Pressure, Volume, and Temperature Relationships in Real Gases

For an ideal gas, a plot of PV/nRT versus P gives a horizontal line with an intercept of 1 on the PV/nRT axis. Real gases, however, show significant deviations from the behavior expected for an ideal gas, particularly at high pressures (part (a) in Figure 10.21 "Real Gases Do Not Obey the Ideal Gas Law, Especially at High Pressures"). Only at relatively low pressures (less than 1 atm) do real gases approximate ideal gas behavior (part (b) in Figure 10.21 "Real Gases Do Not Obey the Ideal Gas Law, Especially at High Pressures"). Real gases also approach ideal gas behavior more closely at higher temperatures, as shown in Figure 10.22 "The Effect of Temperature on the Behavior of Real Gases" for N₂. Why do real gases behave so differently from ideal gases at high pressures and low temperatures? Under these conditions, the two basic assumptions behind the ideal gas law—namely, that gas molecules have negligible volume and that intermolecular interactions are negligible—are no longer valid.

Figure 10.21 Real Gases Do Not Obey the Ideal Gas Law, Especially at High Pressures

(a) In these plots of PV/nRT versus P at 273 K for several common gases, there are large negative deviations observed for C₂H₄ and CO₂ because they liquefy at relatively low pressures. (b) These plots illustrate the relatively good agreement between experimental data for real gases and the ideal gas law at low pressures.

Figure 10.22 The Effect of Temperature on the Behavior of Real Gases

A plot of PV/nRT versus P for nitrogen gas at three temperatures shows that the approximation to ideal gas behavior becomes better as the temperature increases.

Because the molecules of an ideal gas are assumed to have zero volume, the volume available to them for motion is always the same as the volume of the container. In contrast, the molecules of a real gas have small but measurable volumes. At low pressures, the gaseous molecules are relatively far apart, but as the pressure of the gas increases, the intermolecular distances become smaller and smaller (Figure 10.23 "The Effect of Nonzero Volume of Gas Particles on the Behavior of Gases at Low and High Pressures"). As a result, the volume occupied by the molecules becomes significant compared with the volume of the container. Consequently, the total volume occupied by the gas is greater than the volume predicted by the ideal gas law. Thus at very high pressures, the experimentally measured value of PV/nRT is greater than the value predicted by the ideal gas law.

Figure 10.23 The Effect of Nonzero Volume of Gas Particles on the Behavior of Gases at Low and High Pressures

(a) At low pressures, the volume occupied by the molecules themselves is small compared with the volume of the container. (b) At high pressures, the molecules occupy a large portion of the volume of the container, resulting in significantly decreased space in which the molecules can move.

Moreover, all molecules are attracted to one another by a combination of forces. These forces become particularly important for gases at low temperatures and high pressures, where intermolecular distances are shorter. Attractions between molecules reduce the number of collisions with the container wall, an effect that becomes more pronounced as the number of attractive interactions increases. Because the average distance between molecules decreases, the pressure exerted by the gas on the container wall decreases, and the observed pressure is less than expected (Figure 10.24 "The Effect of Intermolecular Attractive Forces on the Pressure a Gas Exerts on the Container Walls"). Thus as shown in Figure 10.22 "The Effect of Temperature on the Behavior of Real Gases", at low temperatures, the ratio of PV/nRT is lower than predicted for an ideal gas, an effect that becomes particularly evident for complex gases and for simple gases at low temperatures. At very high pressures, the effect of nonzero molecular volume predominates. The competition between these effects is responsible for the minimum observed in the PV/nRT versus P plot for many gases.

At high temperatures, the molecules have sufficient kinetic energy to overcome intermolecular attractive forces, and the effects of nonzero molecular volume predominate. Conversely, as the temperature is lowered, the kinetic energy of the gas molecules decreases. Eventually, a point is reached where the molecules can no longer overcome the intermolecular attractive forces, and the gas liquefies (condenses to a liquid).

