# Chapter 1

The properties of gases

Equations of state 1.1 1.2 The perfect gas equation of state Using the perfect gas law

Box 1.1 The gas laws and the weather

1.3

Mixtures of gases: partial pressures

The kinetic model of gases 1.4 1.5 1.6 1.7 1.8 The pressure of a gas according to the kinetic model The average speed of gas molecules The Maxwell distribution of speeds Diffusion and effusion Molecular collisions

Although gases are simple, both to describe and in terms of their internal structure, they are of immense importance. We spend our whole lives surrounded by gas in the form of air and the local variation in its properties is what we call the ‘weather’. To understand the atmospheres of this and other planets we need to understand gases. As we breathe, we pump gas in and out of our lungs, where it changes composition and temperature. Many industrial processes involve gases, and both the outcome of the reaction and the design of the reaction vessels depend on a knowledge of their properties.

Equations of state
We can specify the state of any sample of substance by giving the values of the following properties (all of which are deﬁned in the Introduction): V, the volume of the sample p, the pressure of the sample T, the temperature of the sample n, the amount of substance in the sample However, an astonishing experimental fact is that these four quantities are not independent of one another. For instance, we cannot arbitrarily choose to have a sample of 0.555 mol H2O in a volume of 100 cm3 at 100 kPa and 500 K: it is found experimentally that that state simply does not exist. If we select the amount, the volume, and the temperature, then we ﬁnd that we have to accept a particular pressure (in this case, close to 23 MPa). The same is true of all substances, but the pressure in general will be different for each one. This experimental generalization is summarized by saying the substance obeys an equation of state, an equation of the form

Real gases 1.9 Molecular interactions

1.10 The critical temperature 1.11 The compression factor 1.12 The virial equation of state 1.13 The van der Waals equation of state 1.14 The liquefaction of gases
CHECKLIST OF KEY IDEAS TABLE OF KEY EQUATIONS FURTHER INFORMATION 1.1 QUESTIONS AND EXERCISES

16 CHAPTER 1: THE PROPERTIES OF GASES

p = f (n,V,T )

(1.1)
Table 1.1 The gas constant in various units
R= 8.314 47 8.314 47 8.205 74 × 10−2 62.364 1.987 21 J K−1 mol−1 dm3 kPa K−1 mol−1 dm3 atm K−1 mol−1 dm3 Torr K−1 mol−1 cal K−1 mol−1

This expression tells us that the pressure is some function of amount, volume, and temperature and that if we know those three variables, then the pressure can have only one value. The equations of state of most substances are not known, so in general we cannot write down an explicit expression for the pressure in terms of the other variables. However, certain equations of state are known. In particular, the equation of state of a low-pressure gas is known, and proves to be very simple and very useful. This equation is used to describe the behaviour of gases taking part in reactions, the behaviour of the atmosphere, as a starting point for problems in chemical engineering, and even in the description of the structures of stars.

1 dm3 = 10−3 m3 The text’s website contains links to online databases of properties of gases.

1.1 The perfect gas equation of state
The equation of state of a low-pressure gas was among the ﬁrst results to be established in physical chemistry. The original experiments were carried out by Robert Boyle in the seventeenth century and there was a resurgence in interest later in the century when people began to ﬂy in balloons. This technological progress demanded more knowledge about the response of gases to changes of pressure and temperature and, like technological advances in other ﬁelds today, that interest stimulated a lot of experiments. The experiments of Boyle and his successors led to the formulation of the following perfect gas equation of state: pV = nRT (1.2)

A hypothetical substance that obeys eqn 1.2 at all pressures is called a perfect gas. From what has just been said, an actual gas, which is termed a real gas, behaves more and more like a perfect gas as its pressure is reduced towards zero. In practice, normal atmospheric pressure at sea level (p ≈ 100 kPa) is already low enough for most real gases to behave almost perfectly, and unless stated otherwise we shall always assume in this text that the gases we encounter behave like a perfect gas. The reason why a real gas behaves differently from a perfect gas can be traced to the attractions and repulsions that exist between actual molecules and that are absent in a perfect gas (Chapter 15).
A note on good practice A perfect gas is widely called an
‘ideal gas’ and the perfect gas equation of state is commonly called ‘the ideal gas equation’ We use ‘perfect gas’ to imply the absence of molecular interactions; we use ‘ideal’ in Chapter 6 to denote mixtures in which all the molecular interactions are the same but not necessarily zero.

In this equation (which has the form of eqn 1.1 when we rearrange it into p = nRT /V ), the gas constant, R, is an experimentally determined quantity that turns out to have the same value for all gases. It may be determined by evaluating R = pV/nRT as the pressure is allowed to approach zero or by measuring the speed of sound (which depends on R). Values of R in different units are given in Table 1.1. The perfect gas equation of state—more brieﬂy, the ‘perfect gas law’—is so-called because it is an idealization of the equations of state that gases actually obey. Speciﬁcally, it is found that all gases obey the equation ever more closely as the pressure is reduced towards zero. That is, eqn 1.2 is an example of a limiting law, a law that becomes increasingly valid as the pressure is reduced and is obeyed exactly in the limit of zero pressure.

The perfect gas law summarizes three sets of experimental observations. One is Boyle’s law: At constant temperature, the pressure of a ﬁxed amount of gas is inversely proportional to its volume. Mathematically: Boyle’s law: at constant temperature, p ∝ 1 V

We can easily verify that eqn 1.2 is consistent with Boyle’s law: by treating n and T as constants, the perfect gas law becomes pV = constant, and hence p ∝ 1/V. Boyle’s law implies that if we compress (reduce the volume of) a ﬁxed amount of gas at constant temperature into half its original volume, then its pressure will double. Figure 1.1 shows the graph obtained by plotting experimental values of p against V for a ﬁxed amount of gas at different temperatures

where m and b are the slope and y-intercept of the line. from this graph. Each curve is called an isotherm because it depicts the variation of a property (in this case. the expression being plotted should have the form y = mx + b. this common temperature must represent the absolute zero of temperature. in fact). 1/V Fig. Because a volume cannot be negative.3 shows typical plots of volume against temperature for a series of samples of gases at different pressures and conﬁrms that (at low pressures. The isotherms are hyperbolas. A perfect gas would follow the straight line at all pressures. the pressure) at a single constant temperature. p Volume. graphs of xy = constant. V –273. θ θ/°C Fig. use either mathematical software or the Living graphs from the text’s web site.15 Temperature. respectively. This extrapolation suggests that −273. For a sample that obeys Boyle’s law and that is kept at constant temperature. as shown here. 1. a temperature below which it is impossible to cool an object. all gases give straight lines that extrapolate to V = 0 at −273. the ‘thermodynamic’ scale ascribes the value T = 0 to this absolute zero of temperature. However. (b) 373 K from 30 dm3 to 15 dm3. V = A + Bθ Observed Pressure. Indeed. 1. when a straight line should be obtained. We also see that all the volumes extrapolate to zero as θ approaches the same very low temperature (−273. For more information. or y = constant/x (see Appendix 2). and for temperatures that are not too low) the volume varies linearly with the Celsius temperature.2). A note on good practice It is generally the case that a proposed relation is easier to verify if the experimental data are plotted in a form that should give a straight line. the volume of a ﬁxed amount of gas varies linearly with the temperature. When plotted against Celsius temperatures (as here). Figure 1. which asserts that the volume occupied by a gas (at constant pressure) varies linearly with the temperature. interActivity Explore how the pressure of 1. just as we would expect from Boyle’s law (Fig. That is. Fig. to judge how well Boyle’s law is obeyed. In terms of .2 is Charles’s law: At constant pressure.15°C. Mathematically: Charles’s law: at constant pressure. and the curves predicted by Boyle’s law. the graph showing the dependence is a hyperbola.EQUATIONS OF STATE 17 Increasing pressure Pressure.15°C. and hence is an isotherm. see Appendix 2. where θ (theta) is the temperature on the Celsius scale and A and B are constants that depend on the amount of gas and the pressure. we get straight lines. 1.15°C is the lowest attainable temperature. regardless of the identity of the gas.1 The volume of a gas decreases as the pressure on it is increased. V Increasing temperature Observed Perfect gas Volume.2 A good test of Boyle’s law is to plot the pressure against 1/V (at constant temperature). p Perfect gas 1/Volume. real gases obey Boyle’s law in the limit of low pressures. It is hard. when we plot p against 1/V. 1. The second experimental observation summarized by eqn 1. Each curve corresponds to a single temperature. Hint: To solve this and other interActivities.5 mol CO2(g) varies with volume as it is compressed at (a) 273 K. This diagram shows that the observed pressures (the blue line) approach a straight line as the volume is increased and the pressure reduced.3 This diagram illustrates the content and implications of Charles’s law.

