Chloral (CCl₃CHO, trichloracetaldehyde) is produced by chlorinating alcohol. Chloral is used in the preparation of pure chloroform and (by addition of water) of chloral hydrate (trichloracetaldehyde hydrate), the well-known soporific.

Chloroform (CHCl₃, trichlormethane).—Some methods for the preparation of chloroform have been already mentioned (Chloral, Methyl Chloride). Technically it is prepared by distillation of alcohol or acetone with bleaching powder. The workers employed are said to be affected by the stupefying vapours. Further, there is the risk of chlorine gas from use of chloride of lime.

Chloride of nitrogen (NCl₃) is an oily, volatile, very explosive, strongly smelling substance, which irritates the eyes and nose violently and is in every respect dangerous; it is obtained from the action of chlorine or hypochlorous acid on sal-ammoniac. The poisonous nature of these substances may come into play. Risk of formation of chloride of nitrogen can arise in the production of gunpowder from nitre containing chlorine.

Cyanogen chloride (CNCl).—Cyanogen chloride is made from hydrocyanic acid or cyanide of mercury and chlorine. Cyanogen chloride itself is an extremely poisonous and irritating gas, and all the substances from which it is made are also poisonous. According to Albrecht cyanogen chloride can arise in the preparation of red prussiate of potash (by passage of chlorine gas into a solution of the yellow prussiate) if the solution is treated with chlorine in excess; the workers may thus be exposed to great danger.

Chlorobenzene.—In his paper referred to Leymann cites three cases of poisoning by chlorobenzene, one by dinitrochlorobenzene, and, further, three cases of burning by chlorobenzene and one by benzoyl chloride (C₆H₅COCl). The last named is made by treating benzaldehyde with chlorine, and irritates severely the mucous membranes, while decomposing into hydrochloric acid and benzoic acid.[11] Benzal chloride (C₆H₅CHCl₂), benzo trichloride (C₆H₅CCl₃), and benzyl chloride (C₆H₅CH₂Cl) are obtained by action of chlorine on boiling toluene. The vapours of these volatile products irritate the respiratory passages. In the manufacture there is risk from the effect of chlorine gas and toluene vapour (see Benzene, Toluene).

Leymann[12] describes in detail six cases of poisoning in persons employed in a chlorobenzene industry, of which two were due to nitrochlorobenzene. Symptoms of poisoning—headache, cyanosis, fainting, &c.—were noted in a person working for three weeks with chlorobenzene.[13]

In Lehmann’s opinion chlorine rash, the well-recognised skin affection of chlorine workers, may be due to contact with substances of the chlorbenzol group.[14]

Iodine and iodine compounds.—Formerly iodine was obtained almost exclusively from the liquor formed by lixiviation of the ash of seaweed (kelp, &c.); now the principal sources are the mother liquors from Chili saltpetre and other salt industries. From the concentrated liquor the iodine is set free by means of chlorine or oxidising substances and purified by distillation and sublimation. Iodine is used for the preparation of photographic and pharmaceutical preparations, especially iodoform (tri-iodomethane, CHI₃), which is made by acting with iodine and caustic potash on alcohol, aldehyde, acetone, &c.

Apart from possible injurious action of chlorine when used in the preparation of iodine, workers are exposed to the possibility of chronic iodine poisoning. According to Ascher[15] irritation effects, nervous symptoms, and gastric ulceration occur in iodine manufacture and use. He considers that bromide of iodine used in photography produces these irritating effects most markedly. Layet and also Chevallier in older literature have made the same observations.