2

THE EQUATION OF STATE

Introduction 1. The State of a Gas or a Liquid at Equilibrium. Let us assume that I want to design an experiment or an instrument and am forced to use a certain gas (or liquid). An instrument has the best performance if a property, x, of this gas has a value close to x0 . If the experiment is in optics, x could be the index of refraction. If I work in electrostatics, x might be the dielectric constant. If I design a compressor, x might be the molar volume. The bottom line is that conditions must be created that will make x close to x0 . How can the instrument be designed to make sure that this happens? Experience tells me that any intensive property of a bulk liquid or gas depends only on the pressure p and the temperature T . In designing the instrument, I must provide the means to control T and p, so that x can be varied and brought close to the optimal value.
Extensive quantities, such as the total volume, V , depend not only on temperature and pressure but also on the number of moles of substance, n. If an experiment requires control of an extensive variable, it must be designed so that n can also be changed. These rules are for a system consisting of one compound and one phase. The intensive properties of a system that has one phase and several chemical compounds (a solution) depend on temperature, pressure, and composition.

21

22

The Equation of State

For a while we will study systems with one component and one phase. Because its intensive properties depend only on pressure and temperature, we say that the state of the system is determined by the values of p and T. If extensive quantities are of interest, we must also give the number of moles, n.

2. The Equation of State. Among the quantities mentioned above, the molar volume, v, is of interest in thermodynamics. According to the rule I have just stated, the value of v is determined by the chemical nature of the system and by the values of T and p.
Let us examine the kind of experiments that lead me to say that. Suppose you perform an experiment with a gas and you tell me its state, by giving me the values of T and p. Will this determine the value of v? To answer this question, I enclose the gas in a cylinder-and-piston system like the one shown in Fig. 1.1. Appropriate weights are placed on the cylinder to make the pressure in my system equal to that in your system. Then I set the thermostat to have the same temperature as the one you used. You have not told me how many moles, n, of gas you used or what was the volume, V , of your container. Because of this, n and V in my experiment have different values to those in yours. It is, however, an experimental fact that the ratio v = V / n is the same in both experiments, as long as T and p are the same. There is no need for you to tell me the molar volume of the gas: the gas knows it, once the temperature and the pressure are set. For example, the data in Appendix 2 tell me that the molar volume of ethane at 320 K and 100 atm is 92.6 cm3 /mol, whether I have a gram of material or a ton. Moreover, once p and T are xed, v cannot be modied. This observation tells me that p, T , and v are connected through a functional relationship p = f (T , v) (2.1)

which is called the equation of state of the gas. If the values of two of the quantities T , p, and v are known, the value of the third can be calculated from Eq. 2.1. If the same experiment is performed with a liquid, the same conclusion is reached. The only difference is that to see any changes in the volume of the liquid, very large changes in the pressure have to be made. A liquid is not as compressible as a gas.

3. Solids are Different. For a crystalline solid, the mechanical forces acting at a point cannot be described by pressure alone, and the equation of state is more

Introduction

23

complicated than p = f (T , v). To dene the equation of state, I have to use the theory of elasticity, which connects strain and stress. If you do not know what this means do not worry: we are not going to study the thermodynamics of crystals. I just wanted to alert you to the fact that if you need to apply thermodynamics to crystals, you will have to consult a specialized textbook.

4. Why Bother with the Equation of State? Since you are just starting to study thermodynamics, it is hard to explain how the equation of state is used. Nevertheless, here are a few examples. Suppose that the company you work for makes and sells ethane. This is stored in a tank of known volume, equipped with a pressure gauge and a thermometer. The equation of state allows you to calculate how many moles of ethane there are in storage. If you sell some ethane, you can calculate how many moles you sold from the change of pressure caused by the sale.
Ethane is put in the tank by using a compressor, driven by an electric motor, and the equation of state can be used to calculate how much power is required to ll the tank. You can now decide what kind of electric motor you need to buy. As the gas is compressed, it will heat up. To calculate how much heat is produced, and decide whether you need to cool the gas, you use the equation of state. The most important applications are harder to explain, since understanding them requires a knowledge of thermodynamics. You are going to use the equation of state in about half of the chapters in this book.

