Pressurised Hot Water
In traditional open vented systems, as the water is heated, it simply expands into the water tank in the loft. If there's a fault with the thermostat, the water will continue heating and may eventually reach 100°C, and boil. The boiling water will turn to steam and evaporate into the atmosphere.
With an unvented system, the water is typically held under pressure at 3 bar. If the thermostat fails, and the water continues heating, it could reach 100°C. In a vented system the water would boil and evaporate, but remain at 100°C.
With an unvented system, at say 3 bar pressure, the boiling point of water would be 134°C, so the pressure and temperature will continue to increase. At above 100°C, the water would instantly flash into steam when released into normal atmospheric pressure, for example if opening a tap!. This can be extremely dangerous to both people and anything in the surrounding area. It is critical that unvented systems are installed with the correct safety controls to ensure the water never reaches boiling point, and if the temperature or pressure exceeds safe predetermined limits, the safety valves will release to rapidly reduce the temperature and/or pressure.