depends on what you are using it for. White vinegar is considered "light" in consistency and balsamic "heavy". Balsamic, if aged properly, can be almost syrup-like in consistency. So, it will depend on the application. If you are using it for salad dressing, fantastic! if you are using it for a light pickling, not so much. Best advice I can give is to give it a try and see if it works. If not, you know better next time!
Also, good balsamic should never be cooked. It should be used at the last minute, off the heat...if heated at all.