I never add anything directly to the mash, but always prepare liquor before mashing in, simply because, IME, the buffer systems can set up so rapidly that once grain hits water your pH is pretty well locked in. If you mash in, check pH, then try to adjust, you may see a change in pH at first, but if you check back a bit later it will have been pulled back toward the initial value. Take notes, and revise your treatment next time.