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Structure

AsCl3 is a pyramidal molecule with C3v symmetry. The As-Cl bond is 2.161 Å and the angle Cl-As-Cl is 98° 25'±30.²³ AsCl3 has four normal modes of vibration: ν1(A1) 416, ν2(A1) 192, ν3 393, and ν4(E) 152 cm−1.⁴

Synthesis

This colourless liquid is prepared by treatment of arsenic(III) oxide with hydrogen chloride followed by distillation:

As2O3 + 6 HCl → 2 AsCl3 + 3 H2O

It can also be prepared by chlorination of arsenic at 80–85 °C, but this method requires elemental arsenic.⁵

2 As + 3 Cl2 → 2 AsCl3

Arsenic trichloride can be prepared by the reaction of arsenic oxide and sulfur monochloride. This method requires simple apparatus and proceeds efficiently:⁶

2 As2O3 + 6 S2Cl2 → 4 AsCl3 + 3 SO2 + 9 S

A convenient laboratory method is refluxing arsenic(III) oxide with thionyl chloride:⁷

2 As2O3 + 3 SOCl2 → 2 AsCl3 + 3 SO2

Arsenic trichloride can also be prepared by the reaction of hydrochloric acid and arsenic(III) sulfide.

As2S3 + 6 HCl → 2 AsCl3 + 3 H2S

Reactions

Hydrolysis gives arsenous acid and hydrochloric acid:

AsCl3 + 3 H2O → As(OH)3 + 3 HCl

Although AsCl3 is less moisture sensitive than PCl3, it still fumes in moist air.⁸

AsCl3 undergoes redistribution upon treatment with As2O3 to give the inorganic polymer AsOCl. With chloride sources, AsCl3 also forms salts containing the anion [AsCl4]−. Reaction with potassium bromide and potassium iodide give arsenic tribromide and arsenic triiodide, respectively.

AsCl3 is useful in organoarsenic chemistry, for example triphenylarsine is derived from AsCl3:⁹

AsCl3 + 6 Na + C6H5Cl → As(C6H5)3 + 6 NaCl

The chemical weapons called Lewisites are prepared by the addition of arsenic trichloride to acetylene:

AsCl3 + C2H2 → ClCH=CHAsCl2

Safety

Inorganic arsenic compounds are highly toxic,¹⁰ and AsCl3 especially so because of its volatility and solubility (in water).

It is classified as an extremely hazardous substance in the United States as defined in Section 302 of the U.S. Emergency Planning and Community Right-to-Know Act (42 U.S.C. 11002), and is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities.¹¹

References

1. Sabina C. Grund, Kunibert Hanusch, Hans Uwe Wolf "Arsenic and Arsenic Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, VCH-Wiley, 2008, Weinheim.doi:10.1002/14356007.a03_113.pub2 /wiki/Doi_(identifier) ↩

2. P. Kisliuk; C. H. Townes. "The Microwave Spectra and Molecular Structure of Phosphorus and Arsenic Trichloride". J. Chem. Phys. 1950, 18. ↩

3. Jean Galy; Renee Enjalbertl Pierre Lecante; Andrzej Burian "AsCl3: From the crystalline to the liquid state. XRD (176< T (K) < 250) and WAXS (295K) studies" Inorg. Chem 2002, volume 41, pp. 693–698.doi:10.1021/ic0102788 /wiki/Doi_(identifier) ↩

4. Klapoetke, Thomas M. "The vibrational spectrum of arsenic trichloride" Main Group Metal Chemistry 1997, volume 20, pp. 81–83. ↩

5. Sabina C. Grund, Kunibert Hanusch, Hans Uwe Wolf "Arsenic and Arsenic Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, VCH-Wiley, 2008, Weinheim.doi:10.1002/14356007.a03_113.pub2 /wiki/Doi_(identifier) ↩

6. R. C. Smith, "Manufacture of Arsenic trichloride" The Journal of Industrial and Engineering Chemistry 1919, volume 11, pp. 109–110. doi:10.1021/ie50110a009 /wiki/Doi_(identifier) ↩

7. Pandey, S. K.; Steiner, A.; Roesky, H. W. (1997). "Arsenic(III) chloride". Inorganic Syntheses. Vol. 31. p. 148-150. doi:10.1002/9780470132623.ch24. ISBN 978-0-471-15288-0. 978-0-471-15288-0 ↩

8. Holleman, A. F.; Wiberg, E. Inorganic Chemistry Academic Press: San Diego, 2001. ISBN 0-12-352651-5. /wiki/ISBN_(identifier) ↩

9. Shriner, R. L.; Wolf, C. N. (1963). "Tetraphenylarsonium Chloride Hydrochloride". Organic Syntheses; Collected Volumes, vol. 4, p. 910.. Describes the preparation of As(C6H5)3. http://www.orgsyn.org/demo.aspx?prep=cv4p0910 ↩

10. Sabina C. Grund, Kunibert Hanusch, Hans Uwe Wolf "Arsenic and Arsenic Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, VCH-Wiley, 2008, Weinheim.doi:10.1002/14356007.a03_113.pub2 /wiki/Doi_(identifier) ↩

11. 40 C.F.R.: Appendix A to Part 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities (PDF) (Report) (July 1, 2008 ed.). Government Printing Office. Archived from the original (PDF) on February 25, 2012. Retrieved October 29, 2011. https://web.archive.org/web/20120225051612/http://edocket.access.gpo.gov/cfr_2008/julqtr/pdf/40cfr355AppA.pdf ↩