Sorry to say they seem to be generally wasted money, unless for possibly replacing a bit of the 10% annual losses on an otherwise working system....But even then Id prefer to have it done properly for optimal performance
Which presumably gets replaced with air, making adding more refrigerant in via silly diy kits a mission doomed to failure...
No. Air can only get in if the pressure in the A/C system drops to or below atmospheric pressure (nominally 1 bar).
The AC system is protected by a low pressure (LP) switch which cuts the compressor out if the gas pressure in the pipes drops below (about) 2 bar (30 psi). There is a second high pressure (HP) switch that cuts the compressor out if the gas pressure exceeds (IIRC) about 8 bar (120 psi). There is also a mechanical 'dump' safety valve on the compressor that will vent the gas to atmosphere if the pressure exceeds another limit - 20 bar (290 psi) IIRC.
With the engine not running, the entire A/C system will sit at a pressure dependent on ambient temperature and the amount of gas in the system - usually 3-4 bar ish. When you start the engine, and the compressor starts, the output of the compressor pumps up to 8 bar, and the input to the compressor drops close to 2 bar. This keeps all the pressure switches happy. However, if you put too much gas in, then the compressor output pressure may exceed the HP switch limit, and the compressor will cut out. On the other hand if there is not enough gas in the system, then the compressor may or may not start. If it does start, the output pressure rises, and the input pressure drops. If the input pressure drops below the LP cut-out then the compressor will stop again.
Due to the high pressures involved (up to 8 bar) A/C gas will escape from the system through the slightest pipework or seal leak. However, air can't start to contaminate the A/C gas until/unless the pressure drops to near ambient. If the pressure is that low, it's unlikely a single can of gas would raise the pressure enough to get above the minimum LP (2 bar) to allow the compressor to start.
All that said, I'd still rather get the system properly vacumed down and re-gassed with the correct mass of refridgerant that try and use a diy kit. And a system shouldn't lose anything like 10% a year. My Carlton was last re-gassed over 10 years ago and it's still working.