Stewing with Apple Cider Vinegar
I'm working on making a long cooked version of a stew which uses apple cider vinegar as part of the flavor.
I was wondering what happens to the flavor of the vinegar when it's cooked for a long time. I have technical constraints and it needs to cook for about 24 hours, and I was wondering if it would lose the flavor.
Also I was wondering if adding vinegar is pointless, seeing as long cooked stews tend to get very brown, it'll end up being a very alkaline environment, and maybe that would cancel out the acidity.
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An acid in a stew serves much the same purpose it would in a marinade. It aids in the tenderizing (typical 'stew meat' is cut from inferior cuts of the beef and can be tough) and balances the flavors. (As such I would disagree with @lspare about adding it "at the end", it needs time to do it's work)
Browning is a separate issue. Browning is the result of the Maillard reaction and should occur when stew meat is seared prior to being incorporated into the stew. In a stew the 'cooking temperature' is never above 212°F (100°C) and this will not 'brown' the meat.
Add the vinegar in at the end of the cooking time if, after tasting, you think it needs the brightness. Long cooking times mellow flavors (as you have pointed out), and acidic/bright ingredients like vinegar are usually added toward the end so they don't get lost.
The only exception I can think of to this is when making bone broth, but the vinegar in that is not as much for acidity as for freeing up the collagen in the bones for the added nutrition.
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