Mercury(II) thiocyanate - Wikipedia, the free encyclopedia

http://en.wikipedia.org/wiki/Mercury(II)_thiocyanate[4/20/2014 9:44:06 PM]

Mercury(II) thiocyanate
Mercury(II) thiocyanate
Mercuric thiocyanate
Mercuric sulfocyanate
Identifiers
CAS number 592-85-8

PubChem 11615
EC number 209-773-0
J mol-3D images Image 1
Properties
Molecular formula Hg(SCN)
2
Molar mass 316.755 g/mol
Appearance White monoclinic powder
Odor odorless
Density 3.71 g/cm, solid
Melting point 165 C (329 F; 438 K)
(decomposes)
Solubility in water 0.069 g/100 mL
Solubility Soluble in dilute hydrochloric
acid, KCN, ammonia
slightly soluble in alcohol,
ether
Hazards
NFPA 704
LD
50
46 mg/kg (rat, oral)
Except where noted otherwise, data are given for
materials in their standard state (at 25 C (77 F),
100 kPa)
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From Wikipedia, the free encyclopedia

Mercury(II) thiocyanate (Hg(SCN)
2
) is an
inorganic chemical compound, the coordination
complex of Hg
2+
and the thiocyanate anion. It is a
white powder. It is best known for its former use in
pyrotechnics , as it will produce a large, winding
snake when ignited, an effect known as the
Pharaohs Serpent.
[1]
Contents [hide]
1 Synthesis
2 Pharaoh's serpent
3 Uses
3.1 Use in chloride analysis
4 References
5 External links
Synthesis [edit]
The first synthesis of mercury thiocyanate was
probably completed in 1821 by J ns J acob Berzelius:
HgO +2 HSCN Hg(SCN)
2
+H
2
O
Evidence for the first pure sample was presented in
1866 prepared by a chemist named J . Hermes.
[1]
It is
prepared by treating solutions containing mercury(II)
and thiocyanate ions. The low solubility product of
mercury thiocyanate causes it to precipitate from
solution.
[2]
Most syntheses are achieved by
precipitation:
Hg(NO
3
)
2
+2 KSCN Hg(SCN)
2
+2KNO
3
Pharaoh's serpent [edit]
Mercury thiocyanate was formerly used in pyrotechnics
causing an effect known as the Pharaoh's serpent or
Pharaoh's snake. When the compound is in the
Other names [hide]
SMILES [show]
InChI [show]
1
3 1
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Mercury(II) thiocyanate - Wikipedia, the free encyclopedia
http://en.wikipedia.org/wiki/Mercury(II)_thiocyanate[4/20/2014 9:44:06 PM]
Infobox references
presence of a strong enough heat source, a rapid
exothermic reaction is started which produces a large
mass of coiling serpent-like solid. An inconspicuous
flame which is often blue but can also occur in yellow/orange accompanies the combustion. The resulting
solid can range from dark graphite grey to light tan in color with the inside generally much darker than
the outside.
[1]
This property was discovered by Whler in 1821, soon after the first synthesis of mercury thiocyanate:
"winding out from itself at the same time worm-like processes, to many times its former bulk, a very
light material the color of graphite...". For some time, a firework product called "Pharaoschlangen" was
available to the public in Germany, but was eventually banned when the toxic properties of the product
were discovered through the death of several children mistakenly eating the resulting solid.
[1]
A similar, although less extreme, effect to the Pharaoh's serpent can be achieved using a firework known
as a black snake . These are generally benign products, usually consisting of sodium bicarbonate or a
mixture of linseed oil and naphthalenes .
[citation needed]
Uses [edit]
Mercury thiocyanate has a few uses in chemical synthesis. It is the precursor to potassium
tris(thiocyanato)mercurate(II) (K[Hg(SCN)
3
]) and caesium tris(thiocyanato)mercurate(II)
(Cs[Hg(SCN)
3
]). The Hg(SCN)
3
-
ion can also exist independently and is easily reacted to form the
compounds above amongst others.
[3]
Its reactions with organic halides yield two products, one with the sulfur bound to the organic compound
and one with the nitrogen bound to the organic compound.
[4]
Use in chloride analysis [edit]
It was discovered that mercury thiocyanate can improve detection limits in the determination of chloride
ions in water by UV-visible spectroscopy. This technique was first suggested in 1952 and has been a
common method for determination of chloride ions in laboratories worldwide ever since. An automated
system was invented in 1964 and then a commercial chloroanalyzer was made available in 1974 by
Technicon (Tarrytown, NY , USA). The basic mechanism involves the addition of mercury thiocyanate to
a solution with unknown concentration of chloride ions and iron as a reagent . The chloride ions cause
the mercury thiocyanate salt to dissociate and the thiocyanate ion to bind Fe(III), which absorbs intensely
at 450 nm. This absorption allows for the measurement of concentration of the iron complex. This value
allows one to calculate the concentration of chloride.
[5]
It can be used for determining the concentration of chloride ions in aqueous solution. Mercury thiocyanate
without iron (III) is added to a solution with an unknown concentration of chloride ions, forming a
complex of the mercury thiocyanate and chloride ion that absorbs light at a 254 nm, allowing more
accurate measurements of concentration than the aforementioned technique using iron.
[5]
References [edit]
1. ^
a

b

c

d
Davis, T. L. (1940). "Pyrotechnic Snakes". Journal of Chemical Education 17 (6): 268
270. doi:10.1021/ed017p268 .
2. ^ Sekine, T.; Ishii, T. (1970). "Studies of the Liquid-Liquid Partition systems. VIII. The Solvent
Mercury(II) thiocyanate - Wikipedia, the free encyclopedia
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[show] V T E
Extraction of Mercury (II) Chloride, Bromide, Iodide and Thiocyanate with Some Organic
Solvents" (pdf). Bulletin of the Chemical Society of Japan 43 (8): 24222429.
doi:10.1246/bcsj.43.2422 .
3. ^ Bowmaker, G. A.; Churakov, A. V.; Harris, R. K.; Howard, J . A. K.; Apperley, D. C. (1998).
"Solid-State
199
Hg MAS NMR Studies of Mercury(II) Thiocyanate Complexes and Related
Compounds. Crystal Structure of Hg(SeCN)
2
". Inorganic Chemistry 37 (8): 17341743.
doi:10.1021/ic9700112 .
4. ^ Kitamura, T.; Kobayashi, S.; Taniguchi, H. (1990). "Photolysis of Vinyl Halides. Reaction of
Photogenerated Vinyl Cations with Cyanate and Thiocyanate Ions". Journal of Organic
Chemistry 55 (6): 18011805. doi:10.1021/jo00293a025 .
5. ^
a

b
Cirello-Egamino, J .; Brindle, I. D. (1995). "Determination of chloride ions by reaction with
mercury thiocyanate in the absence of iron(III) using a UV-photometric, flow injection method".
Analyst 120 (1): 183186. doi:10.1039/AN9952000183 .
External links [edit]
"Pharaoh's snake" . YouTube. September 2, 2008.
Mercury compounds
Categories : Hazardous air pollutants Pollutants Pyrotechnic chemicals Thiocyanates
Mercury compounds