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Fabric softeners work by coating the surface of the cloth fibers with a thin layer of chemicals; these chemicals have lubricant properties and are electrically conductive, thus making the fibers feeling smoother and preventing buildup of static electricity.
Cationic softeners bind by electrostatic attraction to the negatively charged groups on the surface of the fibers and neutralizing their charge; the long aliphatic chains are then oriented towards the outside of the fiber, imparting lubricity. Vinegar works on some materials in a similar way, as the hydrogen ions bind to the anionic groups on the fibers.
Contemporary fabric softeners tend to be based on quaternary ammonium salts with one or two long alkyl chains, a typical compound being dipalmitoylethyl hydroxyethylmonium methosulfate. Other cationic compounds can be derived from imidazolinium, substituted amine salts, or quarternary alkoxy ammonium salts. One of the most common compounds of the early formulations was dihydrogenated tallow dimethyl ammonium chloride (DHTDMAC).