Here's an old post from Ed Goist on the subject of pH change during cold stabilization. A very interesting wine phenomena. I've had the big drop of pH in wines with low pH before cold stabilization and I'm a believer.
Bill Frazier Olathe, Kansas
From Ed Goist, February 2001 In wines with 11 to 13% alcohol cold stabilization will affect pH as follows;
start pH pH change due to cold stabilization 3.20 or less noticeable, substantial decrease in pH 3.21-3.40 slight decrease in pH 3.41-3.60 very minimal change in pH 3.61-3.75 slight increase in pH 3.76 or more noticeable, substantial increase in pH
This is because of the pKa for potassium bitartrate of 3.55 bitartrates are effectively an alkaline substance for a wine with an overall pH of 3.5 or lower, and they are effectively an acid substance for a wine with an overall pH of 3.6 or higher.
When tartrates are removed from wine with a very low pH, an alkaline constituent is effectively being removed and a greater proportion of acid constituents overall will be dissociated. This will cause the pH to decrease.
When tartrates are removed from a wine with a very high pH, an acidic constituent is effectively being removed and a smaller proportion of acid constituents overall will be dissociated. This will cause the pH to increase.