Mercury(II) chloride
Encyclopedia
Mercury chloride or mercuric chloride (formerly corrosive sublimate), is the chemical compound
with the formula
Hg
Cl2. This white crystalline solid
is a laboratory reagent and a molecular compound. It is no longer used for medicinal purposes (e.g. treatment of syphilis
) because it is highly toxic and superior treatments have become available.
s with Hg---Cl distance of 2.38 Å; four more chlorides are more distant at 3.38 Å.
Mercuric chloride is obtained by the action of chlorine
on mercury or mercury(I) chloride
, by the addition of hydrochloric acid
to a hot, concentrated solution of mercury(I) compounds such as the nitrate
:
Heating a mixture of solid mercury(II) sulfate
and sodium chloride
also affords volatile HgCl2, which sublimes
and condenses in the form of small rhombic crystals.
Its solubility increases from 6% at 20 °C to 36% in boiling water. In the presence of chloride ions, it dissolves to give the tetrahedral coordination complex [HgCl4]2-.
to vinyl chloride
, the precursor to polyvinylchloride:
For this application, the mercuric chloride is supported on carbon in concentrations of about 5 weight percent. This technology has been eclipsed by the thermal cracking of 1,2-dichloroethane
. Other significant applications of mercuric chloride include its use as a depolarizer
in batteries and as a reagent in organic synthesis
and analytical chemistry
(see below).
It is being used in plant tissue culture for surface sterilisation of explants such as leaf or stem nodes.
with metals, such as aluminium
. Upon treatment with an aqueous solution of mercuric chloride, aluminium strips quickly become covered by a thin layer of the amalgam. Normally, aluminium is protected by a thin layer of oxide making it inert. Once amalgamated, aluminium can undergo a variety of reactions. For example, it will dissolve in water (this can be dangerous, as hydrogen gas and heat are generated). Halocarbon
s react with amalgamated aluminium in the Barbier reaction
. These alkylaluminium compounds are nucleophilic and can be used in a similar fashion to the Grignard reagent. Amalgamated aluminium is also used as a reducing agent
in organic synthesis. Zinc is also commonly amalgamated using mercuric chloride.
Mercuric chloride is used to remove dithiane
groups attached to a carbonyl in an umpolung
reaction. This reaction exploits the high affinity of Hg2+ for anionic sulfur ligands.
of the 1800s. When applied to a negative, the mercury(II) chloride whitens and thickens the image, thereby increasing the opacity of the shadows and creating the illusion of a positive image.
, and ultimately creosote
; were found to be less toxic. Limited kyanizing was used for some railroad ties in the 1890s and early 1900s.
was frequently treated with mercuric chloride before the advent of antibiotics. It was inhaled, ingested, injected, and applied topically. Poisoning was so common that its symptoms were confused with those of syphilis. This usage of 'salts of white mercury' is referred to in the English
folk-song, The Unfortunate Rake.
Chemical compound
A chemical compound is a pure chemical substance consisting of two or more different chemical elements that can be separated into simpler substances by chemical reactions. Chemical compounds have a unique and defined chemical structure; they consist of a fixed ratio of atoms that are held together...
with the formula
Chemical formula
A chemical formula or molecular formula is a way of expressing information about the atoms that constitute a particular chemical compound....
Hg
Mercury (element)
Mercury is a chemical element with the symbol Hg and atomic number 80. It is also known as quicksilver or hydrargyrum...
Cl2. This white crystalline solid
Solid
Solid is one of the three classical states of matter . It is characterized by structural rigidity and resistance to changes of shape or volume. Unlike a liquid, a solid object does not flow to take on the shape of its container, nor does it expand to fill the entire volume available to it like a...
is a laboratory reagent and a molecular compound. It is no longer used for medicinal purposes (e.g. treatment of syphilis
Syphilis
Syphilis is a sexually transmitted infection caused by the spirochete bacterium Treponema pallidum subspecies pallidum. The primary route of transmission is through sexual contact; however, it may also be transmitted from mother to fetus during pregnancy or at birth, resulting in congenital syphilis...
) because it is highly toxic and superior treatments have become available.
Production and basic properties
Mercuric chloride is not a salt but a linear triatomic molecule, hence its tendency to sublime. In the crystal, each mercury atom is bonded to two close chloride ligandLigand
In coordination chemistry, a ligand is an ion or molecule that binds to a central metal atom to form a coordination complex. The bonding between metal and ligand generally involves formal donation of one or more of the ligand's electron pairs. The nature of metal-ligand bonding can range from...
s with Hg---Cl distance of 2.38 Å; four more chlorides are more distant at 3.38 Å.
Mercuric chloride is obtained by the action of chlorine
Chlorine
Chlorine is the chemical element with atomic number 17 and symbol Cl. It is the second lightest halogen, found in the periodic table in group 17. The element forms diatomic molecules under standard conditions, called dichlorine...
on mercury or mercury(I) chloride
Mercury(I) chloride
Mercury chloride is the chemical compound with the formula Hg2Cl2. Also known as calomel or mercurous chloride, this dense white or yellowish-white, odorless solid is the principal example of a mercury compound...
