The Learning Objective of this Module is to understand the significance of the kinetic molecular theory of gases.
The laws that describe the behavior of gases were well established long before anyone had developed a coherent model of the properties of gases. In this section, we introduce a theory that describes why gases behave the way they do. The theory we introduce can also be used to derive laws such as the ideal gas law from fundamental principles and the properties of individual particles.
A Molecular Description
The kinetic molecular theory of gases explains the laws that describe the behavior of gases. Developed during the mid-19th century by several physicists, including the Austrian Ludwig Boltzmann (1844–1906), the German Rudolf Clausius (1822–1888), and the Englishman James Clerk Maxwell (1831–1879), who is also known for his contributions to electricity and magnetism, this theory is based on the properties of individual particles as defined for an ideal gas and the fundamental concepts of physics. Thus the kinetic molecular theory of gases provides a molecular explanation for observations that led to the development of the ideal gas law. The kinetic molecular theory of gases is based on the following five postulates:
- A gas is composed of a large number of particles called molecules (whether monatomic or polyatomic) that are in constant random motion.
- Because the distance between gas molecules is much greater than the size of the molecules, the volume of the molecules is negligible.
- Intermolecular interactions, whether repulsive or attractive, are so weak that they are also negligible.
- Gas molecules collide with one another and with the walls of the container, but these collisions are perfectly elastic; that is, they do not change the average kinetic energy of the molecules.
- The average kinetic energy of the molecules of any gas depends on only the temperature, and at a given temperature, all gaseous molecules have exactly the same average kinetic energy.
Figure 10.7.1 Visualizing molecular motion. Molecules of a gas are in constant motion and collide with one another and with the container wall.
Although the molecules of real gases have nonzero volumes and exert both attractive and repulsive forces on one another, for the moment we will focus on how the kinetic molecular theory of gases relates to the properties of gases we have been discussing. In Section 10.8, we explain how this theory must be modified to account for the behavior of real gases.
The Relationships among Pressure, Volume, and Temperature
We now describe how the kinetic molecular theory of gases explains some of the important relationships we have discussed previously.
- Pressure versus Volume: At constant temperature, the kinetic energy of the molecules of a gas and hence the rms speed remain unchanged. If a given gas sample is allowed to occupy a larger volume, then the speed of the molecules does not change, but the density of the gas (number of particles per unit volume) decreases, and the average distance between the molecules increases. Hence the molecules must, on average, travel farther between collisions. They therefore collide with one another and with the walls of their containers less often, leading to a decrease in pressure. Conversely, increasing the pressure forces the molecules closer together and increases the density, until the collective impact of the collisions of the molecules with the container walls just balances the applied pressure. This is expressed in Boyle's Law:
- Volume versus Temperature: Raising the temperature of a gas increases the average kinetic energy and therefore the rms speed (and the average speed) of the gas molecules. Hence as the temperature increases, the molecules collide with the walls of their containers more frequently and with greater force. This increases the pressure, unless the volume increases to reduce the pressure, as we have just seen. Thus an increase in temperature must be offset by an increase in volume for the net impact (pressure) of the gas molecules on the container walls to remain unchanged. This is expressed in Charles' Law:
- Pressure of Gas Mixtures: Postulate 3 of the kinetic molecular theory of gases states that gas molecules exert no attractive or repulsive forces on one another. If the gaseous molecules do not interact, then the presence of one gas in a gas mixture will have no effect on the pressure exerted by another. This is expressed in Dalton’s law of partial pressures: