Kinetic Theory of Gases

chemistry.

Chapter 1

EQUATIONS OF STATE OF CASES;

EMPIRICAL RESULTS

1-1   The primary properties, mass, volume, pressure, and temperature

Gases are substances which completely fill any container into which they are introduced. Let us suppose that standing before the student on his desk as he reads this chapter is a flask containing some gaseous substance such as air. The air in this flask has a great many properties—color, odor, density, velocity, viscosity, thermal conductivity, electrical conductivity, magnetic susceptibility, dielectric constant, chemical composition, and so on. In this chapter, however, we shall be concerned with four particularly important properties of a gaseous substance: mass, volume, pressure, and temperature. Because they are so important and are so frequently measured by chemists we shall call them the primary properties. Before considering their relationship to each other, let us be sure that we understand what we mean by these four properties.

The properties in question are expressible as numbers, and can be best defined if we describe how one goes about determining these numbers. (This way of looking at scientific concepts is almost always the safest way of being sure that one knows exactly what a concept means, and deciding the circumstances under which the concept loses or changes its significance.)

The mass of a gas in a vessel can be determined by weighing the vessel when it contains the gas, and then weighing the vessel again after the gas has been pumped out. This procedure is straightforward, and although it is possible to imagine some subtle complications regarding the concept of mass, these complications play no role in physical chemistry, at least not under ordinary circumstances.

The volume of a gas can be most easily determined by weighing the water required to fill the vessel containing the gas, since the volume of a unit mass of water between 0°C and 100°C is very accurately known. The procedure is simple in principle, but a complication arises if the gas and the vessel are at an elevated temperature, where the mass of water per unit of volume may not be so well known. This complication can be overcome, of course, by using other liquids whose densities are known at the desired temperature. Furthermore, if the vessel has a simple geometry (a cube, sphere, cylinder, etc.), we may measure its dimensions and the volume may then be determined by means of a suitable geometric formula.

A more awkward complication arises in determining the mass of a given volume or the volume of a given mass of a gas when the gas is not in a container—say when it is flowing out of a nozzle or around the wing of an airplane. We shall avoid complications of this kind for the present, however, by considering only gases in closed vessels. On the other hand, we shall be very much concerned with vessels whose volumes can be altered—particularly with vessels in which one wall can be moved—for instance, a gas contained in a piston chamber or a gas under compression by a liquid in a gas burette (Fig. 1-1). Clearly, each position of the piston or of the liquid corresponds to a volume which can be determined in principle in the manner described above.

The concept of pressure, although apparently simple in principle, is in practice subject to a good many qualifications. It may be measured by means of a manometer, with which one observes the height of a column of an inert liquid, such as mercury, that is balanced by the force exerted by the gas on the liquid surface. (This measurement will be described in more detail below, in Section 1-3.¹). If a gas and its container are at rest, and if they are located in a region free of gravitational fields, then the pressure that the gas exerts on the container walls is the same at all points on all of the walls. Under these conditions one can speak of the pressure on the walls as the pressure of the gas, and this pressure can be regarded as a property of the entire gas sample. On the other hand, if the system is located in a gravitational field, the pressure on the walls will not be uniform. A gas at the earth’s surface exerts a force on the bottom of its container which is greater by the weight of the gas than the force on the top of the container. Strictly speaking, such a gas sample as a whole does not have a pressure. If the box is small, however, and if the gas is not highly compressed, these pressure differences will be negligible so that one is in the habit of speaking of the pressure of the gas despite the fact that it cannot be precisely defined under these circumstances.

FIG. 1-1 Devices for observing the behavior of the volume of a gas when the pressure on the gas is changed, (a) Conceptual piston-chamber device. The pressure may be changed by changing the weights on the platform. (b) Gas burette. Pressure may be changed by moving the reservoir up and down and the volume may be read off from the graduations on the burette.

EXERCISE One liter of air at room temperature and at one atmosphere pressure (= about 1 kg/cm² at the earth’s surface) has a mass of about 1 g. What is the percentage difference in pressure between the top and bottom of a column which is 1 m in height, filled with air at one atmosphere and located at the earth’s surface?

A more awkward complication arises if a gas moves relative to the walls of its container—as will be the case if the gas is swirling about or if one of the walls (say the piston in Fig. 1-1) is in motion. The pressure may then be quite different on different walls, and again it is not possible to speak of the pressure of the whole gas sample. This complication will be discussed in a later volume of this series. It will also arise in Chapter 5 when we consider the flow of a gas through a tube.

