Well, if you read my reply carefully you'll see I qualify "not available" with the caveat that that depends on whether you have a lower temperature heat sink available. (I have to cover the options because I know what a nitpicking and deliberately obtuse git you can be.)
The energy in an unburnt gallon of gas is not in the form of heat, so it is, of course, available. Once the gasoline has been burnt and is thereby turned to high temperature heat, some of it is available to do work pushing the pistons of your car, but this lowers its temperature, at which point the heat then comes out (of the exhaust and via the radiator), into the atmosphere as low temperature waste heat. At this point it is unavailable.
Got it?