2 Using the perfect gas law Here we review three elementary applications of the perfect gas equation of state.1).25 g of nitrogen gas in a flask of volume 250 cm3 at 20°C.7896* 24.2 if we treat p and T as constants. The second is the prediction of the change in pressure arising from changes in the conditions. We can therefore write: Avogadro’s principle: at constant temperature and pressure. equal volumes of gas contain the same numbers of molecules. 1. Vm. Even though there is no longer any doubt that molecules exist. corresponding to an increase from 27°C to 327°C) doubles the volume. The third is the calculation of the molar volume of a perfect gas under any conditions.18 CHAPTER 1: THE PROPERTIES OF GASES the thermodynamic temperature.2 is Avogadro’s principle: At a given temperature and pressure. V ∝ T It follows that doubling the temperature (such as from 300 K to 600 K.1 Predicting the pressure of a sample of gas A chemist is investigating the conversion of atmospheric nitrogen to usable form by the bacteria that inhabit the root systems of certain legumes.4 24.8 24.8 * At STP (0°C. Strategy For this calculation we need to arrange eqn 1. the units of molar volume are cubic decimetres per mole (dm3 mol−1). in this case as a collection of molecules. Calculations like these underlie more advanced considerations. Example 1. Select the . because it is based on a model of a gas. That is. of any substance (not just a gas) is the volume it occupies per mole of molecules.3) With volume in cubic decimetres and amount in moles.2 The molar volumes of gases at standard ambient temperature and pressure (SATP: 298. Now we can see that eqn 1.00 dm3 of oxygen at 100 kPa and 300 K contains the same number of molecules as 1. The data in Table 1. we rearrange it into V = nRT/p. as required.8 24. at the same temperature and pressure. To use this expression. p) in terms of the information supplied: p= nRT V Vm = V n Volume of sample Amount of substance in sample (1.00 dm3 of carbon dioxide.15 K and 1 bar) Gas Perfect gas Ammonia Argon Carbon dioxide Nitrogen Oxygen Hydrogen Helium Vm /(dm3 mol−1) 24.2 (pV = nRT ) into a form that gives the unknown (the pressure. It is calculated by dividing the volume of the sample by the amount of molecules it contains: Table 1. which we can obtain from the mass and the molar mass (by using n = m/M) and to convert the temperature to the Kelvin scale (by adding 273. and then note that when the amount n and the pressure p are both constant.2 is consistent with Charles’s law. Avogadro’s suggestion is a principle rather than a law (a direct summary of experience). and needs to know the pressure in kilopascals exerted by 1.15 to the Celsius temperature). Avogadro’s principle implies that the molar volume of a gas should be the same for all gases at the same temperature and pressure.2 show that this conclusion is approximately true for most gases under normal conditions (normal atmospheric pressure of about 100 kPa and room temperature).8 24. The ﬁrst is the prediction of the pressure of a gas given its temperature.4140 dm3 mol−1. therefore. 1 atm). its chemical amount. this relation remains a principle rather than a law. The principle implies that if we double the number of molecules. V ∝ n This result follows easily from eqn 1.8 24. or any other gas. including the way that meteorologists understand the changes in the atmosphere that we call the weather (Box 1. Charles’s law takes the simpler form Charles’s law: at constant pressure. and the volume it occupies. First. then the volume of the sample will double. Vm = 24. provided the pressure remains the same. The molar volume. but keep the temperature and pressure constant.6 24. The third feature of gases summarized by eqn 1. we need to know the amount of molecules (in moles) in the sample. 1. we can write V ∝ T.

Self-test 1.1 Calculate the pressure exerted by 1.4) The temperature of the sample is T/K = 20 + 273. we get V = nRT/p V nRT / p RT Vm = = = n n p Deﬁnition (1.02 of gas molecules has not changed. the initial temperature is T1.1 using the units that match the data and the information required (pressure in kilopascals and volume in litres). all gases have the same molar volume. We can rearrange it to calculate any one unknown (such as p2.0 kPa to 150.2 What is the final volume of a sample of gas that has been heated from 25°C to 1000°C and its pressure increased from 10. which is still encountered. The standard pressure is denoted pa.25 = = mol MN 2 28. We use the perfect gas law as follows.3 cm3] We have used the relation 1 J = 1 Pa m3 and 1 kPa = 103 Pa. and carry it out in a single step. because R is a constant and the amount This expression lets us calculate the molar volume of any gas (provided it is behaving perfectly) from its pressure and its temperature.5) In some cases. and the pressure changes to p2 as a result.3 expresses the molar volume in terms of the volume of a sample. When we combine the two. we are given the pressure under one set of conditions and are asked to predict the pressure of the same sample under a different set of conditions. for instance) in terms of the other variables.79 dm3 mol−1.5.2 by the temperature we can write p1V1 = nR T1 Suppose now that the conditions are changed to T2 and V2. Suppose the initial pressure is p1. Equation 1. The molar volume of a perfect gas at SATP is 24.15 K) and a pressure of exactly 1 bar (100 kPa). [Answer: 143 kPa] Finally. for a given temperature and pressure. as can be veriﬁed by substituting the values of the temperature and pressure into eqn 1. This value implies that at SATP. and the initial volume is V1. Chemists have found it convenient to report much of their data at a particular set of ‘standard’ conditions. Solution The amount of N2 molecules (of molar mass 28. By standard ambient temperature and pressure (SATP) they mean a temperature of 25°C (more precisely. we see how to use the perfect gas law to calculate the molar volume of a perfect gas at any temperature and pressure. given that its initial volume was 15 cm3? [Answer: 4. namely 0°C and 1 atm. .0 kPa.25 g 1.EQUATIONS OF STATE 19 value of R from Table 1. It also shows that. This expression is known as the combined gas equation. An earlier set of standard conditions.41 dm3 mol−1. from p = nRT/V. This procedure avoids rounding errors. is standard temperature and pressure (STP).02 g mol−1 28.22 g of carbon dioxide confined to a flask of volume 500 cm3 at 37°C. Self-test 1.15 Therefore. eqn 1. It follows that we can combine the two equations into a single equation: p1V1 p2V2 = T1 T2 (1.2 tells us that p2V2 = nR T2 The nR on the right of these two equations is the same in each case. Then under the new conditions eqn 1. so pa = 1 bar exactly. Note how the units cancel like ordinary numbers.2 in the form V = nRT/p expresses the volume in terms of the pressure. The molar volume of a perfect gas at STP is 22. A note on good practice It is best to postpone the actual numerical calculation to the last possible stage. 1 mol of perfect gas molecules occupies about 25 dm3 (a cube of about 30 cm on a side).02 g mol−1) present is nN 2 = m 1. 298. provided they are behaving perfectly. Then by dividing both sides of eqn 1.