It is common practice to talk of the pressure of a gas at points in the gas not adjacent to a wall, where the gas exerts forces only on itself. There is no difficulty in defining such a local pressure if the gas and its container are at rest. In a stationary gas the local pressure at any point (i.e., the pressure that the gas would exert on a stationary surface introduced at that point) is the same in all directions (i.e., is independent of the orientation of the surface), and it is usually a simple matter either to measure this pressure by inserting a suitable pressure gauge or to calculate it from a knowledge of the forces acting on the gas. On the other hand, if the gas is in motion, care must be taken in formulating the concept of pressure as a local property of the gas. If a large body of gas moves relative to its surroundings, we can imagine that a pressure gauge calibrated in a static system can be inserted into the gas. If the gauge moves at the same velocity as the gas in its immediate vicinity, it will provide us with a local pressure which is physically meaningful. A meteorologist may be able to make such a local pressure measurement in a turbulent storm cloud by sending a pressure gauge into the cloud by means of a balloon. It is, however, hardly practical to use this means of defining a local pressure in a stream of gas flowing at high velocity through a nozzle in a turbine or rocket or past the wing of a jet airplane. Clearly, the concept of pressure under such circumstances may require considerable abstraction and discussion before it can be defined or measured. It is fortunate that we shall not have to deal with these difficulties here.

The temperature of a gas is an even more subtle property. We must first assume that two objects can be said to have the same temperature if no heat flows between them when they are brought into intimate contact. For our present purposes we may say that the temperature of a gas is the temperature read on some thermometer that has remained in contact with the gas until the flow of heat between the gas and the thermometer has stopped. A convenient thermometer is a glass bulb to which is attached a uniform capillary, the bulb and a portion of the capillary being filled with some liquid—commonly mercury. The scale on the thermometer may be established by inserting the thermometer first in an ice-water mixture and marking the position of the mercury in the capillary as 0°. The thermometer is then inserted in water boiling at 1 atm pressure and the position of the mercury in the capillary is marked as 100°. The thermometer capillary between the two marks being uniform, 100 equal divisions are marked between them. The scale below 0° and above 100° will be temporarily assumed to be marked off on the capillary with scale divisions of the same magnitude. Obviously this thermometer cannot be used below the freezing point of mercury (−39°) or much above its boiling point (357°). Furthermore, there is no reason to believe that a mercury temperature scale defined in this way will be identical with one using another fluid or with thermometers whose bulbs and capillaries are built of different kinds of glass, or of materials other than glass. Later in this chapter we shall find that more satisfactory temperature scales can be constructed in other ways, but for the time being it will be sufficient to make use of the above method of attaching a numerical value to the property of temperature.

1-2   The concept of an equation of state of a gas

Consider the following problem. A scientist is performing some experiments on pure oxygen gas which will have to be repeated several times at widely different occasions. What must he know about the samples of oxygen on which the measurements are made in order to be sure that these samples are in precisely the same condition or state for each measurement? What is the minimum number of properties of pure oxygen that must be specified in order to fix completely the condition of the oxygen?

Experience tells us that under ordinary conditions this minimum number is precisely three.² That is, if any three of the four primary properties, mass, volume, pressure, and temperature, are specified for any substance, then the magnitude of the fourth primary property, as well as the values of all other properties of that substance, are completely determined. Thus if one fills a vessel having a volume of 100 ml at a temperature of 30°C with 32 g of oxygen, then the pressure inside the vessel will be found to be 239 atm. It is important to realize that two properties are not sufficient for this; the statement that one has 32 g of oxygen at 30°C is not sufficient to specify the state of the oxygen because any pressure between zero and infinity is consistent with these two properties, depending on the volume chosen for the container, which may have any value from infinity to zero.

The very fundamental observation concerning the nature of matter that has just been presented may be expressed in mathematical language by the statement that the properties of a sample of any given substance are functions of three independent variables. If we agree to restrict our choice of independent variables to the set of the four primary properties, pressure, P, volume, V, temperature, T, and mass, m (an arbitrary restriction which we make for reasons of convenience alone since these properties are particularly easy to measure), then we may say that there exist for any sample of a given substance four functions: P(V, T, m), V(P, T, m), T(P, V, m), and m(P, T, V). These four functions are, of course, related to one another, in the sense that if one function is known, then the other three functions can, at least in principle, be evaluated. Furthermore, it is clear that functions must exist which give the numerical values of all other properties of any given sample of a substance in terms of any three of the four primary variables. For instance, if E is the energy content of oxygen, then functions such as E(P, V, T) and E(V, T, m) must exist.

