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If the vapor pressure of the liquid is greater than the total ambient pressure, including that of any air (or other gas), the liquid evaporates rapidly; in other words, it boils. Thus, the boiling point of a liquid at a given pressure is the temperature at which its vapor pressure equals the ambient pressure. Liquid and gas phases are in equilibrium at the boiling temperature ( [link] ). If a substance is in a closed container at the boiling point, then the liquid is boiling and the gas is condensing at the same rate without net change in their amounts.

Figure a shows a tank of water that is half filled. An arrow going up from the water is labeled vaporization. An arrow going down from the air within the tank to the water is labeled condensation. A pressure gauge and thermometer are attached to the tank. Figure b shows the same setup. The pressure and temperature in figure b are higher than those in figure a. The arrows indicating vaporization and condensation are also longer than those in figure a.
Equilibrium between liquid and gas at two different boiling points inside a closed container. (a) The rates of boiling and condensation are equal at this combination of temperature and pressure, so the liquid and gas phases are in equilibrium. (b) At a higher temperature, the boiling rate is faster, that is, the rate at which molecules leave the liquid and enter the gas is faster. This increases the number of molecules in the gas, which increases the gas pressure, which in turn increases the rate at which gas molecules condense and enter the liquid. The pressure stops increasing when it reaches the point where the boiling rate and the condensation rate are equal. The gas and liquid are in equilibrium again at this higher temperature and pressure.

For water, 100 ° C is the boiling point at 1.00 atm, so water and steam should exist in equilibrium under these conditions. Why does an open pot of water at 100 ° C boil completely away? The gas surrounding an open pot is not pure water: it is mixed with air. If pure water and steam are in a closed container at 100 ° C and 1.00 atm, they will coexist—but with air over the pot, there are fewer water molecules to condense, and water boils away. Another way to see this is that at the boiling point, the vapor pressure equals the ambient pressure. However, part of the ambient pressure is due to air, so the pressure of the steam is less than the vapor pressure at that temperature, and evaporation continues. Incidentally, the equilibrium vapor pressure of solids is not zero, a fact that accounts for sublimation.

Check Your Understanding Explain why a cup of water (or soda) with ice cubes stays at 0 ° C, even on a hot summer day.

The ice and liquid water are in thermal equilibrium, so that the temperature stays at the freezing temperature as long as ice remains in the liquid. (Once all of the ice melts, the water temperature will start to rise.)

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Phase change and latent heat

So far, we have discussed heat transfers that cause temperature change. However, in a phase transition, heat transfer does not cause any temperature change.

For an example of phase changes, consider the addition of heat to a sample of ice at −20 ° C ( [link] ) and atmospheric pressure. The temperature of the ice rises linearly, absorbing heat at a constant rate of 2090 J/kg · ºC until it reaches 0 ° C . Once at this temperature, the ice begins to melt and continues until it has all melted, absorbing 333 kJ/kg of heat. The temperature remains constant at 0 ° C during this phase change. Once all the ice has melted, the temperature of the liquid water rises, absorbing heat at a new constant rate of 4186 J/kg · ºC . At 100 ° C , the water begins to boil. The temperature again remains constant during this phase change while the water absorbs 2256 kJ/kg of heat and turns into steam. When all the liquid has become steam, the temperature rises again, absorbing heat at a rate of 2020 J/kg · ºC . If we started with steam and cooled it to make it condense into liquid water and freeze into ice, the process would exactly reverse, with the temperature again constant during each phase transition.

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Source:  OpenStax, University physics volume 2. OpenStax CNX. Oct 06, 2016 Download for free at http://cnx.org/content/col12074/1.3
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