The elongated regions of high and low pressure are known. and composition in the troposphere are manifest as ‘weather’. The former result in the formation of regions of high pressure (‘highs’ or anticyclones) and the latter result in regions of low pressure (‘lows’. The pressure and temperature vary with altitude. In the troposphere the average temperature is 15°C at sea level. 24 18 Altitude.7 × 10−6 7.3 × 10−6 Nitrogen. it expands without transfer of heat from its surroundings and it cools.0 × 10−3 1. If we suppose that the temperature has its average value all the way up to the edge of the troposphere. particularly the local turbulence called eddies) but the pressure and temperature vary with altitude and with the local conditions. or cyclones). O2 Argon. Horizontal pressure differentials result in the flow of air that we call wind. respectively. so the moisture forms clouds. The motion of air in the upper altitudes may lead to an accumulation in some regions and a loss of molecules from other regions. This variation is much less pronounced when expressed on the Kelvin scale. He Methane. Because the Earth is rotating from west to east. so the density of the moist sample is less than that of the dry sample. Cloudy skies can therefore be associated with rising air and clear skies are often associated with descending air.53 23.0 × 10−6 75. about 3 Torr)—marked on it are called isobars.28 0. Local variations of pressure.0 × 10−4 1. H = RT/Mg. h/km 12 6 0 0 0. The lines of constant pressure—differing by 4 mbar (400 Pa. Cool air can absorb lower concentrations of water vapour than warm air.031 5. temperature.7 × 10−6 3. The presence of water vapour results in a lower density of air at a given temperature and pressure. the layer extending up to about 11 km. The numbers of molecules in 1 m3 of moist air and dry air are the same (at the same temperature and pressure). NO Xenon. as ridges and troughs. The composition is maintained moderately constant by diffusion and convection (winds.1 × 10−4 5. In meteorology.0 × 10−5 8. Xe Ozone. O3 Summer: Winter: where M is the average molar mass of air and T is the temperature. falling to −57°C at the bottom of the tropopause at 11 km. CO2 Hydrogen.3 × 10−3 7.0 × 10−6 2. CH4 Krypton. These regions are shown as H and L on the accompanying weather map. First. A small region of air is termed a parcel. More specifically. but the mass of an H2O molecule is less than that of all the other major constituents of air (the molar mass of H2O is 18 g mol−1. as we may conclude from Avogadro’s principle.14 1. winds are deflected towards the right in . large-scale vertical movement is called convection.08 20. depressions. As a parcel rises.8 × 10−3 5.2 × 10−5 1. It implies that the pressure of the air and its density fall to half their sea-level value at h = H ln 2. particularly in the troposphere (the ‘sphere of change’). and the humidity it causes. then the pressure varies with altitude. Ne Helium. according to the barometric formula: p = p0e−h/H where p0 is the pressure at sea level and H is a constant approximately equal to 8 km.20 CHAPTER 1: THE PROPERTIES OF GASES Box 1. a mixture of gases with the composition summarized in the table. h. The barometric formula fits the observed pressure distribution quite well even for regions well above the troposphere (see the illustration).95 0.1 × 10−4 3.2 × 10−4 1.2 × 10−4 2. Kr Nitric oxide. ranging from 288 K to 216 K. One of the most variable constituents of air is water vapour. we note that a parcel of warm air is less dense than the same parcel of cool air. interActivity How would the graph shown in the illustration change if the temperature variation with altitude were taken into account? Construct a graph allowing for a linear decrease in temperature with altitude.2 × 10−5 3. Ar Carbon dioxide.9 × 10−5 1. N2 Oxygen. p/p0 1 The variation of atmospheric pressure with altitude as predicted by the barometric formula.5 Pressure.0 × 10−4 1. or 6 km. The composition of the Earth’s atmosphere Substance Percentage By volume By mass 78.1 The gas laws and the weather The biggest sample of gas readily accessible to us is the atmosphere. the average molar mass of air molecules is 29 g mol−1).93 0.047 2. H2 Neon. an average of 268 K.

A less dramatic manifestation of an inversion layer is the presence of hazy skies. the winds tend to travel perpendicular to the isobars from high to low pressure. descending air is associated with clear skies. At the surface. These hazes give rise to the various ‘Blue Mountains’ of the world. In winter. 1. or the mixtures of hydrogen and nitrogen used in the industrial synthesis of ammonia. where wind speeds are lower. the cold surface air may prevent the complete fall of air. and result in a temperature inversion. It also becomes warmer by compression as it descends. the composition of exhaled air in medicine. Hazy skies also form over vegetation that generate aerosols of terpenes or other plant transpiration products. Geographical conditions may also trap cool air. The Blue Ridge section of the Appalachians is another example. this one for Western Europe on 3 May 2008. respectively. and pine and fir. and we knew that a certain mass of carbon dioxide exerts a pressure of . with low pressure to their left in the northern hemisphere and to the right in the southern hemisphere.. as in Los Angeles.EQUATIONS OF STATE 21 N Wind L Rotation L S The horizontal flow of air relative to an area of low pressure in the northern and southern hemispheres. particularly in industrial areas. such as the Great Dividing Range in New South Wales. pJ is the pressure that the gas J would exert if it were alone in the container at the same temperature. so regions of high pressure are associated with high surface temperatures. such as when we are considering the properties of the atmosphere in meteorology. the range in Jamaica. This differential motion results in a spiral outward flow of air clockwise in the northern hemisphere around a high and an inward counterclockwise flow around a low. but it can be treated as valid under most conditions we encounter. A typical weather map.3 Mixtures of gases: partial pressures We are often concerned with mixtures of gases. A brief illustration Suppose we were interested in the composition of inhaled and exhaled air. In the early nineteenth century.. (1. As we have seen. John Dalton carried out a series of experiments that led him to formulate what has become known as Dalton’s law: The pressure exerted by a mixture of perfect gases is the sum of the pressures that each gas would exert if it were alone in the container at the same temperature: p = pA + pB + .6) In this expression. The air lost from regions of high pressure is restored as an influx of air converges into the region and descends. and the range stretching from central Oregon into southeastern Washington. the northern hemisphere and towards the left in the southern hemisphere. Winds travel nearly parallel to the isobars. which are dense with eucalyptus. Dalton’s law is strictly valid only for mixtures of perfect gases (or for real gases at such low pressures that they are behaving perfectly). tree ferns. and the photochemical pollutants we know as smog may be trapped under the warm layer. with a layer of warm air over a layer of cold air. We need to be able to assess the contribution that each component of a gaseous mixture makes to the total pressure.

and the sum of these partial pressures is the total pressure (because the sum of all the mole fractions is 1).. xA = 1 and xB = 0. a small square represents one molecule of A (yellow squares) or B (green squares).229 xB = 0. according to Dalton’s law. .780. 2 2 The value of nJRT/V is the pressure that an amount nJ of J would exert in the otherwise empty container. we get p = nRT/V xJ = nJ n amount of J molecules in the mixture total amount of molecules in the mixture (1. When only B is present. this general expression becomes xA = nA nA + nB xB = nB nA + nB xA + xB = 1 (1. Self-test 1.. Fig.7. There are 48 squares in each sample. That is.22 CHAPTER 1: THE PROPERTIES OF GASES 20 5 kPa kPa kPa 25 pA pB pA + pB A B xA = 0.771 5 kPa when present alone in a container. .708 xB = 0. 1.292 A B A+B xA = 0. nB B molecules. [Answer: 0. If the gases are real. 1.4 The partial pressure pA of a perfect gas A is the pressure that the gas would exert if it occupied a container alone. Mole fractions are unitless because the unit mole in numerator and denominator cancels.5 A representation of the meaning of mole fraction. 23. When both are present in the same amounts. 0.375 Fig.625 xA = 0.0 g of air consists of 75.2 g of O2. O2. . and so on (where the nJ are amounts in moles). In each case. if we introduce p = nRT/V into eqn 1. similarly.8b) When only A is present. of the gas J is deﬁned as pJ = xJ p (1.. provided all the gases in the mixture behave perfectly.7. or 25 kPa (Fig.4).8a) nJ nRT RT RT pJ = x J p = x J × = nxJ × = nJ × V V V Deﬁnition where n = nA + nB + .. when both gases are present in the container. and Ar in dry air at sea level. the partial pressure pB of a perfect gas B is the pressure that the gas would exert if it occupied the same container alone. and 1. for that deﬁnition applies to all gases. In a mixture that consists of nA A molecules. Hint: Begin by converting each mass to an amount in moles.7) Calculate the mole fractions of N2. The total pressure p when both perfect gases simultaneously occupy the container is the sum of their partial pressures. we can identify the partial pressure of J with the contribution that J makes to the total pressure. one that consists of two species.) is For a mixture of perfect gases. 0. 1. pJ. the carbon dioxide in the mixture contributes 5 kPa to the total pressure and oxygen contributes 20 kPa. Then.5 g of N2. xB = 0. the partial pressure of J as deﬁned by eqn 1. the partial pressure.210.009] where xJ is the mole fraction of the gas J in the mixture. B. xA = 1 and xB = 1 . the mole fraction of J (where J = A. and that a certain mass of oxygen exerts 20 kPa when present alone in the same container at the same temperature.3 For any type of gas (real or perfect) in a mixture.3 g of Ar. For a binary mixture. the total pressure of the mixture is the sum of these two pressures. given that 100.7 is the pressure of J used in Dalton’s law. The mole fraction of J is the amount of J molecules expressed as a fraction of the total amount of molecules in the mixture. their partial pressures are still given by eqn 1. xB = 1 and xA = 0. Thus.

0 kPa and pAr = 0. The assumption that the molecules do not interact unless they are in contact implies that the potential energy of the molecules (their energy due to their position) is independent of their separation and may be set equal to zero.1 for a derivation of this equation.1).50 g of oxygen and 6. Now we develop this model of the gaseous state of matter to see how it accounts for the perfect gas law. and in the absorption of oxygen by blood in our lungs (see Box 6. the partial pressure of nitrogen is pN2 = xN2p = 0. an important component of science as a whole is its technique of proposing a qualitative model and then expressing that model mathematically. we square each speed. This quantity is deﬁned as the square root of the mean value of the squares of the speeds. for a sample consisting of N molecules with speeds v1. the walls experience a virtually constant force. . One of the most important functions of physical chemistry is to convert qualitative notions into quantitative statements that can be 1. The ‘kinetic model’ (or the ‘kinetic molecular theory’.) Here c is the root-mean-square speed (rms speed) of the molecules. add the squares together. The point-like molecules move randomly with a wide range of speeds and in random directions. v2. and xAr = 0. 1.3..780.0 kPa Similarly. The molecules do not interact. and the quantitative prediction (the perfect gas law) is experimentally veriﬁable. It follows that the faster the molecules travel (and hence the greater their kinetic energy). for the other two components we find pO2 = 21. A gas consists of molecules in ceaseless random motion. It then follows from eqn 1. 2. On the basis of this model.THE KINETIC MODEL OF GASES 23 however.009 for dry air at sea level. The kinetic model of gases is based on three assumptions: 1. vN.6). 57 kPa] The kinetic model of gases We remarked in the Introduction that a gas may be pictured as a collection of particles in ceaseless.9 kPa. Self-test 1. Calculate the partial pressures of a sample of gas consisting of 2. (See Further information 1. v.6 The model used for discussing the molecular basis of the physical properties of a perfect gas.7 that when the total atmospheric pressure is 100 kPa. That is.780 × (100 kPa) = 78. and hence the gas exerts a steady pressure.4 The pressure of a gas according to the kinetic model The kinetic model accounts for the steady pressure exerted by a gas in terms of the collisions the molecules make with the walls of the container. Indeed. except during collisions. but as billions of collisions take place every second.. A brief illustration From Self-test 1. 3. each partial pressure is no longer the pressure that the gas would exert when alone in the container. the pressure exerted by a gas of molar mass M in a volume V is p= nMc2 3V (1. [Answer: 31 kPa. tested experimentally by making measurements and comparing the results with predictions. both of which change when they collide with the walls or with other molecules.43 g of carbon dioxide with a total pressure of 88 kPa. of the molecules. The size of the molecules is negligible in the sense that their diameters are much smaller than the average distance travelled between collisions. Provided the gases are perfect.. the greater the total energy of the gas. these partial pressures are the pressures that each gas would exert if it were separated from the mixture and put in the same container on its own. . to enable aquatic life to thrive. The total energy of a sample of gas is therefore the sum of the kinetic energies (the energy due to motion) of all the molecules present in it.4 The partial pressure of molecular oxygen in air plays an important role in the aeration of water. random motion (Fig. we have xN2 = 0. 1. Each impact gives rise to a brief force on the wall.9) Fig. KMT) of gases is an excellent example of this procedure: the model is very simple. xO2 = 0.210.

.24 CHAPTER 1: THE PROPERTIES OF GASES divide by the total number of molecules (to get the mean.15 is that The rms speed of molecules in a gas is proportional to the square root of the temperature. 〈Ek〉. denoted by 〈.. on a cold day.00 (1) km h−1.06 km h−1.957 and compare it to pV = nRT.. we can think of it as a measure of the mean kinetic energy of the molecules of the gas.13 is unreliable for such small samples. A brief illustration Cooling a sample of air from 25°C Equation 1. because sound is a wave of pressure variation transmitted by the movement of molecules. That being so.00 (5).00 (4). The rms speed is quite close in value to another and more readily visualized measure of molecular speed.0 g mol−1) and a temperature corresponding to 25°C (that is.) [Answer: (a) 49.10) The rms speed might at ﬁrst sight seem to be a rather peculiar measure of the mean speeds of the molecules. so the speed of propagation of a wave should be approximately the same as the speed at which molecules can adjust their locations. and for qualitative arguments. Self-test 1.15) For samples consisting of large numbers of molecules. This conclusion is a major success of the kinetic model. of the molecules: C= v1 + v2 + .96 km h−1] Substitution of the molar mass of O2 (32. the mean speed is slightly smaller than the rms speed..9 already resembles the perfect gas equation of state. doubling the thermodynamic temperature (that is. we do not need to distinguish between the two measures of average speed. the same is true of the mean speed too (because the two quantities are proportional to each other). or 1 mc2..12) The great usefulness of this expression is that we can rearrange it into a formula for the rms speed of the gas molecules at any temperature: ⎛ 3RT ⎞ c=⎜ ⎟ ⎝ M ⎠ 1/ 2 (1. doubling the temperature on the Kelvin scale) increases the mean and the rms speed of molecules by a factor of 21/2 = 1.. Both these values are not far off the speed of sound in air (346 m s−1 at 25°C).00 (9).14) (298 K) to 0°C (273 K) reduces the original rms speed of the molecules by a factor of ⎛ 273 K ⎞ ⎜ ⎜ 298 K ⎟ ⎟ ⎝ ⎠ 1/ 2 ⎛ 273 ⎞ =⎜ ⎜ 298 ⎟ ⎟ ⎝ ⎠ 1/ 2 = 0. the mean speed.5 Cars pass a point travelling at 45.921c (1. (b) 48. Calculate (a) the rms speed and (b) the mean speed of the cars. wherever c appears.13) For elementary purposes.11) Therefore. + vN ⎞ =⎜ 1 ⎟ ⎜ ⎟ N ⎝ ⎠ 1/ 2 1. (Hint: Use the definitions directly. but its signiﬁcance becomes clear when we make use of the fact that the kinetic energy of a molecule of mass m travelling at a speed v is Ek = 1 mv 2. The same calculation for nitrogen molecules gives 515 m s−1..5 The average speed of gas molecules We now suppose that the expression for pV derived from the kinetic model is indeed the equation of state of a perfect gas. Because the mean speed is proportional to the rms speed. pV = nRT pV = 1 nMc2 3 (1. the average speed of air molecules (which is changed by the same factor) is about 4 per cent less than on a warm day.14 to nRT. + vN N (1. but for precise work the distinction is important.414. where the number of cars is given in parentheses. 57. Therefore. The precise relation is ⎛ 8⎞ C=⎜ ⎟ ⎝ 3π ⎠ 1/ 2 c ≈ 0.〉). 298 K) gives an rms speed for these molecules of 482 m s−1. is the average of this quantity. That similarity is reasonable. It follows from the 2 relation 1 mc 2 = 〈Ek〉 that 2 ⎛ 2〈Ek 〉 ⎞ c=⎜ ⎟ ⎝ m ⎠ 1/ 2 which gives 1 nMc2 3 = nRT The ns now cancel. we can equate the expression on the right of eqn 1. which 2 implies that the mean kinetic energy. C. 53. 47.. the relation in eqn 1.00 (7). 50. So. for we can rearrange it into pV = 1 nMc2 3 (1. to give 1 Mc2 3 = RT (1. The important conclusion to draw from eqn 1. for the model implies an experimentally veriﬁed result. .. and ﬁnally take the square root of the result: c = 〈v 〉 2 1/ 2 2 2 ⎛ v2 + v2 + .

between 300 m s−1 and 310 m s−1. the distribution might tell us that at 20°C 19 out of 1000 O2 molecules have a speed in the range between 300 and 310 m s−1. The mathematical expression that tells us the fraction of molecules that have a particular speed at any instant is called the distribution of molecular speeds. the term F(s) = 4π(M/2πRT)3/2 s2 e−Ms /2RT . however. like the impact of a bat on a ball). we have dealt only with the average speed of molecules in a gas. and get accelerated to a high speed. we see that the fraction in the range Δs increases in proportion to the width of the range. One of the skills to develop in physical chemistry is the ability to interpret the message carried by equations. Although eqn 1. Equations convey information. Its presence implies that the fraction of molecules with very high speeds will be very small because 2 e−x becomes very small when x2 is large. 2 (1. then the fraction of molecules in that range doubles too. so the exponential factor falls towards zero . • The factor M/2RT multiplying s2 in the exponent. which it reaches as x approaches inﬁnity (Fig. Now let’s consider the content of eqn 1. There is a ceaseless redistribution of speeds among molecules as they undergo collisions. • Equation 1. This function approaches zero more rapidly as a increases. Not all molecules. that 21 out of 1000 have a speed in the range 400 to 410 m s−1. and so on. but be brought to a sudden stop when they collide. Before we begin. 2 • The opposite is true when the temperature.16) This formula was used to calculate the numbers quoted above. 2 s2 e−Ms 2 / 2RT The illustration also shows the behaviour of the two functions for negative values of x. corresponding to s = 300 m s−1 and Δs = 10 m s−1) is f = F(s)Δs with ⎛ M ⎞ F(s) = 4π ⎜ ⎟ ⎝ 2πRT ⎠ 3/ 2 Fig. Each molecule collides once every nanosecond (1 ns = 10−9 s) or so in a gas under normal conditions. • Because f is proportional to the range of speeds Δs. and it is far more important to be able to read that information than simply to remember the equation. is large. M. The enlargement on the right shows the behaviour for x > 0 in more detail. also starts off at 1 when x = 0 and decays to zero as x increases. e−x.16. the fraction f of molecules that have a speed in a narrow range between s and s + Δs (for example.16 piece by piece. starts off at 1 when x = 0 and decays toward zero. That tells us that heavy molecules are unlikely to be found with very high speeds. The exponential function e−ax rises rapidly to inﬁnity. If at a given speed we double the range of interest (but still ensure that it is narrow). its decay is initially slower but then plunges down to zero more rapidly than an exponential function (Fig.16 includes a decaying exponential function. however. and the bell-shaped 2 Gaussian function. Here. is large when the molar mass. T. e−x . 1.THE KINETIC MODEL OF GASES 25 1. is high: then the factor M/2RT in the exponent is small. e−ax and e−ax . a function of the form e−ax . 1. • An exponential function. Thus. it will be useful to know the shape of exponential functions. but the Gaussian function falls back to zero and traces out a bell-shaped curve.7 The exponential function. travel at the same speed: some move more slowly than the average (until they collide.16 looks complicated. we 2 deal with two types. and his expression is known as the Maxwell distribution of speeds. and others may brieﬂy move at much higher speeds than the average. so the exponential factor goes most rapidly towards zero when M is large. The precise form of the distribution was worked out by James Clerk Maxwell towards the end of the nineteenth century. F(s) = 4π(M/2πRT)3/2 s2 e−Ms /2RT . and in preparation for their occurrence throughout the text. Note that both are equal to 1 at x = 0 but the exponential function rises to infinity as x → −∞. According to Maxwell. 1.7). its features can be picked out quite readily. • A Gaussian function. a function of the form e−ax. Let’s read the information in eqn 1.7).6 The Maxwell distribution of speeds 10 1 9 8 7 6 5 4 3 2 1 0 –5 –4 –3 –2 –1 0 x 1 2 3 4 5 e–x e–x 2 0 0 1 x 2 3 So far.

