen chloride gas is either reused directly or absorbed in water, resulting in hydrochloric acid of technical or industrial grade.

Laboratory methods

Small amounts of HCl gas for laboratory use can be generated in an HCl generator by dehydrating hydrochloric acid with either sulfuric acid or anhydrous calcium chloride. Alternatively, HCl can be generated by the reaction of sulfuric acid with sodium chloride:^[10]

NaCl + H₂SO₄ → NaHSO₄ + HCl

This reaction occurs at room temperature. Provided there is NaCl remaining in the generator and it is heated above 200 °C, the reaction proceeds further:

NaCl + NaHSO₄ → HCl + Na₂SO₄

For such generators to function, the reagents should be dry.

HCl can also be prepared by the hydrolysis of certain reactive chloride compounds such as phosphorus chlorides, thionyl chloride (SOCl₂), and acyl chlorides. For example, cold water can be gradually dripped onto phosphorus pentachloride (PCl₅) to give HCl:

PCl₅ + H2O → POCl₃ + 2 HCl

High-purity streams of the gas require lecture bottles or cylinders, both of which can be expensive. In comparison, the use of a generator requires only apparatus and materials commonly available in a laboratory.

Applications

Most hydrogen chloride is used in the production of hydrochloric acid. It is also an important reagent in other industrial chemical transformations, e.g.:

Hydrochlorination of rubber
Production of vinyl and alkyl chlorides

In the semiconductor industry, it is used to both etch semiconductor crystals and to purify silicon via trichlorosilane (SiHCl₃).

It may also be used to treat cotton to delint it, and to separate it from wool.

In the laboratory, anhydrous forms of the gas are particularly useful for generating chloride-based Lewis acids, which must be absolutely dry for their Lewis sites to function. It can also be used to dry the corresponding hydrated forms of these materials by passing it over as they are heated; the materials would otherwise fume HCl gas themselves and decompose. Neither can these hydrates be dried using standard desiccator methods.

History

Alchemists of the Middle Ages recognized that hydrochloric acid (then known as spirit of salt or acidum salis) released vaporous hydrogen chloride, which was called marine acid air. In the 17th century, Johann Rudolf Glauber used salt (sodium chloride) and sulfuric acid for the preparation of sodium sulfate, releasing hydrogen chloride gas (see production, below). In 1772, Carl Wilhelm Scheele also reported this reaction and is sometimes credited with its discovery. Joseph Priestley prepared hydrogen chloride in 1772, and in 1810 Humphry Davy established that it is composed of hydrogen and chlorine.^[11]

During the Industrial Revolution, demand for alkaline substances such as soda ash increased, and Nicolas Leblanc developed a new industrial-scale process for producing the soda ash. In the Leblanc process, salt was converted to soda ash, using sulfuric acid, limestone, and coal, giving hydrogen chloride as by-product. Initially, this gas was vented to air, but the Alkali Act of 1863 prohibited such release, so then soda ash producers absorbed the HCl waste gas in water, producing hydrochloric acid on an industrial scale. Later, the Hargreaves process was developed, which is similar to the Leblanc process except sulfur dioxide, water, and air are used instead of sulfuric acid in a reaction which is exothermic overall. In the early 20th century the Leblanc process was effectively replaced by the Solvay process, which did not produce HCl. However, hydrogen chloride production continued as a step in hydrochloric acid production.

Historical uses of hydrogen chloride in the 20th century include hydrochlorinations of alkynes in producing the chlorinated monomers chloroprene and vinyl chloride, which are subsequently polymerized to make polychloroprene (Neoprene) and polyvinyl chloride (PVC), respectively. In the production of vinyl chloride, acetylene (C₂H₂) is hydrochlorinated by adding the HCl across the triple bond of the C₂H₂ molecule, turning the triple into a double bond, yielding vinyl chloride.

The "acetylene process", used until the 1960s for making chloroprene, starts out by joining two acetylene molecules, and then adds HCl to the joined intermediate across the triple bond to convert it to chloroprene as shown here:

This "acetylene process" has been replaced by a process which adds Cl₂ to one of the double bonds in 1,3-butadiene instead, and subsequent elimination produces HCl instead, as well as chloroprene.

Safety

Hydrogen chloride forms corrosive hydrochloric acid on contact with water found in body tissue. Inhalation of the fumes can cause coughing, choking, inflammation of the nose, throat, and upper respiratory tract, and in severe cases, pulmonary edema, circulatory system failure, and death. Skin contact can cause redness, pain, and severe skin burns. Hydrogen chloride may cause severe burns to the eye and permanent eye damage.

The gas, being strongly hydrophilic, can be easily scrubbed from the exhaust gases of a reaction by bubbling it through water, producing useful hydrochloric acid as a byproduct.

Any equipment handling hydrogen chloride gas must be checked on a routine basis; particularly valve stems and regulators. The gas requires the use of specialized materials on all wetted parts of the flow path, as it will interact with or corrode numerous materials hydrochloric acid alone will not; such as stainless and regular polymers.