5. A Table is a Poor Mans Equation of State. For gases as important as ethane, there is considerable data showing how the molar volume depends on pressure and temperature. This displays the connection among p, v, and T in a table like the one given in Appendix 2. This gives the equation of state in a tabular form. Tables like this are inconvenient. Getting numbers from a table, when you do calculations, is slow, tiresome, and error-prone. An algebraic expression for the equation of state p = f (v, T ) is a more compact and convenient way to communicate the data contained in the table. Moreover, I can use this function for interpolation to obtain information about states for which measurements have not been made. Calculations of heat, work, the concentrations of reactants and products in chemical equilibrium, etc., require us to perform integrals or derivatives involving p, v, or T . This is tedious and inaccurate when data are given in a table; it is much easier if you know the equation of state.
For all these reasons, and others, much hard work went into nding the function f in Eq. 2.1 for gases that are important to industry or science. In the remainder

24

The Equation of State

of this chapter, I describe four equations of state. Two of them, the ideal gas law and the van der Waals equation, have mostly historical and conceptual importance. The other two are sufciently accurate to be useful in plant design, thermodynamic calculations, and the analysis of experimental data.

The Ideal Gas Equation 6. The earliest, simplest, and least accurate equation of state is
pv = RT (2.2)

This is called the ideal gas equation of state or the ideal gas law. T is the temperature in kelvin, p is the pressure, and v is the molar volume. R is the gas constant or the universal gas constant.

7. Units. Since p, T , and v are quantities used in many practical activities, they are expressed in many units. Every trade group uses a unit that is most convenient for their own craft. It is very easy to make mistakes when temperature is given in degrees Fahrenheit and the pressure in pounds per square inch, and you want the molar volume in cubic meters per mole. Because of this, I will spend some time on units.
First, I remind you (see your mechanics book) that the units of force, energy, pressure and molar volume are mass length time2

force = mass acceleration = energy = force length = pressure = force length

2

(2.3)

mass length2 time2

(2.4) (2.5)

mass length time2

volume =

length3 mol

(2.6)

The Ideal Gas Equation

25

Next I show that the unit of pv is energy per mole. This can be obtained by combining Eq. 2.5 with Eq. 2.6 and then using Eq. 2.4: mass length time2 mass length2 mol time2 (2.7) length3 mol

unit(pv) =

= energy/mole

You see now that liter atm is a unit of energy and so is psi foot3 . You may nd this hard to believe, but it is sometimes more convenient to use liter atm as an energy unit than to use joules. The unit of R is energy/(mol K), where K stands for kelvin: energy energy/mol = mol temperature temperature

unit(R) = unit(pv/ T ) =

(2.8)

Appendix 3 gives the values of R in several other units. If these manipulations of units bore you, consider this. A few years ago NASA sent a Mars probe, worth several hundred million dollars, to nowhere, because of a unit error in a calculation. The engineers sent velocity data in foot/second and the scientists using it assumed that it was in meter/second. You do not have a chance to make such a catastrophic error twice in your career. I hope this makes you eager to do the exercises given below. Exercise 2.1 Find the conversion factor that satises the equation 1 liter atm = joule. (Answer. 1 liter atm = 101.325 joule.) Example. To practice using units correctly, use the ideal gas law to calculate the pressure in atm and in Pa when you know that v = 20 liter/mol and T = 400 K.

26

The Equation of State

Because v is in liter/mol, I can use R = 0.082 liter atm/mol K to obtain p, in atm: p= 0.082(liter atm/mol K) 400 K = 1.64 atm 20(liter/mol)

To obtain p in Pa, I could use the conversion factor 1 atm = 1.01325 105 Pa. Here I use SI units in the ideal gas law: p= 8.134(joule/mol K) 400 K = 162.68 103 Pa 20 103 (m3 /mol)

Here I used 1 liter = 1000 cm3 = 1000 (102 m)3 = 103 m3 .

8. It is Simple, but is it Right? The ideal gas equation predicts that all gases have the same molar volume when they are held at the same temperature and pressure. This seems a bit strange: it is hard to imagine a property that is independent of the chemical nature of the compound. This prediction provides an opportunity to test the equation. The molar volumes of several gases, at T = 250 K and p = 10 atm, are listed in Table 2.1. These data show clearly that the prediction is wrong. However, it is not erroneous at all temperatures and pressures. You can see in Table 2.2 that the molar volumes of different gases at T = 400 K and p = 1 atm are very close to each other, as predicted by Eq. 2.2. 9. When and Why is the Ideal Gas Law Valid? By comparing the ideal gas law with data, we nd that Eq. 2.2 works well whenever the molar volume is very large. From experiments we know that v is large when the temperature is high or the
Table 2.1 Experimental values of the molar volume, v, at T = 260 K and p = 10 atm. The last column gives the value calculated from ideal gas law.
Compound C2 H6 N2 CH4 Ideal v (liter/mol) 6.8562 2.0355 1.9880 2.1320

The Ideal Gas Equation

27

Table 2.2 Molar volume, v, of several gases at T = 400 K and p = 1 atm.