(c) Based on your observations. 1. That narrow spread means that most molecules will be found with speeds close to the average. but they also have a signiﬁcantly narrower spread of speeds.02 g mol−1) and helium (4. a greater fraction of the molecules can be expected to have high speeds than at low temperatures. interActivity (a) Plot different distributions by keeping the molar mass constant at 100 g mol−1 and varying the temperature of the sample between 200 K and 2000 K. then we get 1. As we deduced from the equation. and Ar at 500 K.1).8 is a graph of the Maxwell distribution. The speed of rotation of the disks brings the slots into line for molecules travelling at a particular speed. • A factor s2 (F(s) = 4π(M/2πRT )3/2 s2 e−Ms /2RT ) multiplies the exponential.10). not only do heavy molecules have lower average speeds than light molecules at a given temperature.9 The Maxwell distribution of speeds also depends on the molar mass of the molecules. Fig.00 g mol−1) are very rare in the Earth’s atmosphere. we see that only small fractions of molecules in the sample have very low or very high speeds. This feature plays an important role in determining the composition of planetary atmospheres. (b) Use mathematical software or the Living graph applet from the text’s web site to evaluate numerically the fraction of molecules with speeds in the range 100 m s−1 to 200 m s−1 at 300 K and 1000 K.8 The Maxwell distribution of speeds and its variation with the temperature.26 CHAPTER 1: THE PROPERTIES OF GASES Low temperature Number of molecules Number of molecules Heavy molecules High temperature Light molecules Speed Speed Fig. This factor goes to zero as s goes to zero. because it means that a signiﬁcant fraction of light molecules travel at suAciently high speeds to escape from the planet’s gravitational attraction. 2 • The remaining factors 2 (the term F(s) = 4π(M/2πRT)3/2 s2 e−Ms /2RT ) simply ensure that when we add together the fractions over the entire range of speeds from zero to inﬁnity. The ability of light molecules to escape is one reason why hydrogen (molar mass 2. Molecules of low molar mass have a broad spread of speeds. In contrast. By varying the . This feature plays an important role in the rates of gas-phase chemical reactions. and shows these features pictorially for the same gas (the same value of M) but different temperatures. for (as we shall see in Section 10. as the tail of the distribution reaches up to higher speeds. which in turn depends on their speeds. relatively slowly as s increases. The Maxwell distribution has been veriﬁed experimentally by passing a beam of molecules from an oven at a given temperature through a series of coaxial slotted disks. air (see Box 1. Figure 1. light molecules (such as H2) have high average speeds and a wide spread of speeds: many molecules will be found travelling either much more slowly or much more quickly than the average. The distribution is much narrower for heavy molecules.9 is a plot of the Maxwell distribution for molecules with different molar masses at the same temperature. the fraction with very high speeds increases sharply as the temperature is raised. interActivity Plot distributions for He. Note the broadening of the distribution and the shift of the rms speed to higher values as the temperature is increased. the rate of a reaction in the gas phase depends on the energy with which two molecules crash together. so only molecules with that speed pass through and are detected. This tells us that at high temperatures. provide a molecular interpretation of temperature. As can be seen. and a significant fraction may be found travelling much faster than the rms speed. Figure 1. and most of them travel with speeds close to the rms value. However. so the fraction of molecules with very low speeds will also be very small. 1.

The rate . you need to specify that it is the rate in terms of amount of molecules.7 Diffusion and effusion Diffusion is the process by which the molecules of different substances mingle with each other. the ratio of the rates of effusion is only (1.01⎞ =⎜ ⎜ 2. however. 1. but the process is very slow.10). 1.THE KINETIC MODEL OF GASES 27 rotation speed. The rates of diffusion and effusion of gases increase with increasing temperature. Gaseous diffusion is much faster.02 g mol−1) and carbon dioxide (44. Note of good practice Always make it clear what terms mean: in this instance ‘rate’ alone is ambiguous. as in a puncture in an inﬂated balloon or tyre (Fig. proposed by Thomas Graham in 1833: At a given pressure and temperature. The dependence on molar mass. Thousands of successive effusion stages are therefore required to achieve a signiﬁcant separation. The high rate of effusion of hydrogen and helium is one reason why these two gases leak from containers and through rubber diaphragms so readily. the rate of effusion of a gas is inversely proportional to the square root of its molar mass: Rate of effusion ∝ 1 M1/ 2 (1. The process of effusion is the escape of a gas through a small hole. for if a gas is produced by a localized source (such as carbon dioxide from the respiration of animals.01 g mol−1 ⎞ ⎟ =⎜ ⎜ 2. the shape of the speed distribution can be explored and is found to match that predicted by eqn 1. the process of mixing is accelerated by winds: such bulk motion of matter is called convection. only a single substance is in motion. The process depends on the formation of uranium hexaﬂuoride. oxygen from photosynthesis by green plants. The diffusion of a solid through a liquid solvent is much faster but mixing normally needs to be encouraged by stirring or shaking the solid in the liquid (the process is then no longer pure diffusion).17) Rate in this context means the number (or number of moles) of molecules that escape per second. because although nearly 5 times as many hydrogen molecules escape. and pollutants from vehicles and industrial sources). (b) Effusion is the escape of molecules through a small hole in a confining wall. The different rates of effusion through a porous barrier are employed in the separation of uranium-235 from the more abundant and less useful uranium-238 in the processing of nuclear fuel. A brief illustration The rates (in terms of amounts of molecules) at which hydrogen (molar mass 2. is simple only in the case of effusion. because the ratio of the molar masses of 238 UF6 and 235 UF6 is only 1. However. (b) Fig.004. The experimental observations on the dependence of the rate of effusion of a gas on its molar mass are summarized by Graham’s law of effusion. not the two or more intermingling gases involved in diffusion. and molecular speeds increase with temperature. a volatile solid.16.672 1/ 2 1/ 2 (a) The mass of carbon dioxide that escapes in a given interval is greater than the mass of hydrogen. as molecular speeds decrease with increasing molar mass. The atoms of two solids diffuse into each other when the two solids are in contact. 1. In effusion. In practice.01 g mol−1) effuse under the same conditions of pressure and temperature are in the ratio ⎛M ⎞ Rate of effusion of H2 CO2 ⎟ =⎜ Rate of effusion of CO2 ⎜ MH2 ⎟ ⎝ ⎠ ⎛ 44. Note that molecules of both substances move. each carbon dioxide molecule has over 20 times the mass of a molecule of hydrogen.016 ⎟ ⎟ ⎝ ⎠ 1/ 2 ⎛ 44. then the molecules of gas will diffuse from the source and in due course be distributed throughout the atmosphere. and each substance diffuses into the other.008.016 g mol−1 ⎟ ⎝ ⎠ = 4. It accounts for the largely uniform composition of the atmosphere.10 (a) Diffusion is the spreading of the molecules of one substance into the region initially occupied by another species.008)1/2 = 1. The rates also decrease with increasing molar mass. as both processes depend on the motion of molecules.

