Octane boosting additives do work provided that your car has cylinder at a time knock detection and correction (whereby it will automatically advance as far as possible under all conditions until it's just short of the point where combustion starts too early), or you advance the ignition timing throughout the rev/load range either mechanically or electronically.
As Waynne says, petrol is very volatile and the vapour flashpoint is very low.
The best, and safest way, to mix is in the tank itself. Stick the additive in first and then fill with your favourite brand of petrol. This ensures thorough mixing.