Zinc chloride

From Academic Kids

Zinc chloride
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Zinc chloride hydrate

Zinc chloride hydrate
Systematic name Zinc chloride
Other names Zinc(II) chloride

Zinc dichloride

Butter of zinc

Molecular formula ZnCl2
Molecular weight 136.29 g/mol
Appearance White crystalline solid
CAS number [7646-85-7]
MSDS Zinc chloride MSDS
Bulk properties
Density 2.907 g/cm3
Solubility Water: 432 g/100 cm3 (25 C)

Ethanol: 100 g/100 cm3 (12.5 C)

Acetone: soluble

Diethyl ether: very soluble

Melting point 275 C[1] (548 K)
Boiling point 756 C (1029 K)
Hazards Irritant, corrosive
Coordination geometry Tetrahedral (4-coordinate)

Linear in the gas phase

Crystal structure Four forms known

Hexagonal close-packed

(delta) is the only stable

form when anhydrous

Hydrates Many possible.
Related compounds
Other anions Zinc fluoride

Zinc bromide

Zinc iodide

Other cations Copper(II) chloride

Cadmium chloride



Zinc chloride (ZnCl2) is a colorless or white compound of zinc and chlorine that is extremely hygroscopic.

Four crystalline structures have been reported, although in pure form (i.e. water-free) only the delta (hexagonal close-packed) phase can form. It can be quenched from the melt to form a glassy material.

Concentrated aqueous solutions of zinc chloride have the interesting property of dissolving starch, silk and cellulose, so that solutions cannot be filtered through standard filter papers.

Zinc chloride finds wide application in textile processing, metallurgical fluxes and chemical synthesis.

Chemical properties

Zinc chloride is an ionic salt, though some covalent character is indicated by its low melting point (275 C) and its high solubility in solvents such as diethyl ether. It behaves as a mild Lewis acid, and aqueous solutions have a pH around 4. It is hydrolyzed to an oxychloride when hydrated forms are heated.

In aqueous solution, zinc chloride is a useful source of Zn2+ for the preparation of other zinc salts, for example zinc carbonate:

ZnCl2(aq) + Na2CO3(aq) → ZnCO3(s) + 2 NaCl(aq)

Preparation & purification

Anhydrous zinc chloride can be prepared from zinc and hydrogen chloride.

Zn + 2 HCl(g) → ZnCl2(s) + H2(g)

Hydrated forms and aqueous solutions may be readily prepared using standard acid-base methods, or from one of its ores, zinc sulfide:

ZnS(s) + 2 HCl(aq) → ZnCl2(aq) + H2S(l)

Commercial samples of zinc chloride typically contain water and zinc oxychloride, the main hydrolysis product. Such samples may be purified as follows: 100 g of crude ZnCl2 are heated to reflux in 800 mL anhydrous dioxan in the presence of zinc metal dust. The mixture is filtered while hot (to remove Zn), then allowed to cool to give pure ZnCl2 as a white precipitate. Anhydrous samples can be purified by sublimation in a stream of hydrogen chloride gas, followed by heating up to 400 C in a stream of dry nitrogen gas.


One use for zinc chloride is as a flux for soldering. This is because of its ability (when molten) to dissolve metal oxides. This property also leads to its use in the manufacture of magnesia cements for dental fillings. ZnCl2 has also been used as a fireproofing agent and for etching metals.

In the laboratory, zinc chloride finds wide use, principally as a moderate-strength Lewis acid. It can catalyse (A) the Fischer indole synthesis[9], and also (B) Friedel-Crafts acylation reactions involving activated aromatic rings[10].

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Related to the latter is the classical preparation[8] of the dye fluorescein from phthalic anhydride and resorcinol, which involves a Friedel-Crafts acylation. This has in fact been done successfully using the wet ZnCl2 sample shown in the picture above.

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Hydrochloric acid alone reacts poorly with primary alcohols and secondary alcohols, but a combination of HCl with ZnCl2 (known together as the "Lucas reagent") at 130 C is effective for the preparation of alkyl chlorides. This probably reacts via an SN2 mechanism with primary alcohols but via SN1 with secondary alcohols.

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Zinc chloride is also able to activate benzylic and allylic halides towards substitution by weak nucleophiles such as alkenes[11]:

Missing image

In similar fashion, ZnCl2 promotes selective NaBH3CN reduction of tertiary, allylic or benzylic halides to the corresponding hydrocarbons.

Zinc chloride is also a useful starting point for the synthesis of many organozinc reagents, such as those used in the palladium catalysed Negishi coupling with aryl halides or vinyl halides[12]. In such cases the organozinc compound is usually prepared by transmetallation from an organolithium or a Grignard reagent, for example:

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Zinc enolates, prepared from alkali metal enolates and ZnCl2, provide control of stereochemistry in aldol condensation reactions due to chelation on to the zinc. In the example shown below, the threo product was favored over the erythro by a factor of 5:1 when ZnCl2 in DME/ether was used[13]. This is because the chelate is more stable when the bulky phenyl group is pseudo-equatorial rather than pseudo-axial, i.e., threo rather than erythro.

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Corrosive, irritant. Wear gloves and goggles.


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Template: inorganic_stylesheet1


  1. N. N. Greenwood, A. Earnshaw, Chemistry of the Elements, 2nd ed., Butterworth-Heinemann, Oxford, UK, 1997.
  2. Handbook of Chemistry and Physics, 71st edition, CRC Press, Ann Arbor, Michigan, 1990.
  3. The Merck Index, 7th edition, Merck & Co, Rahway, New Jersey, USA, 1960.
  4. D. Nicholls, Complexes and First-Row Transition Elements, Macmillan Press, London, 1973.
  5. A. F. Wells, 'Structural Inorganic Chemistry, 5th ed., Oxford University Press, Oxford, UK, 1984.
  6. J. March, Advanced Organic Chemistry, 4th ed., p. 723, Wiley, New York, 1992.
  7. G. J. McGarvey, in Handbook of Reagents for Organic Synthesis, Volume 1: Reagents, Auxiliaries and Catalysts for C-C Bond Formation, (R. M. Coates, S. E. Denmark, eds.), pp. 220-3, Wiley, New York, 1999.
  8. B. S. Furnell et al., Vogel's Textbook of Practical Organic Chemistry, 5th edition, Longman/Wiley, New York, 1989.
  9. R. L. Shriner, W. C. Ashley, E. Welch, in Organic Syntheses Collective Volume 3, p 725, Wiley, New York, 1955.
  10. (a) S. R. Cooper, in Organic Syntheses Collective Volume 3, p 761, Wiley, New York, 1955. (b) S. Y. Dike, J. R. Merchant, N. Y. Sapre, Tetrahedron, 47, 4775 (1991).
  11. E. Bauml, K. Tschemschlok, R. Pock, H. Mayr, Tetrahedron Letters, 29, 6925 (1988).
  12. S. Kim, Y. J. Kim, K. H. Ahn, Tetrahedron Letters, 24, 3369 (1983).
  13. H. O. House, D. S. Crumrine, A. Y. Teranishi, H. D. Olmstead, Journal of the American Chemical Society, 95, 3310 (1973).de:Zinkchlorid

ja:塩化亜鉛 nl:Zinkchloride


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