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Learning objectives

By the end of this section, you will be able to:

  • Interpret a phase diagram.
  • State Dalton’s law.
  • Identify and describe the triple point of a gas from its phase diagram.
  • Describe the state of equilibrium between a liquid and a gas, a liquid and a solid, and a gas and a solid.

Up to now, we have considered the behavior of ideal gases. Real gases are like ideal gases at high temperatures. At lower temperatures, however, the interactions between the molecules and their volumes cannot be ignored. The molecules are very close (condensation occurs) and there is a dramatic decrease in volume, as seen in [link] . The substance changes from a gas to a liquid. When a liquid is cooled to even lower temperatures, it becomes a solid. The volume never reaches zero because of the finite volume of the molecules.

Line graph of volume versus temperature showing the relationship for an ideal gas and a real gas. The line for an ideal gas is linear starting at absolute zero showing a linear increase in volume with temperature. The line for a real gas is linear above a temperature of negative one hundred ninety degrees Celsius and follows that of the ideal gas. But below that temperature, the graph shows an almost vertical drop in volume with temperature as the temperature drops and the gas condenses.
A sketch of volume versus temperature for a real gas at constant pressure. The linear (straight line) part of the graph represents ideal gas behavior—volume and temperature are directly and positively related and the line extrapolates to zero volume at 273 . 15 º C size 12{ +- "273" "." "15"°C} {} , or absolute zero. When the gas becomes a liquid, however, the volume actually decreases precipitously at the liquefaction point. The volume decreases slightly once the substance is solid, but it never becomes zero.

High pressure may also cause a gas to change phase to a liquid. Carbon dioxide, for example, is a gas at room temperature and atmospheric pressure, but becomes a liquid under sufficiently high pressure. If the pressure is reduced, the temperature drops and the liquid carbon dioxide solidifies into a snow-like substance at the temperature 78 º C size 12{ +- "78"°C} {} . Solid CO 2 size 12{"CO" rSub { size 8{2} } } {} is called “dry ice.” Another example of a gas that can be in a liquid phase is liquid nitrogen ( LN 2 ) size 12{ \( "LN" rSub { size 8{2} } \) } {} . LN 2 size 12{"LN" rSub { size 8{2} } } {} is made by liquefaction of atmospheric air (through compression and cooling). It boils at 77 K ( 196 º C ) size 12{ \( –"196"°C \) } {} at atmospheric pressure. LN 2 size 12{"LN" rSub { size 8{2} } } {} is useful as a refrigerant and allows for the preservation of blood, sperm, and other biological materials. It is also used to reduce noise in electronic sensors and equipment, and to help cool down their current-carrying wires. In dermatology, LN 2 size 12{"LN" rSub { size 8{2} } } {} is used to freeze and painlessly remove warts and other growths from the skin.

PV Diagrams

We can examine aspects of the behavior of a substance by plotting a graph of pressure versus volume, called a PV diagram    . When the substance behaves like an ideal gas, the ideal gas law describes the relationship between its pressure and volume. That is,

PV = NkT ( ideal gas ) . size 12{ ital "PV"= ital "NkT"``` \( "ideal gas" \) "." } {}

Now, assuming the number of molecules and the temperature are fixed,

PV = constant ( ideal gas, constant temperature ) . size 12{ size 11{ ital "PV"="constant"``` \( "ideal gas, constant temperature" \) "." }} {}

For example, the volume of the gas will decrease as the pressure increases. If you plot the relationship PV = constant size 12{ size 11{ ital "PV"="constant"}} {} on a PV size 12{ ital "PV"} {} diagram, you find a hyperbola. [link] shows a graph of pressure versus volume. The hyperbolas represent ideal-gas behavior at various fixed temperatures, and are called isotherms . At lower temperatures, the curves begin to look less like hyperbolas—the gas is not behaving ideally and may even contain liquid. There is a critical point    —that is, a critical temperature    —above which liquid cannot exist. At sufficiently high pressure above the critical point, the gas will have the density of a liquid but will not condense. Carbon dioxide, for example, cannot be liquefied at a temperature above 31 . 0 º C size 12{"31" "." 0°C} {} . Critical pressure is the minimum pressure needed for liquid to exist at the critical temperature. [link] lists representative critical temperatures and pressures.

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Source:  OpenStax, College physics for ap® courses. OpenStax CNX. Nov 04, 2016 Download for free at https://legacy.cnx.org/content/col11844/1.14
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