The Occupational Safety and Health Administration and the National Institute for Occupational Safety and Health have established occupational exposure limits for hydrogen chloride at a ceiling of 5 ppm (7 mg/m³).^[12]

References

↑ "hydrogen chloride (CHEBI:17883)". Chemical Entities of Biological Interest (ChEBI). UK: European Bioinformatics Institute.
↑ Haynes, William M. (2010). Handbook of Chemistry and Physics (91 ed.). Boca Raton, Florida: CRC Press. p. 4–67. ISBN 978-1439820773.
↑ Hydrogen Chloride. Gas Encyclopaedia. Air Liquide
↑ Tipping, E.(2002) . Cambridge University Press, 2004.
1 2 "Hydrogen chloride". Immediately Dangerous to Life and Health. National Institute for Occupational Safety and Health (NIOSH).
1 2 3 "NIOSH Pocket Guide to Chemical Hazards #0332". National Institute for Occupational Safety and Health (NIOSH).
↑ Natta, G. (1933). "Struttura e polimorfismo degli acidi alogenidrici". Gazzetta Chimica Italiana (in Italian) 63: 425–439.
↑ Sándor, E.; Farrow, R. F. C. (1967). "Crystal Structure of Solid Hydrogen Chloride and Deuterium Chloride". Nature 213 (5072): 171–172. Bibcode:1967Natur.213..171S. doi:10.1038/213171a0.
↑ Hydrochloric Acid – Compound Summary. Pubchem
↑ Francisco J. Arnsliz (1995). "A Convenient Way To Generate Hydrogen Chloride in the Freshman Lab". J. Chem. Ed. 72 (12): 1139. Bibcode:1995JChEd..72.1139A. doi:10.1021/ed072p1139.
↑ Hartley, Harold (1960). "The Wilkins Lecture. Sir Humphry Davy, Bt., P.R.S. 1778–1829". Proceedings of the Royal Society A 255 (1281): 153–180. Bibcode:1960RSPSA.255..153H. doi:10.1098/rspa.1960.0060.
↑ CDC – NIOSH Pocket Guide to Chemical Hazards

External links

Wikimedia Commons has media related to Hydrogen chloride.

International Chemical Safety Card 0163
Thames & Kosmos Chem C2000 Experiment Manual

Hydrogen compounds

Molecules detected in outer space

Molecules

Diatomic	Aluminium monochloride Aluminium monofluoride Aluminium monoxide Argon hydride Carbon monophosphide Carbon monosulfide Carbon monoxide Carborundum Cyanogen radical Diatomic carbon Fluoromethylidynium Hydrogen chloride Hydrogen fluoride Hydrogen (molecular) Hydroxyl radical Iron(II) oxide Magnesium monohydride cation Methylidyne radical Nitric oxide Nitrogen (molecular) Nitrogen monohydride Nitrogen sulfide Oxygen (molecular) Phosphorus monoxide Phosphorus mononitride Potassium chloride Silicon carbide Silicon mononitride Silicon monoxide Silicon monosulfide Sodium chloride Sodium iodide Sulfur monohydride Sulfur monoxide Titanium oxide

Triatomic	Aluminium hydroxide Aluminium isocyanide Amino radical Carbon dioxide Carbonyl sulfide CCP radical Chloronium Diazenylium Dicarbon monoxide Disilicon carbide Ethynyl radical Formyl radical Hydrogen cyanide Hydrogen isocyanide (HCN) Hydrogen isocyanide (HNC) Hydrogen sulfide Hydroperoxyl Iron cyanide Isoformyl Magnesium cyanide Magnesium isocyanide Methylene radical N₂H⁺ Nitrous oxide Nitroxyl Ozone Phosphaethyne Potassium cyanide Protonated molecular hydrogen Sodium cyanide Sodium hydroxide Silicon carbonitride c-Silicon dicarbide Silicon naphthalocyanine Sulfur dioxide Thioformyl Thioxoethenylidene Titanium dioxide Tricarbon Water

Four atoms	Acetylene Ammonia Cyanic acid Cyanoethynyl Cyclopropynylidyne Formaldehyde Fulminic acid HCCN Hydrogen peroxide Hydromagnesium isocyanide Isocyanic acid Isothiocyanic acid Ketenyl Methylene amidogen Methyl radical Propynylidyne Protonated carbon dioxide Protonated hydrogen cyanide Silicon tricarbide Thioformaldehyde Tricarbon monoxide Tricarbon sulfide Thiocyanic acid

Five atoms	Ammonium Ion Butadiynyl Carbodiimide Cyanamide Cyanoacetylene Cyanoformaldehyde Cyanomethyl Cyclopropenylidene Formic acid Isocyanoacetylene Ketene Methane Methoxy radical Methylenimine Propadienylidene Protonated formaldehyde Protonated formaldehyde Silane Silicon-carbide cluster

Six atoms	Acetonitrile Cyanobutadiynyl radical E-Cyanomethanimine Cyclopropenone Diacetylene Ethylene Formamide HC₄N Ketenimine Methanethiol Methanol Methyl isocyanide Pentynylidyne Propynal Protonated cyanoacetylene

Seven atoms	Acetaldehyde Acrylonitrile Cyanodiacetylene Ethylene oxide Hexatriynyl radical Methylacetylene Methylamine Methyl isocyanate Vinyl alcohol

Eight atoms	Acetic acid Aminoacetonitrile Cyanoallene Ethanimine Glycolaldehyde Heptatrienyl radical Hexapentaenylidene Methylcyanoacetylene Methyl formate Propenal

Nine atoms	Acetamide Cyanohexatriyne Cyanotriacetylene Dimethyl ether Ethanol Methyldiacetylene Octatetraynyl radical Propene Propionitrile

Ten atoms or more	Acetone Benzene Buckminsterfullerene (C₆₀ fullerene) ("bucky-ball") C₇₀ fullerene Cyanodecapentayne Cyanopentaacetylene Cyanotetra-acetylene Ethylene glycol Ethyl formate Methyl acetate Methyl-cyano-diacetylene Methyltriacetylene Propanal n-Propyl cyanide Pyrimidine

Deuterated
molecules

Unconfirmed

Book:Chemistry
Category:Astrochemistry
Category:Molecules
Portal:Astrobiology
Portal:Chemistry

Authority control	GND: 4147850-2 NDL: 00561990

This article is issued from Wikipedia - version of the Wednesday, April 13, 2016. The text is available under the Creative Commons Attribution/Share Alike but additional terms may apply for the media files.