Arsenic trichloride

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.
2 As + 3 Cl2 → 2 AsCl3
Arsenic trichloride can also be prepared by the reaction of arsenic
oxide and sulfur monochloride. This method requires simple
apparatus and proceeds efficiently:
2 As2O3 + 6 S2Cl2 → 4 AsCl3 + 3 SO2 + 9 S
A convenient laboratory method is refluxing arsenic(III) oxide with
thionyl chloride:
2 As2O3 + 3 SOCl2 → 2 AsCl3 + 3 SO2
 Arsenic trioxide
Arsenic trioxide can be generated via routine processing of arsenic
compounds including the oxidation (combustion) of arsenic and
arsenic-containing minerals in air. Illustrative is the roasting of
orpiment, a typical arsenic sulfide ore.
2 As2S3 + 9 O2 → 2 As2O3 + 6 SO2
Most arsenic oxide is, however, obtained as a volatile by-product of
the processing of other ores. For example, arsenopyrite, a common
impurity in gold- and copper-containing ores, liberates arsenic
trioxide upon heating in air. The processing of such minerals has led
to numerous cases of poisonings.Only in China are arsenic ores
intentionally mined.
In the laboratory, it is prepared by hydrolysis of arsenic trichloride:
2 AsCl3 + 3 H2O → As2O3 + 6 HCl

As2O3 occurs naturally as two minerals, arsenolite (cubic) and

claudetite (monoclinic). Both are relatively rare secondary minerals
found in oxidation zones of As-rich ore deposits. Sheets of As2O3
stand for part of structures of the recently discovered minerals
lucabindiite, (K,NH4)As4O6(Cl,Br), and its sodium-analogue
torrecillasite.
 Arsine

AsH3 is generally prepared by the reaction of As3+ sources with H−

equivalents.
4 AsCl3 + 3 NaBH4 → 4 AsH3 + 3 NaCl + 3 BCl3
As reported in 1775, Carl Scheele reduced arsenic(III) oxide with
zinc in the presence of acid. This reaction is a prelude to the Marsh
test, described below.
Alternatively, sources of As3− react with protonic reagents to also
produce this gas. Zinc arsenide and sodium arsenide are suitable
precursors:
Zn3As2 + 6 H+ → 2 AsH3 + 3 Zn2+
Na3As + 3 HBr → AsH3 + 3 NaBr
As2O3 + 6 Zn + 12 HNO3 → 2 AsH3 + 6 Zn(NO3)2 + 3 H2O
 Lewisite (L)

The compound is prepared by the addition of arsenic trichloride to

acetylene in the presence of a suitable catalyst:
AsCl3 + C2H2 → ClCHCHAsCl2 (Lewisite)
Lewisite, like other arsenous chlorides, hydrolyses in water to form
hydrochloric acid and chlorovinylarsenous oxide (a less-powerful
blister agent):
ClCHCHAsCl2 + 2 H2O → ClCHCHAs(OH)2 + 2 HCl
This reaction is accelerated in alkaline solutions, and forms acetylene
and trisodium arsenate.
Lewisite will also react with metals to form hydrogen gas. It is
combustible, but difficult to ignite.
Acetylene reacts with AsCl3 in hydrochloric acid solution, with
mercuric chloride as a catalyst, to give Lewisite in 80 to 85 percent
yield (based on AsCl 3)
 Methyldichloroarsine
Focusing on the arsenic center, the molecule is pyramidal with the
Cl-As-Cl and C-As-Cl angles approaching 90° (see image). Virtually
all related arsenic(III) compounds adopt similar structures.
Methyldichloroarsine is produced by the reaction of
methylmagnesium chloride and arsenic trichloride:
AsCl3 + CH3MgCl → CH3AsCl2 + MgCl2

Typically such syntheses are conducted in ether or THF solutions and

typically the product is isolated by distillation. Use of larger amounts
of the magnesium reagent affords greater amounts of
dimethylchloroarsine ((CH3)2AsCl) and trimethylarsine ((CH3)3As).
In World War I, the German manufacturing method consisted of a
three-step reaction beginning with methylation of sodium arsenite:
2 Na3AsO3 + (CH3O)2SO2 → 2 CH3AsO(ONa)2 + Na2SO4,

followed by reduction of the disodium monomethylarsonate with

sulfur dioxide:
CH3AsO(ONa)2 + SO2 → CH3AsO + Na2SO4,

subsequently reacting the monomethylarsine oxide thus formed with

hydrogen chloride to yield methyldichloroarsine:
CH3AsO + 2 HCl → CH3AsCl2 + H2O

The As-Cl bonds in MD are susceptible toward nucleophilic attack.

Reduction of MD with sodium metal affords the polymer [CH3As]n.