An equation which relates the four primary properties, P, V, T, and m, for a substance is called the equation of state of that substance. We shall now consider the equations of state of gases that have been observed by physical chemists.³ The general procedure that is followed in determining empirically the form of these equations is to keep two of the primary properties constant while varying the third, and observing the resultant behavior of the fourth property.

1-3   The ideal gas laws

If the pressure, volume, and temperature of a gas are measured at low pressures (say, below a few atmospheres), they are found to obey quite closely the so-called ideal gas law,

where n is the number of moles of gas occupying a volume V at an absolute temperature T and pressure P, and R is a universal constant called the gas constant. As will now be shown, this concise law is a consequence of four generalizations discovered over a period of nearly two hundred years, known as Boyle’s law, Gay-Lussac’s law, Avogadro’s law, and Dalton’s law.

a. BOYLE’S LAW In 1662 Robert Boyle described the following simple experiment. He prepared a tube in the form of a J, the short side of the J being sealed off (Fig. 1-2; this is prototype of the manometer, mentioned in Section 1-1, above). Mercury was added through the open end, trapping some gas in the closed end. Since the tube was uniform in cross section the volume of the gas trapped in the J is proportional to the length of the column of gas, l. Part of the pressure exerted on this gas was proportional to the distance, h, between the menisci of the mercury in the two arms of the J. It was also necessary to add the pressure exerted by the earth’s atmosphere on the meniscus at the open end of the tube. This pressure was proportional to h0, the height of a mercury column in a mercury barometer, measured at the time of the experiment. Boyle observed that as mercury was poured into the open end of the J-tube, the volume, as measured by l, decreased in inverse proportion to the pressure, as measured by h +h0. That is,

The accuracy of this equation in expressing the results was quite good; it was possible for Boyle to predict h + h0 to better than 1 % for a fourfold variation in l (h being varied from 0 to 3h0). The experiment was performed in a room whose temperature was essentially constant, and the law is valid only under conditions of constant temperature. This result, now known as Boyle’s law, can be written in the form

FIG. 1-2 Boyle’s J-tube experiment.

where P and V are the pressure and volume of the gas sample. Boyle’s law can be written more concisely in the form

where A(m, T) is a quantity whose magnitude is fixed when the mass and temperature of the gas is fixed, but which does not depend explicitly on the pressure and volume of the gas. The quantity A(m, T) also depends on the nature of the gas, and would be expected, for given m and T, to have different values for, say, air and carbon dioxide.

Boyle’s experiment played a large part in the development of modern concepts of gases because it showed that by lowering the pressure sufficiently, one could approach the state of a vacuum—a notion that appeared to contradict the Aristotelian doctrine that nature abhors a vacuum.⁴

b. GAY-LUSSAC’S LAW In 1802, Gay-Lussac showed⁵ that if Vf is the volume of a gas at the temperature of the freezing point of water and at a pressure of one atmosphere, and if Vb is the volume of the same gas at the temperature of the boiling point of water and at the same pressure, then

where the constant K was the same for all of the gases studied. Gay-Lussac’s measurements indicated a value of about 1.375 for the constant K, but more precise measurements reveal that the ratio differs slightly for different gases. If the pressure used in making the measurements is sufficiently low (well below one atmosphere) careful observation indicates that the ratio does approach a universal value. This value is 1.36609 for all gases.

Gay-Lussac’s observation suggests that the thermal expansion of gases can provide a logical basis for establishing a temperature scale. Ordinary thermometers, such as those described earlier in this chapter, depend on the thermal expansion of some liquid, but all liquids do not expand in exactly the same way with temperature so the temperatures given by different liquid thermometers do not agree precisely. Since all gases expand in the same way when the temperature is changed, the pressure being held constant at a sufficiently low value, a thermometer based on gas expansion should give the same reading regardless of the gas employed.

Therefore we may define the temperature scale by the relation

where V is the volume at temperature t, V0 is the volume when t is related to the constant K in Eq. (1-5). Two temperature scales are in common use—the Fahrenheit scale and the Celsius scale (also called the centrigrade scale—a practice now discouraged by international agreement). For the Farenheit scale the freezing point of water at a pressure of one atmosphere is given the value t = 32° and the boiling point of water at one atmosphere is given the value t = 212°. Setting

has the value 1/491.7. For the Celsius scale the freezing point of water is given the value t = 0° and the boiling point of water is set at