I always thought that pure water cannot exceed 100° Celsius at atmospheric pressure without first turning into its gaseous state. How is it that the water heated in the microwave oven can superheat and exceed 100° Celsius? — AC
The relative stabilities of liquid and gaseous water depend on both temperature and pressure. To understand this, consider what is going on at the surface of a glass of water. Water molecules in the liquid water are leaving the water’s surface to become gas above it and water molecules in the gas are landing and joining the liquid water below. It’s like a busy airport, with lots of take-offs and landings. If the glass of water is sitting in an enclosed space, the arrangement will eventually reach equilibrium—the point at which there is no net transfer of molecules between the liquid in the glass and the gas above it. In that case, there will be enough water molecules in the gas to ensure that they land as often as they leave.
The leaving rate (the rate at which molecules break free from the liquid water) depends on the temperature. The hotter the water is, the more frequently water molecules will be able to break away from their buddies and float off into the gas. The landing rate (the rate at which molecules land on the water’s surface and stick) depends on the density of molecules in the gas. The more dense the water vapor, the more frequently water molecules will bump into the liquid’s surface and land.
As you raise the temperature of the water in your glass, the leaving rate increases and the equilibrium shifts toward higher vapor density and less liquid water. By the time you reach 100° Celsius, the equilibrium vapor pressure is atmospheric pressure, which is why water tends to boil at this temperature (it can form and sustain steam bubbles). Above this temperature the equilibrium vapor pressure exceeds atmospheric pressure. The liquid water and the gas above it can reach equilibrium, but only if you allow the pressure in your enclosed system to exceed atmospheric pressure. However, if you open up your enclosed system, the water vapor will spread out into the atmosphere as a whole and there will be a never-ending stream of gaseous water molecules leaving the glass. Above 100° C, liquid water can’t exist in equilibrium with atmospheric pressure gas, even if that gas is pure water vapor.
So how can you superheat water? Don’t wait for equilibrium! The road to equilibrium may be slow; it may take minutes or hours for the liquid water to evaporate away to nothing. In the meantime, the system will be out of equilibrium, but that’s ok. It happens all the time: a snowman can’t exist in equilibrium on a hot summer day, but that doesn’t mean that you can’t have a snowman at the beach… for a while. Superheated water isn’t in equilibrium and, if you’re patient, something will change. But in the short run, you can have strange arrangements like this without any problem.