The van der Waals Equation

The Dutch physicist Johannes van der Waals (1837–1923; Nobel Prize in Physics, 1910) modified the ideal gas law to describe the behavior of real gases by explicitly including the effects of molecular size and intermolecular forces. In his description of gas behavior, the so-called van der Waals equationA modification of the ideal gas law designed to describe the behavior of real gases by explicitly including the effects of molecular volume and intermolecular forces.,

a and b are empirical constants that are different for each gas. The values of a and b are listed in Table 10.5 "van der Waals Constants for Some Common Gases" for several common gases. The pressure term—P + (an²/V²)—corrects for intermolecular attractive forces that tend to reduce the pressure from that predicted by the ideal gas law. Here, n²/V² represents the concentration of the gas (n/V) squared because it takes two particles to engage in the pairwise intermolecular interactions of the type shown in Figure 10.24 "The Effect of Intermolecular Attractive Forces on the Pressure a Gas Exerts on the Container Walls". The volume term—V − nb—corrects for the volume occupied by the gaseous molecules.

Figure 10.24 The Effect of Intermolecular Attractive Forces on the Pressure a Gas Exerts on the Container Walls

(a) At low pressures, there are relatively few attractive intermolecular interactions to lessen the impact of the molecule striking the wall of the container, and the pressure is close to that predicted by the ideal gas law. (b) At high pressures, with the average intermolecular distance relatively small, the effect of intermolecular interactions is to lessen the impact of a given molecule striking the container wall, resulting in a lower pressure than predicted by the ideal gas law.

The correction for volume is negative, but the correction for pressure is positive to reflect the effect of each factor on V and P, respectively. Because nonzero molecular volumes produce a measured volume that is larger than that predicted by the ideal gas law, we must subtract the molecular volumes to obtain the actual volume available. Conversely, attractive intermolecular forces produce a pressure that is less than that expected based on the ideal gas law, so the an²/V² term must be added to the measured pressure to correct for these effects.

Liquefaction of Gases

LiquefactionThe condensation of gases into a liquid form. of gases is the condensation of gases into a liquid form, which is neither anticipated nor explained by the kinetic molecular theory of gases. Both the theory and the ideal gas law predict that gases compressed to very high pressures and cooled to very low temperatures should still behave like gases, albeit cold, dense ones. As gases are compressed and cooled, however, they invariably condense to form liquids, although very low temperatures are needed to liquefy light elements such as helium (for He, 4.2 K at 1 atm pressure).

Liquefaction can be viewed as an extreme deviation from ideal gas behavior. It occurs when the molecules of a gas are cooled to the point where they no longer possess sufficient kinetic energy to overcome intermolecular attractive forces. The precise combination of temperature and pressure needed to liquefy a gas depends strongly on its molar mass and structure, with heavier and more complex molecules usually liquefying at higher temperatures. In general, substances with large van der Waals a coefficients are relatively easy to liquefy because large a coefficients indicate relatively strong intermolecular attractive interactions. Conversely, small molecules with only light elements have small a coefficients, indicating weak intermolecular interactions, and they are relatively difficult to liquefy. Gas liquefaction is used on a massive scale to separate O₂, N₂, Ar, Ne, Kr, and Xe. After a sample of air is liquefied, the mixture is warmed, and the gases are separated according to their boiling points. In Chapter 11 "Liquids", we will consider in more detail the nature of the intermolecular forces that allow gases to liquefy.

The ultracold liquids formed from the liquefaction of gases are called cryogenic liquidsAn ultracold liquid formed from the liquefaction of gases., from the Greek kryo, meaning “cold,” and genes, meaning “producing.” They have applications as refrigerants in both industry and biology. For example, under carefully controlled conditions, the very cold temperatures afforded by liquefied gases such as nitrogen (boiling point = 77 K at 1 atm) can preserve biological materials, such as semen for the artificial insemination of cows and other farm animals. These liquids can also be used in a specialized type of surgery called cryosurgery, which selectively destroys tissues with a minimal loss of blood by the use of extreme cold.

Figure 10.25 A Liquid Natural Gas Transport Ship

Moreover, the liquefaction of gases is tremendously important in the storage and shipment of fossil fuels (Figure 10.25 "A Liquid Natural Gas Transport Ship"). Liquefied natural gas (LNG) and liquefied petroleum gas (LPG) are liquefied forms of hydrocarbons produced from natural gas or petroleum reserves. LNG consists mostly of methane, with small amounts of heavier hydrocarbons; it is prepared by cooling natural gas to below about −162°C. It can be stored in double-walled, vacuum-insulated containers at or slightly above atmospheric pressure. Because LNG occupies only about 1/600 the volume of natural gas, it is easier and more economical to transport. LPG is typically a mixture of propane, propene, butane, and butenes and is primarily used as a fuel for home heating. It is also used as a feedstock for chemical plants and as an inexpensive and relatively nonpolluting fuel for some automobiles.