Many organic arsenic compounds are known, analogous to those of
nitrogen and phosphorus, but apparently the primary and secondary
arsines, AsH2.CH3 and AsH(CH3)2, do not exist, although the
corresponding chlorine derivatives, AsCl2.CH3, methyl arsine chloride,
and AsCl(CH4)2, dimethyl arsine chloride, are known. The tertiary
arsines, such as As(CH3)3, trimethyl arsine, and the quaternary
arsonium iodides and hydroxides, (CH3)4AsI and (CH3)4As.OH,
tetramethyl arsonium iodide and hydroxide, have been obtained. The
arsines and arsine chlorides are liquids of overpowering smell, and in
some cases exert an extremely irritating action on the mucous
membrane. They do not possess basic properties; the halogen in the
chlorine compounds is readily replaced by oxygen, and the oxides
produced behave like basic oxides. The chlorides AsCl2.CH3 and
AsCl(CH3)2 as well as As(CH3)3 are capable of combining with two atoms
of chlorine, the arsenic atom apparently changing from the tri- to the
penta-valent condition, and the corresponding oxygen compounds can
also be oxidized to compounds containing one oxygen atom or two
hydroxyl groups more, forming acids or oxides. The compounds of the
type AsX5, e.g. AsCl4.CH3, AsCl3(CH3)2, on heating break down, with
separation of methyl chloride and formation of compounds of the type
AsX3; the breaking down taking place more readily the fewer the number
of methyl groups in the compound. The dimethyl arsine (or cacodyl)
compounds have been most studied. On distillation of equal parts of
dry potassium acetate and arsenious oxide, a colourless liquid of
unbearable smell passes over, which is spontaneously inflammable and
excessively poisonous. It is sometimes called Cadet's fuming liquid,
and its composition was determined by R. Bunsen, who gave it the name
cacodyl oxide ([Greek: kakodes], stinking); its formation may be shown
thus:
As4O6 + 8CH3CO2K = 2[(CH3)2As]2O + 4K2CO3 + 4CO2.
The liquid is spontaneously inflammable owing to the presence of free
cacodyl, As2(CH3)4, which is also obtained by heating the oxide with
zinc clippings in an atmosphere of carbon dioxide; it is a liquid of
overpowering odour, and boils at 170 deg.C. Cacodyl oxide boils at 150
deg. C., and on exposure to air takes up oxygen and water and passes
over into the crystalline cacodylic acid, thus:
[(CH3)2As]2O + H2O + O2 = 2(CH3)2As.O.OH.
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