[
start of tooting my own horn] I looked for the relation between taste and brew parameters in 2002, after I got my Tea and could play with them somewhat. The only thing I found at the time, after a lot of searching, was a 2 separate notes in Schomer that in Italy the further south one went, the darker the roast, and the lower the pstat settings. This meant Italians tended to pull darker roasts at lower temperatures.
People were PIDing their Silvia's at the time, so this is one of those bits of info that was rapidly confirmed by everyone who tried it. I've been collecting tips on this ever since; and most are posted in my espresso guide here:
http://home-barista.com/espresso-guide-skills.html.
Shorter time and more lungo pulls also favor acidic, whereas longer time, more ristretto pulls favor bitters. So this too is a way of compensating if one cannot change the temperature
[end of tooting my own horn]
I don't know much chemistry, but in general, every substance dissolves more if the water is hotter or one exposes the solid to it for longer. Also, in general, substances with low molecular weights dissolve more readily than those with high molecular weights. Coffee acids and origin aromas tend to be lighter than the bitter, roasty aromatics (see flavor wheel)
So my guess is that the acidic components dissolve more readily, and will be overrepresented when brew temperature is cooler or the pull is shorter. The bitter components dissolve more slowly, and require more heat and time. This means the acidic taste of cool shots is not from more acids, but from the changed flavor balance resulting from fewer bitters.
The thing that doesn't work in this theory is that really low temperature brews (toddy coffee and the recent aeropress) have no discernable flavor at all, except sweetish caramels. If the molecular weight idea is correct, these should be intermediate between the acidic and bitter flavors. They also predominate in the middle part of the espresso pull, which supports the molecular weight idea. But in toddy coffee, they are the only things to make it into the brew.