8 Molecular collisions The average distance that a molecule travels between collisions is called its mean free path. λ) divided by the time of ﬂight (1/z). The collision frequency. is therefore the area of a circle of radius d. then the mean free path in a typical gas would be about the length of a tennis court.46 0. . C2H4 Helium. such as mass spectrometry. σ (sigma). The basic kinetic model supposes that the molecules are effectively point-like. because a molecule in a liquid meets a neighbour even if it moves only a fraction of a diameter. CH4 Nitrogen.18) To ﬁnd expressions for λ and z we need a slightly more elaborate version of the kinetic model. The collision cross-section. A molecule will hit another molecule if the centre of the former lies within a circle of radius d.43 0. O2 Sulfur dioxide.3 Collision cross-sections of atoms and molecules Species Argon. then we can ﬁnd the other from this equation and the value of c given in eqn 1. It follows that the mean free path and the collision frequency are related by c= mean free path λ = = λz time of flight 1/ z (1. 1/z.58 Therefore. Ar Benzene.19) Table 1.21 0. which is in accord with Graham’s law. where d can be thought of as the diameter of the molecules (Fig. d Fig. CO2 Chlorine. the target area presented by one molecule to another. z is the average number of collisions one molecule makes in a given time interval divided by the length of the interval. the average time that a molecule spends in ﬂight between two collisions (for instance. As we shall see. if there are 10 collisions per second. then the 1 average time between collisions is 10 of a second and 1 the time of ﬂight is 10 s). H2 Methane. However. However. z. in gases. the mean free paths of molecules can be several hundred molecular diameters. is the average length of the ﬂight of a molecule between collisions (that is. however. it is possible to show that Use z = c/l /l λ= RT 21/2N Aσ p z= 21/2N Aσ cp RT (1. The mean free path in a liquid is less than the diameter of the molecules. If we think of a molecule as the size of a tennis ball. N2 Oxygen. the mean free path. the rms speed c. which we can loosely think of as the average speed.15). Speciﬁcally. it follows that the rate should be inversely proportional to M 1/2. pd 2. we need to assume that two ‘points’ score a hit whenever they come within a certain range d of each other.52 0. d Radius. He Hydrogen. C6H6 Carbon dioxide.36 0.88 0. the collision frequency in a typical gas is about 109 s−1 at 1 atm and room temperature. σ /nm2 0. SO2 1 nm2 = 10−18 m2. to obtain collisions. λ (lambda). Diameter. 1. there are now much more precise methods available. so σ = πd 2. Graham’s law is explained by noting that the rms speed of molecules of a gas is inversely proportional to the square root of the molar mass (eqn 1. Because the rate of effusion through a hole in a container is proportional to the rate at which molecules pass through the hole.3 lists the collision cross-sections of some common atoms and molecules.11). It follows that the inverse of the collision frequency. Because speed is distance travelled divided by the time taken for the journey. The collision cross-section is the target area.15.93 0. is the average rate of collisions made by one molecule.11 To calculate features of a perfect gas that are related to collisions.27 0. is the time of ﬂight.40 0. When this quantity is built into the kinetic model. if we can calculate either λ or z. Cl2 Ethene. 1.28 CHAPTER 1: THE PROPERTIES OF GASES of effusion of gases was once used to determine molar mass by comparison of the rate of effusion of a gas or vapour with that of a gas of known molar mass. Table 1. so the time of ﬂight in a gas is typically 1 ns. 1. a point is regarded as being surrounded by a sphere of diameter d. so the collision frequency is 10 s−1.64 0.

Molecular interactions—the attractions and repulsions between molecules—give rise to a potential energy that contributes to the total energy of a gas. under most conditions the criterion λ >> d is satisﬁed and the gas can be treated as though it is perfect.0 bar to 2. we should interpret the essence of the two expressions in eqn 1. higherpressure gas. = 7. in fact all molecules do interact with one another provided they are close enough together. Because λ ∝ 1/σ.19 rather than trying to remember them. providing their collision cross-sections are the same. This decrease is a result of the increase in the number of molecules present in a given volume as the pressure is increased.0 bar at 25°C.2 billion collisions each second. For instance. heavy molecules have lower collision frequencies than light molecules.0 bar and the same temperature the collision frequency is doubled. At low enough temperatures the molecules of a gas have insuAcient kinetic energy to escape from each other’s attraction and they stick together. the molecule takes less time to travel to its neighbour in a denser. so the ‘kinetic energy only’ model is only an approximation. For example. at 2.022 × 10 NA 23 mol ) × (0. 1.88 nm2) is about four times greater than that of a helium atom (0. although molecules attract each other when they are a few diameters apart. and we know that c ∝ 1/M1/2. as soon as they come into contact they repel each other. Second. provided the temperature is the same. Because λ ∝ 1/p.40 × 10 s –1 m ) × (1. This dependence follows from the fact that. we have also used 1 J = 1 Pa m3 and 1 nm = 10−9 m. a perfect gas is a gas for which the mean free path. of the molecules in the sample is much greater than d. This attraction is responsible for the condensation of gases into liquids at low temperatures. Because z ∝ p. to 1. the collision cross-section of a benzene molecule (0. Under the same conditions. l= (8. . everything we have said applies to perfect gases.19 shows that z ∝ c. so each molecule makes 6. λ. Once again. However. the mean free path of an O2 molecule decreases from 73 nm to 36 nm when the pressure is increased from 1. although the collision frequency for an O2 molecule in oxygen gas at SATP is 6.00 × 10 5 × 6.31447 × 298 1/2 J × 1. Heavy molecules travel more slowly on average than light molecules do (at the same temperature).3 we can calculate that the mean free path of O2 molecules in a sample of oxygen at SATP (25°C. Nevertheless.022 × 10 23 × 0. the separation at which they are regarded as being in contact: Condition for perfect-gas behaviour: λ >> d As a result of this large average separation. we see that the mean free path decreases as the pressure increases.2 × 1010 s−1. At relatively large separations (a few molecular diameters).2 × 109 s−1. a perfect gas is a gas in which the only contribution to the energy comes from the kinetic energy of the motion of the molecules and there is no contribution to the total energy from the potential energy arising from the interaction of the molecules with one another. molecules attract each other. and at the same pressure and temperature its mean free path is four times shorter. 1 bar) is R T –1 Because eqn 1. the mean free path is shorter for molecules with large collision cross-sections. This repulsion is responsible for the fact that liquids and solids have a deﬁnite bulk and do not collapse to an inﬁnitesimal point. For example. the collision frequency is 6. in which the average separation of the molecules is so great that they move independently of one another.REAL GASES 29 A brief illustration From the information in Table 1.40 × 10 –18 Pa m2 Pa m3 Pa m2 Real gases So far.9 Molecular interactions There are two types of contribution to the interaction between molecules. so they collide with other molecules less frequently.21 nm2). so each molecule travels a shorter distance before it collides with a neighbour.00 × 10 Pa) p 2 5 = 2 8. In terms of the quantities introduced in the previous section.2 × 109 s−1.3 × 10–8 m = 73 nm 10–9 m = 1 nm We have used R in one of its SI unit forms: this form is usually appropriate in calculations based on the kinetic model. the collision frequency increases with the pressure of the gas.31447 J K 2 1/2 mol ) × (298 K) –18 –1 × (6.