, by the addition of hydrochloric acid
Hydrochloric acid
Hydrochloric acid is a solution of hydrogen chloride in water, that is a highly corrosive, strong mineral acid with many industrial uses. It is found naturally in gastric acid....
to a hot, concentrated solution of mercury(I) compounds such as the nitrate
Mercury(I) nitrate
Mercury nitrate is a chemical compound with the formula Hg22. It is used in the preparation of other mercury compounds, and, like all other mercury compounds, it is toxic.-Reactions:...
:
- HgNO3 + 2 HCl → HgCl2 + H2O + NO2,
Heating a mixture of solid mercury(II) sulfate
Mercury(II) sulfate
Mercury sulfate, commonly called mercuric sulfate is the chemical compound Hg S O4. It is an odorless solid that forms white granules or crystalline powder...
and sodium chloride
Sodium chloride
Sodium chloride, also known as salt, common salt, table salt or halite, is an inorganic compound with the formula NaCl. Sodium chloride is the salt most responsible for the salinity of the ocean and of the extracellular fluid of many multicellular organisms...
also affords volatile HgCl2, which sublimes
Sublimation (physics)
Sublimation is the process of transition of a substance from the solid phase to the gas phase without passing through an intermediate liquid phase...
and condenses in the form of small rhombic crystals.
Its solubility increases from 6% at 20 °C to 36% in boiling water. In the presence of chloride ions, it dissolves to give the tetrahedral coordination complex [HgCl4]2-.
Applications
The main application of mercuric chloride is as a catalyst for the conversion of acetyleneAcetylene
Acetylene is the chemical compound with the formula C2H2. It is a hydrocarbon and the simplest alkyne. This colorless gas is widely used as a fuel and a chemical building block. It is unstable in pure form and thus is usually handled as a solution.As an alkyne, acetylene is unsaturated because...
to vinyl chloride
Vinyl chloride
Vinyl chloride is the organochloride with the formula H2C:CHCl. It is also called vinyl chloride monomer, VCM or chloroethene. This colorless compound is an important industrial chemical chiefly used to produce the polymer polyvinyl chloride . At ambient pressure and temperature, vinyl chloride...
, the precursor to polyvinylchloride:
- C2H2 + HCl → CH2=CHCl
For this application, the mercuric chloride is supported on carbon in concentrations of about 5 weight percent. This technology has been eclipsed by the thermal cracking of 1,2-dichloroethane
1,2-Dichloroethane
The chemical compound 1,2-dichloroethane, commonly known by its old name of ethylene dichloride , is a chlorinated hydrocarbon, mainly used to produce vinyl chloride monomer , the major precursor for PVC production. It is a colourless liquid with a chloroform-like odour...
. Other significant applications of mercuric chloride include its use as a depolarizer
Depolarizer
A depolarizer or depolariser, in electrochemistry, according to an IUPAC definition, is a synonym of electroactive substance, i.e., a substance which changes its oxidation state, or partakes in a formation or breaking of chemical bonds, in a charge-transfer step of an electrochemical reaction.In...
in batteries and as a reagent in organic synthesis
Organic synthesis
Organic synthesis is a special branch of chemical synthesis and is concerned with the construction of organic compounds via organic reactions. Organic molecules can often contain a higher level of complexity compared to purely inorganic compounds, so the synthesis of organic compounds has...
and analytical chemistry
Analytical chemistry
Analytical chemistry is the study of the separation, identification, and quantification of the chemical components of natural and artificial materials. Qualitative analysis gives an indication of the identity of the chemical species in the sample and quantitative analysis determines the amount of...
(see below).
It is being used in plant tissue culture for surface sterilisation of explants such as leaf or stem nodes.
As a chemical reagent
Mercuric chloride is occasionally used to form an amalgamAmalgam (chemistry)
An amalgam is a substance formed by the reaction of mercury with another metal. Almost all metals can form amalgams with mercury, notable exceptions being iron and platinum. Silver-mercury amalgams are important in dentistry, and gold-mercury amalgam is used in the extraction of gold from ore.The...
with metals, such as aluminium
Aluminium
Aluminium or aluminum is a silvery white member of the boron group of chemical elements. It has the symbol Al, and its atomic number is 13. It is not soluble in water under normal circumstances....
