How does fabric softener work?

From wikipedia:

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 feel smoother and preventing buildup of static electricity.

Therefore vinegar should not work, as it is volatile?

No, white vinegar should work.

http://www.thriftyfun.com/tf159285.tip.html

No offense, but that source is just someone saying it works and nothing more. Do you have any clue WHY it would work? My contention is my wife is accomplishing nothing with the vinegar, but if it does work I’d like to understand why.

I don’t see vinegar working as a fabric softener. It helps as a rinsing agent, in that it strips the build up of fabric softener residue and other residue. The pH of vinegar will strip the waxy/fat residue. It’s not a matter of it being ‘volatile’. It’s a matter of acid vs base. Vinegar is rather acid and the things that coat the fabric are more base. They are like soap, with a pH of over 7, I think… and it has an emulsifier in it so it dissolves in water.

http://www.enotes.com/how-products-encyclopedia/fabric-softener.

There are two ways to get the fabric softener feel….. you can add it to your washing or put a dryer sheet in. Both will coat your fabric with a cationic softeners. If you are out of fabric softeners, you can try hair conditioner, or in a real pinch, rubbing your static clingy clothes with a bar of soap on the inside. This works well with skirts that stick to your legs.

I’m old school. I don’t like the silicone based ones. ;o)

Any qualified chemist out there want to correct me or tweak my info, please do!..... I’m a novice and am always learning.

@cockswain “Mechanical friction in the washing process induces static charges that cause the microfibrils to project orthogonally from the fiber bundle
upon drying. These microfibrils act as barbs which inhibit
fiber–fiber slippage, interfere with fiber flexibility, and are
perceived as a source of drag when drawn across the skin
All of these phenomena contribute to the total perception
of roughness. Softening materials can reduce
fiber–fiber interactions by reducing static and allowing microfibrils
to lay parallel to the fiber bundle and/or by coating
and lubricating the fiber bundle to minimize friction.
Further, they can provide a lubricating layer between the
fiber surface and human epidermis. The net result is the
perception of a less abrasive, more pliable fabric. By this
coating/lubricating mechanism, lime soaps, oils, flat clay
platelets, and cationic surfactants all function to greater or
lesser extent to improve fabric hand.”

http://www.springerlink.com/content/c3gm782357095555/fulltext.pdf

@cockswain to argue for your wife’s use of vinegar in the washer, I’d say it works to soften the material of the clothing because of the acidic property of vinegar: http://www.apple-cider-vinegar-benefits.com/properties-of-vinegar.html

@bkcunningham Your first answer makes total sense and corroborates @Math321 ‘s first answer, so I’m sold on that explanation. Regarding vinegar and your link, I still don’t see how it helps but maybe I scanned your link too fast. I can see how vinegar could dissolve off built up residues from clothing, but it doesn’t soften by the same way the coating agents do. I’m guessing vinegar might seem to make a difference if used occasionally, but if used every wash I can’t see how it could possibly produce the same effect as traditional fabric softeners.

@cazzie I was referring to the volatility of vinegar since I figured it would be evaporating away in the dryer, if it hadn’t been previously rinsed away, and thus I didn’t see how it could have any effect.