Compound NH3 CH4 N2 C2 H6 Ideal gas law v (liter/mol) 32.730 32.808 32.833 32.726 32.800

pressure is low (you reach the same conclusion if you assume that Eq. 2.2 is correct). What is this telling us about the ideal gas law? If I divide v by the number of molecules in one mole (Avogadros number), I get the average volume per molecule. This is the real estate owned by a molecule. If the molar volume is large, each molecule lives far from its neighbors. If it is assumed that molecules separated by large distances do not interact with each other, a large molar volume means a very small interaction between molecules. This suggests that a gas behaves in accordance with the ideal gas law when the molar volume is so large that the interactions between molecules become negligible. There is an additional, more subtle reason, why the ideal gas law is valid at high temperature. In your physics course, you learned that temperature is proportional to the average kinetic energy of a molecule in the gas. If the temperature of the gas is increased, at constant volume, the kinetic energy of the molecules becomes higher and higher. However, the interaction energy stays the same, since it depends on the distance between molecules, which does not change (the volume is constant) when I heat the gas. At sufciently high temperature, the kinetic energy can become so large that the interaction energy becomes a negligible part of the total energy; the molecules behave as if there is no interaction between them and obey the ideal gas law. The fact that, at low pressure and high temperature, the molar volume of all gases is the same offers one more mystery on which to ponder. The gas exerts a pressure because the molecules move about and collide with the wall of the container. I expect that a heavier molecule hits the wall harder and will exert more pressure. If I must collide with someone I prefer a ten-year-old kid to an NFL linebacker. It would seem that, at the same temperature and molar volume, the

28

The Equation of State

heavier molecules should exert more pressure. The ideal gas law suggests otherwise: the pressure is the same, regardless of the mass of the molecules; the kid hits as hard as a linebacker. How could this be? Simple: the kid must be moving faster! So I have to conclude that, at the same temperature and pressure, the lighter molecules must move faster than the heavier ones. When they hit the wall, their high velocity compensates for their small mass, and they exert the same pressure as the heavy ones. As you can see, the validity of the ideal gas law (for certain states of the gas) leads us to interesting speculations about the properties of molecules. As you learn more you will discover that all these guesses follow from the fundamental laws of statistical mechanics.

The van der Waals Equation of State 10. It was a stroke of luck that at room temperature and atmospheric pressure, air satises the ideal gas law (within the accuracy of the primitive instruments of the time). Otherwise, it would have been difcult to discover the mathematical law connecting p, v, and T . This discovery had a tremendous psychological and methodological impact: it conrmed the notion that quantitative natural laws exist and that we are smart enough to discover them by careful experimentation. As our ability to compress gases and cool them increased, it became clear that the ideal gas law needed improvement. The rst successful extension was the equation
p= proposed by van der Waals. The rst term is obtained from the ideal gas law by replacing the molar volume v with v b. This is a reasonable correction: it accounts for the fact that the molecules have a nite volume and the molar volume of the gas cannot be diminished indefinitely by increasing the pressure. This term is also troublesome since it makes the pressure innite when v = b and negative when v is very small. Obviously, at high pressures, when v approaches b this equation breaks down. The second term in Eq. 2.9 is harder to explain. To derive this equation from a molecular theory one has to make some rather articial assumptions about the interaction between molecules. van der Waals had some rationalization for it that was not quite correct. I prefer to view this term as a lucky guess on his part. a RT v b v2 (2.9)

Accurate Equations of State

29

The equation is famous not for its accuracy, which is rather poor, but for a number of remarkable semi-quantitative consequences that van der Waals derived from it. He concluded that all gases can be liqueed at high pressure and low temperature, he discovered and analyzed the critical point in the liquidvapor phase transition (see Chapter 22, on liquidvapor equilibrium), and proposed the principle of corresponding states. These discoveries earned van der Waals the Nobel Prize for physics in 1910. You can read his biography and his Nobel lecture at www.nobel.se/physics/laureates/1910/waals-lecture.html. Nowadays, Eq. 2.9 belongs to pedagogical physics: it is the simplest equation that illustrates several important concepts, but its accuracy is not satisfactory.