. Upon treatment with an aqueous solution of mercuric chloride, aluminium strips quickly become covered by a thin layer of the amalgam. Normally, aluminium is protected by a thin layer of oxide making it inert. Once amalgamated, aluminium can undergo a variety of reactions. For example, it will dissolve in water (this can be dangerous, as hydrogen gas and heat are generated). Halocarbon
Halocarbon
Halocarbon compounds are chemicals in which one or more carbon atoms are linked by covalent bonds with one or more halogen atoms resulting in the formation of organofluorine compounds, organochlorine compounds, organobromine compounds, and organoiodine compounds...
s react with amalgamated aluminium in the Barbier reaction
Barbier reaction
The Barbier reaction is an organic reaction between an alkyl halide and a carbonyl group as an electrophilic substrate in the presence of magnesium, aluminium, zinc, indium, tin or its salts. The reaction product is a primary, secondary or tertiary alcohol...
. These alkylaluminium compounds are nucleophilic and can be used in a similar fashion to the Grignard reagent. Amalgamated aluminium is also used as a reducing agent
Redox
Redox reactions describe all chemical reactions in which atoms have their oxidation state changed....
in organic synthesis. Zinc is also commonly amalgamated using mercuric chloride.
Mercuric chloride is used to remove dithiane
Dithiane
A dithiane is a heterocyclic compound composed of a cyclohexane core structure wherein two methylene units are replaced by sulfur centres. The three isomeric parent heterocycles are 1,2-dithiane, 1,3-dithiane and 1,4-dithiane....
groups attached to a carbonyl in an umpolung
Umpolung
Umpolung or polarity inversion in organic chemistry is the chemical modification of a functional group with the aim of the reversal of polarity of that group. This modification allows secondary reactions of this functional group that would otherwise not be possible. The concept was introduced by...
reaction. This reaction exploits the high affinity of Hg2+ for anionic sulfur ligands.
Historic use in photography
Mercury(II) chloride was used as a photographic intensifier to produce positive pictures in the collodion processCollodion process
The collodion process is an early photographic process. It was introduced in the 1850s and by the end of that decade it had almost entirely replaced the first practical photographic process, the daguerreotype. During the 1880s the collodion process, in turn, was largely replaced by gelatin dry...
of the 1800s. When applied to a negative, the mercury(II) chloride whitens and thickens the image, thereby increasing the opacity of the shadows and creating the illusion of a positive image.
Historic use in preservation
For the preservation of anthropological and biological specimens during the late 19th and early 20th centuries, objects were dipped in or were painted with a "mercuric solution". Objects in drawers were protected by scattering crystalline mercuric chloride over them. It finds minor use in tanning, and wood was preserved by kyanizing (soaking in mercuric chloride). Mercuric chloride was one of the three chemicals used for railroad tie wood treatment between 1830 and 1856 in Europe and the United States. Limited railroad ties were treated in the United States until there were concerns over lumber shortages in the 1890s. The process was generally abandoned because mercuric chloride was water soluble and not effective for the long term, as well as poisonous. Furthermore, alternative treatment processes, such as copper sulfate, zinc chlorideZinc chloride
Zinc chloride is the name of chemical compound with the formula ZnCl2 and its hydrates. Zinc chlorides, of which nine crystalline forms are known, are colorless or white, and are highly soluble in water. ZnCl2 itself is hygroscopic and even deliquescent. Samples should therefore be protected from...
, and ultimately creosote
Creosote
Creosote is the portion of chemical products obtained by the distillation of a tar that remains heavier than water, notably useful for its anti-septic and preservative properties...
; were found to be less toxic. Limited kyanizing was used for some railroad ties in the 1890s and early 1900s.
Historic use in medicine
SyphilisSyphilis
Syphilis is a sexually transmitted infection caused by the spirochete bacterium Treponema pallidum subspecies pallidum. The primary route of transmission is through sexual contact; however, it may also be transmitted from mother to fetus during pregnancy or at birth, resulting in congenital syphilis...
was frequently treated with mercuric chloride before the advent of antibiotics. It was inhaled, ingested, injected, and applied topically. Poisoning was so common that its symptoms were confused with those of syphilis. This usage of 'salts of white mercury' is referred to in the English
English language
English is a West Germanic language that arose in the Anglo-Saxon kingdoms of England and spread into what was to become south-east Scotland under the influence of the Anglian medieval kingdom of Northumbria...
folk-song, The Unfortunate Rake.
Toxicity
Mercuric chloride is highly toxic, not only acutely but as a cumulative poison.External links
- Agency for toxic substances and disease registry. (2001, May 25). Toxicological profile for Mercury. Retrieved on April 17, 2005.
- National institutes of health. (2002, October 31). Hazardous substances data bank: Mercuric chloride. Retrieved on April 17, 2005.
- Young, R.(2004, October 6). Toxicity summary for mercury. The risk assessment information system. Retrieved on April 17, 2005.
- ATSDR - ToxFAQs: Mercury
- ATSDR - Public Health Statement: Mercury
- ATSDR - Medical Management Guidelines (MMGs) for Mercury (Hg)
- ATSDR - Toxicological Profile: Mercury
- National Pollutant Inventory - Mercury and compounds Fact Sheet
- NIOSH Pocket Guide to Chemical Hazards
- Mercury chloride toxicity - includes excerpts from research reports.