This testing & boiling is all pretty unnecessary, in my opinion.
First and foremost, what is your current pH, KH, and GH? If the pH is high already and the KH and GH are high, the addition of some rocks what may be alkaline aren't going to matter a lick.
Secondly, how much are you going to add? Estimate what percentage of substrate will be these pebbles you found? 1%? 5%? 10%? The reason I ask is again, if it is only a small amount of pebbles you are going to add, it isn't going to matter.
Thirdly, boiling can be dangerous because if there is an air pocket in the rock and you heat up that air pocket... increased temperature in a gas means increased pressure in a gas, especially when the volume is held constant, and the rock may pop and shoot high velocity projectiles at you. Or at the very least damage your pot. A good cleaning, I'd use soap and water, but if you feel a really strong need you can use bleach, and then a very, very good rinsing is sufficient.
Part of the issue here is, if you think about it, what can that rock have on it that can be dangerous to fish? The majority of fish parasites/diseases are obligate fish parasites -- that is, they have to have fish to continue their life cycles. Ich, for example, has to have fish, otherwise the parasite will die. Unless you got these pebbles from a polluted beach, or were buried in the nest of some other animal or some otherwise extraordinary circumstances, they are going to be safe. One of the biggest things to make sure that there is nothing dangerous to fish on them is to spread them out and let them dry off. Very, very few things that are dangerous to fish can survive being dried out.
Finally, if you do insist on testing how alkaline the rocks are, the vinegar test isn't too accurate. Vinegar is a very weak acid, and it takes a very acidic rock to see significant fizzing. If you have a 2 bottle nitrate test, you can use the liquid in the second bottle. It is nitric acid, a strong acid, and is much more likely to react significantly than a weak acid.