Accurate Equations of State 11. Having accurate equations of state for the gases used in industry is important in the design of chemical plants and for precise calculations describing a variety of thermodynamic phenomena. The equation
p= c 1 RT 1 3 v2 vT v+B bB v A 1 a v

(2.10)

was proposed by Beattie and Bridgemana . It contains ve parameters A, B, a, b, c, whose values are given in Appendix 5, for several gases. Benedict, Webb, and Rubinb proposed the form p = RT + (BRT A C0 T 2 ) 2 + (bRT a) 3 + a 6 + cT 2 3 (1 + 2 ) exp ( 2 ) (2.11)

where = n/ V = 1/ v is the molar density. The values of the parameters A, B, C0 , a, b, , c, and are given in Appendix 6. We will test the accuracy of these equations in Chapter 3 where you will see that they work rather well.

J.A. Beattie and O.C. Bridgeman, J. Am. Chem. Soc. 49, 1665 (1927) M. Benedict, G.B. Webb, and L.C. Rubin, J. Chem. Phys. 8, 334345 (1940); J. Chem. Phys. 10, 747758 (1942)

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The Equation of State

Summary and Perspective 12. The quantities p, T , and v are related by a functional relationship p = f (T , v) called the equation of state. Many functional forms for f are given in the literature. I have shown here only four: two are simple and inaccurate; they serve to illustrate various principles and phenomena and are widely used in textbooks. The other two are more complicated but work rather well. They were not used in textbooks because they made homework complicated. Now that computers are widely used in chemistry, there is no excuse for using inaccurate equations: it is as easy to write a program that uses the BenedictWebbRubin equation as it is to use the ideal gas law.
The equation of state appears in almost every chapter dealing with the applications of thermodynamics. In Chapter 3, I will show how these equations are used for calculating one of p or v or T when the other two are known. I will also compare the predictions of the equations of state with experiments, to determine how accurate they are. In Supplement 3.1 you will learn how to use experimental data to create your own equation of state, which is more accurate than the ones given in the literature. This chapter is an example of the semi-empirical research that goes on in industry. A table of p vs T data displays the equation of state in tabular form. This is cumbersome to use, and much labor can be saved by nding an equation that reproduces the data. Various functional forms were tried and the successful ones were retained. You see a Darwinian selection principle at work in the world of equations. These equations have also stimulated a large body of scientic work. Statistical mechanics connects the equation of state to interactions between molecules. This connection allows us to use p vs T data to determine how molecules interact with each other. Then, we can use these interactions to calculate other measurable quantities, such as the viscosity of the gas or its diffusion coefcient. The results of these calculations agree with experiments, conrming that our theories are sound. The equation of state has played an important role in our history. At the dawn of the scientic revolution, the idea of making measurements, to nd mathematical relationships between the measured quantities, was very new. It was not clear that such relationships ought to exist. This idea would not have taken hold if the practitioners encountered failure after failure. Among the earliest successes was the observation that if the temperature of a gas is changed while the volume is held constant, its pressure is proportional to its temperature. This is, of course, a manifestation of the ideal gas law. Such ndings encouraged the believers to look for more. Without a few early successes the idea might have died after birth. It is also remarkable that Nature offers systems for which such relationships are

Problems

31

at their simplest, so that our limited intelligence can nd them. The pendulum, free fall, and the inclined plane helped to start our understanding of mechanics. The fact that gases are ideal at room temperature and atmospheric pressure helped to start our understanding of thermodynamics. The simple form of the black-body radiation law helped Planck discover the quantization of energy. An essential part in the art of scientic research is to nd a system in which the phenomenon of interest appears in the simplest possible form. I will show you how we use the equations of state in the next chapter. In preparation for this, try these simple exercises.

Problems
Problem 2.1 Use the p vs T data for ethane given in Appendix 2 to calculate the ideal gas constant R. Decide which data points are the best for this calculation. Explain your decision. Problem 2.2 Use the ideal gas law and the van der Waals equation to calculate the pressure of a gas held at T = 400 K for which the molar volume is v = 22 liter/mol. Problem 2.3 You have 22 g of oxygen at a temperature of 500 K and a pressure of 0.5 atm, kept in a vessel of volume V = 56.375 liters. Calculate the molecular mass of oxygen. Problem 2.4 You have a container with gaseous HCN. The volume is 5 liters, the temperature is 298 K. In the evening, the pressure was 1 atm and the next morning it was 0.9 atm. (a) Calculate how many moles of gas have escaped from the vessel. (b) Suppose that the lethal dose of HCN is 0.0001 g/m3 (I made this number up). The dimensions of your lab are 3 m 4 m 3 m. Assuming that no HCN escaped from the room, would the amount of HCN in the room be sufcient to kill you when you went inside in the morning?