Mercury(II) thiocyanate

Mercury(II) thiocyanate
Mercury(II) thiocyanate in crystal
Names
Other names
Mercuric thiocyanate
Mercuric sulfocyanate
Identifiers
3D model (JSmol)
ECHA InfoCard 100.008.886 Edit this at Wikidata
EC Number
  • 209-773-0
UNII
  • InChI=1S/2CHNS.Hg/c2*2-1-3;/h2*3H;/q;;+2/p-2
    Key: GBZANUMDJPCQHY-UHFFFAOYSA-L
  • C(#N)[S-].C(#N)[S-].[Hg+2]
Properties
Hg(SCN)2
Molar mass 316.755 g/mol
Appearance White monoclinic powder
Odor odorless
Density 3.71 g/cm3, solid
Melting point 165 °C (329 °F; 438 K) (decomposes)
0.069 g/100 mL
Solubility Soluble in dilute hydrochloric acid, KCN, ammonia
slightly soluble in alcohol, ether
−96.5·10−6 cm3/mol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 highly toxic
GHS labelling:[1]
GHS06: ToxicGHS08: Health hazardGHS09: Environmental hazard
Danger
H300, H310, H330, H373, H410
P260, P262, P270, P271, P273, P280, P284, P301+P316, P302+P352, P304+P340, P316, P319, P320, P321, P330, P361, P364, P391, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamondHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
3
1
1
Lethal dose or concentration (LD, LC):
46 mg/kg (rat, oral)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Mercury(II) thiocyanate (Hg(SCN)2) is an inorganic chemical compound, the coordination complex of Hg2+ and the thiocyanate anion. It is a white powder. It will produce a large, winding "snake" when ignited, an effect known as the Pharaoh's serpent.[2]

Synthesis and structure

The first synthesis of mercury thiocyanate was probably completed in 1821 by Jöns Jacob Berzelius:

HgO + 2 HSCN → Hg(SCN)2 + H2O

Evidence for the first pure sample was presented in 1866 prepared by a chemist named Otto Hermes.[2] It is prepared by treating solutions containing mercury(II) and thiocyanate ions. The low solubility product of mercury thiocyanate causes it to precipitate from the solution.[3] Most syntheses are achieved by precipitation:

Hg(NO3)2 + 2 KSCN → Hg(SCN)2 + 2 KNO3

The compound adopts a polymeric structure with Hg2+ centres linearly coordinated to two S atoms with a distance of 2.381 Å. Four weak Hg2+--N interactions are indicated with distances of 2.81 Å.[4]

Reactions

Mercury thiocyanate has a few uses in chemical synthesis.

It is the precursor to other thiocyanate complexes such as 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 generated from the compounds above, amongst others.[5]

Organic halides attack Hg(SCN)2 to give a mercuric halide and a mixture of the corresponding thiocyanate and isothiocyanate.[6]

Mercuric thiocyanate catalyzes HSCN or BrSCN addition (either reagent formed in situ) to alkynes.[7]

Use in chloride analysis

Mercury thiocyanate improve detection limits in the determination of chloride ions in water by UV-visible spectroscopy. This technique was a standard method for the determination of chloride ions in laboratories worldwide. The method involves the addition of mercury thiocyanate to a solution with an 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 the concentration of the iron complex. This value allows one to calculate the concentration of chloride.[8]

Pharaoh's serpent

Main article: Black snake (firework)
Pharaoh's serpent demonstration

Mercury thiocyanate was formerly used in pyrotechnics causing an effect known as the Pharaoh's serpent or Pharaoh's snake. The fireworks versions were a mixture with a small amount of potassium nitrate and gum arabic as a binder.[9] This use ceased in most countries in the early 20th century due to the toxicity of mercury, and the existence of a superior alternatives.

