<em>PV</em> Diagrams

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,

\(\phantom{\rule{0.25em}{0ex}}\text{PV}=\phantom{\rule{0.25em}{0ex}}\text{NkT}\phantom{\rule{0.25em}{0ex}}(\text{ideal gas})\text{.}\)

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

\(\text{PV}=\text{constant}\phantom{\rule{0.25em}{0ex}}(\text{ideal gas, constant temperature})\text{.}\)

For example, the volume of the gas will decrease as the pressure increases. If you plot the relationship \(\text{PV}=\text{constant}\) on a \(\text{PV}\) diagram, you find a hyperbola. The figure below 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 \(\text{31}\text{.}0\text{º}\text{C}\). Critical pressure is the minimum pressure needed for liquid to exist at the critical temperature. The table below lists representative critical temperatures and pressures.

Graphs of pressure versus volume at six different temperatures, T one through T five and T critical. T one is the lowest temperature and T five is the highest. T critical is in the middle. Graphs show that pressure per unit volume is greater for greater temperatures. Pressure decreases with increasing volume for all temperatures, except at low temperatures when pressure is constant with increasing volume during a phase change.

\(\text{PV}\) diagrams. (a) Each curve (isotherm) represents the relationship between \(P\) and \(V\) at a fixed temperature; the upper curves are at higher temperatures. The lower curves are not hyperbolas, because the gas is no longer an ideal gas. (b) An expanded portion of the \(\text{PV}\) diagram for low temperatures, where the phase can change from a gas to a liquid. The term “vapor” refers to the gas phase when it exists at a temperature below the boiling temperature.

Critical Temperatures and Pressures

Substance Critical temperature Critical pressure
\(\text{K}\) \(\text{º}\text{C}\) \(\text{Pa}\) \(\text{atm}\)
Water 647.4 374.3 \(\text{22}\text{.}\text{12}×{\text{10}}^{6}\) 219.0
Sulfur dioxide 430.7 157.6 \(7\text{.}\text{88}×{\text{10}}^{6}\) 78.0
Ammonia 405.5 132.4 \(\text{11}\text{.}\text{28}×{\text{10}}^{6}\) 111.7
Carbon dioxide 304.2 31.1 \(7\text{.}\text{39}×{\text{10}}^{6}\) 73.2
Oxygen 154.8 −118.4 \(5\text{.}\text{08}×{\text{10}}^{6}\) 50.3
Nitrogen 126.2 −146.9 \(3\text{.}\text{39}×{\text{10}}^{6}\) 33.6
Hydrogen 33.3 −239.9 \(1\text{.}\text{30}×{\text{10}}^{6}\) 12.9
Helium 5.3 −267.9 \(0\text{.}\text{229}×{\text{10}}^{6}\) 2.27

This lesson is part of:

Temperature, Kinetic Theory, and Gas Laws

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