By the end of this section, you will be able to:
The gas laws that we have seen to this point, as well as the ideal gas equation, are empirical, that is, they have been derived from experimental observations. The mathematical forms of these laws closely describe the macroscopic behavior of most gases at pressures less than about 1 or 2 atm. Although the gas laws describe relationships that have been verified by many experiments, they do not tell us why gases follow these relationships.
The kinetic molecular theory (KMT) is a simple microscopic model that effectively explains the gas laws described in previous modules of this chapter. This theory is based on the following five postulates described here. (Note: The term “molecule” will be used to refer to the individual chemical species that compose the gas, although some gases are composed of atomic species, for example, the noble gases.)
The test of the KMT and its postulates is its ability to explain and describe the behavior of a gas. The various gas laws can be derived from the assumptions of the KMT, which have led chemists to believe that the assumptions of the theory accurately represent the properties of gas molecules. We will first look at the individual gas laws (Boyle’s, Charles’s, Amontons’s, Avogadro’s, and Dalton’s laws) conceptually to see how the KMT explains them. Then, we will more carefully consider the relationships between molecular masses, speeds, and kinetic energies with temperature, and explain Graham’s law.
Recalling that gas pressure is exerted by rapidly moving gas molecules and depends directly on the number of molecules hitting a unit area of the wall per unit of time, we see that the KMT conceptually explains the behavior of a gas as follows:
The previous discussion showed that the KMT qualitatively explains the behaviors described by the various gas laws. The postulates of this theory may be applied in a more quantitative fashion to derive these individual laws. To do this, we must first look at velocities and kinetic energies of gas molecules, and the temperature of a gas sample.
In a gas sample, individual molecules have widely varying speeds; however, because of the vast number of molecules and collisions involved, the molecular speed distribution and average speed are constant. This molecular speed distribution is known as a Maxwell-Boltzmann distribution, and it depicts the relative numbers of molecules in a bulk sample of gas that possesses a given speed (Figure 6.10).p id="fs-idm188037232">The kinetic energy (KE) of a particle of mass (m) and speed (u) is given by:
Expressing mass in kilograms and speed in meters per second will yield energy values in units of joules (J = kg m2 s–2). To deal with a large number of gas molecules, we use averages for both speed and kinetic energy. In the KMT, the root mean square velocity of a particle, urms, is defined as the square root of the average of the squares of the velocities with n = the number of particles:
The average kinetic energy for a mole of particles, KEavg, is then equal to:
where M is the molar mass expressed in units of kg/mol. The KEavg of a mole of gas molecules is also directly proportional to the temperature of the gas and may be described by the equation:
where R is the gas constant and T is the kelvin temperature. When used in this equation, the appropriate form of the gas constant is 8.314 J/mol⋅K (8.314 kg m2s–2mol–1K–1). These two separate equations for KEavg may be combined and rearranged to yield a relation between molecular speed and temperature:
If the temperature of a gas increases, its KEavg increases, more molecules have higher speeds and fewer molecules have lower speeds, and the distribution shifts toward higher speeds overall, that is, to the right. If temperature decreases, KEavg decreases, more molecules have lower speeds and fewer molecules have higher speeds, and the distribution shifts toward lower speeds overall, that is, to the left. This behavior is illustrated for nitrogen gas in Figure 6.11.
At a given temperature, all gases have the same KEavg for their molecules. Gases composed of lighter molecules have more high-speed particles and a higher urms, with a speed distribution that peaks at relatively higher velocities. Gases consisting of heavier molecules have more low-speed particles, a lower urms, and a speed distribution that peaks at relatively lower velocities. This trend is demonstrated by the data for a series of noble gases shown in Figure 6.12.
According to Graham’s law, the molecules of a gas are in rapid motion and the molecules themselves are small. The average distance between the molecules of a gas is large compared to the size of the molecules. As a consequence, gas molecules can move past each other easily and diffuse at relatively fast rates.
The rate of effusion of a gas depends directly on the (average) speed of its molecules:
Using this relation, and the equation relating molecular speed to mass, Graham’s law may be easily derived as shown here:
The ratio of the rates of effusion is thus derived to be inversely proportional to the ratio of the square roots of their masses. This is the same relation observed experimentally and expressed as Graham’s law.