Chemistry of the reaction

When heated, mercury(II) thiocyanate decomposes in an exothermic reaction that can produce a large mass of coiling, serpent-like solid. An inconspicuous flame, which is usually the blue color of burning carbon disulfide but which can be yellow from impurities or incidental combustion of flammable materials on the surface it is ignited on. The resulting solid can range from dark graphite gray to light tan in colour with the inside generally much darker than the outside. This was found to be due to decomposition of the produced β-HgS (black mercury sulfide) and vaporization of the resulting mercury from the othermost and hottest layers of the solid.[10]

The decomposition of Hg(SCN)2 is exothermic on its own, and the CS2 produced ignites easily and burns off. The C3N4 product is a simplification; the actual product contains 0.5% hydrogen and is likely to consist of sheets of triazine rings linked by −N= and −NH− groups similar to g−C3N4 and was found to contain nano-particles of β-HgS (black mercury sulfide).[10]

The number of resonance structures of heptazine and triazine, varying molecular weights of samples, and the fluorescense of the product made acquiring spectra difficult even by relatively exotic methods of NMR (with one spectrum acquisition being run for 12 days straight to get a mostly clean reading). Because of this, a heptazine-based structure similar to Liebig's melon, a compound initially prepared around the same time that the pharoah's snake reaction was discovered, was not ruled out by the authors as a partial component of the solid material.[10] The generalized reaction is as follows:

  • 2 Hg(SCN)2 → 2 β−HgS + CS2 + C3N4
  • β−HgS + O2 → Hg + SO2 (not all mercury sulfide decomposes)

C3N4 is not a product of this decomposition. Cyanogen is generally only produced when Hg(CN)2 or similar is heated to decomposition, and early attempts to form (SCN)2 via the same route starting at this compound failed and only generated SO2, CO2 and N2.[10]

References

  1. ^ "Mercuric thiocyanate (Compound)". pubchem.ncbi.nlm.nih.gov. Retrieved 31 May 2023.
  2. ^ a b Davis, T. L. (1940). "Pyrotechnic Snakes". Journal of Chemical Education. 17 (6): 268–270. doi:10.1021/ed017p268.
  3. ^ Sekine, T.; Ishii, T. (1970). "Studies of the Liquid-Liquid Partition systems. VIII. The Solvent Extraction of Mercury (II) Chloride, Bromide, Iodide and Thiocyanate with Some Organic Solvents". Bulletin of the Chemical Society of Japan. 43 (8): 2422–2429. doi:10.1246/bcsj.43.2422.
  4. ^ Beauchamp, A.L.; Goutier, D. "Structure cristalline et moleculaire du thiocyanate mercuric" Canadian Journal of Chemistry 1972, volume 50, p977-p981. doi:10.1139/v72-153
  5. ^ Bowmaker, G. A.; Churakov, A. V.; Harris, R. K.; Howard, J. A. K.; Apperley, D. C. (1998). "Solid-State 199Hg MAS NMR Studies of Mercury(II) Thiocyanate Complexes and Related Compounds. Crystal Structure of Hg(SeCN)2". Inorganic Chemistry. 37 (8): 1734–1743. doi:10.1021/ic9700112.
  6. ^ 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): 1801–1805. doi:10.1021/jo00293a025.
  7. ^ Kočovský, Pavel. "Mercury(II) thiocyanate". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rm045.{{cite encyclopedia}}: CS1 maint: multiple names: authors list (link)
  8. ^ 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): 183–186. doi:10.1039/AN9952000183.
  9. ^ Weingart, George W. (1947). "Part III. Products of Manufacture and Formulas". Pyrotechnics (2d, rev. and enl ed.). Brooklyn: Chemical Pub. Co. pp. 182–183. ISBN 9780820601120.
  10. ^ a b c d Miller, Thomas S.; d'Aleo, Anita; Suter, Theo; Aliev, Abil E.; Sella, Andrea; McMillan, Paul F. (17 November 2017). "Pharaoh's Serpents: New Insights into a Classic Carbon Nitride Material". Zeitschrift für anorganische und allgemeine Chemie (Journal of Inorganic and General Chemistry). 643 (21): 1572–1580. doi:10.1002/zaac.201700268.