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Chemistry · Ch 7 — The p-Block Elements

Phosphorus Trichloride

7.8.1

Phosphorus Trichloride

Phosphorus trichloride (PCl3PCl_3) is the most important of the phosphorus trihalides.

Preparation

It is prepared simply by passing dry chlorine gas over heated white phosphorus:

P4+6Cl2→4PCl3P_4 + 6Cl_2 \rightarrow 4PCl_3

An alternative route uses thionyl chloride reacting with white phosphorus:

P4+8SOCl2→4PCl3+4SO2+2S2Cl2P_4 + 8SOCl_2 \rightarrow 4PCl_3 + 4SO_2 + 2S_2Cl_2

Properties

PCl3PCl_3 is a colourless, oily liquid that is moisture-sensitive: it hydrolyses readily in the presence of water to give phosphorous acid and hydrochloric acid:

PCl3+3H2O→H3PO3+3HClPCl_3 + 3H_2O \rightarrow H_3PO_3 + 3HCl

It is also reactive toward organic compounds bearing an −OH-OH group, such as acetic acid and ethanol, converting them into their chloro derivatives:

3CH3COOH+PCl3→3CH3COCl+H3PO33CH_3COOH + PCl_3 \rightarrow 3CH_3COCl + H_3PO_3

3C2H5OH+PCl3→3C2H5Cl+H3PO33C_2H_5OH + PCl_3 \rightarrow 3C_2H_5Cl + H_3PO_3 …