13 The experimental isotherms of carbon dioxide at several temperatures. 1. The subsequent reduction in volume. High positive potential energy (at very small separations) indicates that the interactions between them are strongly repulsive at these distances. In terms of intermolecular interactions.04°C (304. for instance). It might be diAcult to make out the surface because the remaining gas is at such a high pressure that its density is similar to that of the liquid. p/atm 0 100 Critical point 80 60 F * E D C 31. the energy-lowering interactions are dominant. the attractive interactions dominate. they make a negative contribution to the potential energy. particularly at high pressures and low temperatures when the interactions are most important. As the sample is compressed to B by pressing in a piston. Although the experimental isotherms resemble the perfect-gas isotherms at high temperatures (and at low pressures.30 CHAPTER 1: THE PROPERTIES OF GASES 140 50°C 120 40°C Potential energy Pressure. but at short distances the energy-raising repulsions dominate.1. 1. and hence trying to overcome the strong repulsive interactions between them. if we could observe the sample we would see it begin to condense to a liquid at C. from E to F. They should be compared with the perfect-gas isotherms shown in Fig.6 Fig. the pressure increases broadly in agreement with Boyle’s law. the piston is resting on the surface of the liquid. a liquid forms.12 The variation of the potential energy of two molecules with their separation. 1. Vm/(dm3 mol–1) 0. At large separations (on the right) the potential energy is zero and there is no interaction between the molecules. repulsions make a positive contribution to the total energy as the molecules squash together. At the special temperature of 31. 1.4 Molar volume. If we could look inside the container at point D. their equations of state. At large separations.13. let’s begin with the isotherm at 20°C.12 illustrates the general form of the variation of the intermolecular potential energy. 0. there are very striking differences between the two at temperatures below about 50°C and at pressures above about 1 bar. Figure 1. The reduction in volume from E to F requires a very large increase in pressure. This variation of pressure with volume is exactly what we expect if the gas at C condenses to a compact liquid at E. the step from C to E corresponds to the molecules being so close on average that they attract each other and cohere into a liquid. the isotherms of real gases have shapes that differ from those implied by Boyle’s law. off the scale on the right of the graph). At intermediate separations. through D to E. At E. Figure 1. Beyond this point. and the increase continues until the sample reaches point C.04°C. where the potential energy is negative. The step from E to F represents the effect of trying to force the molecules even closer together when they are already in contact.19 K) the gaseous state of carbon dioxide appears to transform continuously into the condensed state and at no stage is there .13 shows a set of experimental isotherms for carbon dioxide. in particular. At a slightly higher temperature (at 30°C.04°C (Tc) 20°C B A 0°C 40 20 0 0 Repulsions dominant Attractions dominant Separation Fig. At point A the sample of carbon dioxide is a gas. and the condensation would be complete when the piston was pushed in to E.2 0.10 The critical temperature To understand the signiﬁcance of the isotherms in Fig. we would see a liquid separated from the remaining gas by a sharp surface (Fig. Because attractions correspond to a lowering of total energy as molecules get closer together. For example.14). 1. we ﬁnd that the piston can be pushed in without any further increase in pressure. but a higher pressure is needed to produce it. Indeed. The critical isotherm is at 31. corresponds to the very high pressure needed to compress a liquid into a smaller volume. Molecular interactions affect the bulk properties of a gas and. 1. On the other hand.

Ne Argon. and Tc are the critical constants of a substance. It is an example of a supercritical ﬂuid. Tc. of the substance. Because supercritical carbon dioxide is obtained either from the atmosphere or from renewable organic sources (by fermentation). The critical temperature is sometimes used to distinguish the terms ‘vapour’ and ‘gas’: a vapour is the gaseous phase of a substance below its critical temperature (and which can therefore be liqueﬁed by compression). This disappearance occurs at the critical temperature.4 The critical temperatures of gases Critical temperature/°C Noble gases Helium. Figure 1. C6H6 Methane. Supercritical ﬂuids are also currently of great interest in industrial processes. and can act as a solvent. H2O Organic compounds Benzene. There comes a stage at which the two densities are equal and the interface between the two fluids disappears. He Neon. and at all higher temperatures. The container needs to be strong: the critical temperature of water is at 373°C and the vapour pressure is then 218 atm. the critical point of the gas.19 K for carbon dioxide but varies from substance to substance). the gaseous phase of water at room temperature is a vapour. a visible surface between the two states of matter. At this temperature (which is 304. a gas is the gaseous phase of a substance above its critical temperature (and that cannot therefore be liqueﬁed by compression alone). CO2 Hydrogen. but it behaves like a liquid in many respects—it has a density similar to that of a liquid. pc. Br2 Small inorganic molecules Ammonia. H2 Nitrogen. Oxygen at room temperature is therefore a true gas. pc. However. The pressure and molar volume at the critical point are called the critical pressure. Xe Halogens Chlorine. a single form of matter ﬁlls the container at all stages of the compression and there is no separation of a liquid from the gas.4 lists the critical temperatures of some common gases. Kr Xenon. for instance. Collectively. supercritical carbon dioxide is used to extract caffeine in the manufacture of decaffeinated coffee where. the volumes at each end of the horizontal part of the isotherm have merged to a single point. the ﬂuid is not strictly a liquid because it never possesses a surface that separates it from a vapour phase. The dense ﬂuid obtained by compressing a gas when its temperature is higher than its critical temperature is not a true liquid. it does not result in the formation of an unpleasant and possibly toxic residue.14 also shows that in the critical isotherm. The data there imply.2 K) −229 −123 −64 17 Increasing temperature Fig. Nor is it much like a gas. unlike organic solvents. Cl2 Bromine. CH4 Tetrachloromethane. because it is so dense. Table 1. called the critical temperature. the density of the vapour phase increases and that of the liquid phase decreases. as they can be used instead of chloroﬂuorocarbons (CFC) and hence avoid the environmental damage that CFCs are known to cause. O2 Water. . For example. despite its density. Vc. that liquid nitrogen cannot be formed by the application of pressure unless the temperature is below 126 K (−147°C). Ar Krypton. Vc.REAL GASES 31 Table 1. NH3 Carbon dioxide. Supercritical ﬂuids (SCF) are currently being used as solvents. 1. CCl4 289 −83 283 132 31 −240 −147 −118 374 144 311 −268 (5. and critical molar volume.14 When a liquid is heated in a sealed container. as depicted here by the changing density of shading. for example. the isotherm at the critical temperature. We have to conclude that a gas cannot be condensed to a liquid by the application of pressure unless the temperature is below the critical temperature. its use does not increase the net load of atmospheric carbon dioxide. N2 Oxygen.

and for some gases (hydrogen in the illustration) Z > 1 at all pressures. The compression factor rises above 1 at high pressures 2 H2 1 Perfect gas CH4 C2H4 NH3 0 0 200 400 Pressure. Z = 1. The type of behaviour exhibited depends on the temperature. so we can rewrite this deﬁnition as Definition whatever the identity of the gas... and so on. and it reﬂects the fact that intermolecular forces are now signiﬁcant.20a) The molar volume of a perfect gas is RT/p (recall eqn 1. for real gases. B3. and ammonia. From the graphs in Fig. vary from gas to gas and depend on the temperature.11 The compression factor A useful quantity for discussing the properties of real gases is the compression factor. To do so. all the other gases show negative deviations initially but positive deviations at high pressures. This behaviour indicates that the repulsive forces are dominant. etc. This technique.20b) 1. so deviations of Z from 1 are a measure of how far a real gas departs from behaving perfectly.21) where Vm is the molar volume of the gas we are studying.21 becomes greater than 1.15. and write instead Z = 1+ B C + 2 + . The limiting expression is the ﬁrst approximation to the true expression. it is found to vary with pressure as shown in Fig. C. ethane. with pressure for several gases at 0°C. for instance) have Z < 1. Z. For hydrogen. The coeAcients B. so the molecules are pushed apart slightly. Z..15. When Z is measured for real gases. The negative deviations are a result of the attractive interactions between molecules and the positive deviations are a result of the repulsive interactions. That is. is quite common in physical chemistry. The observation that Z > 1 tells us that the molar volume of the gas is now greater than that expected for a perfect gas of the same temperature and pressure..15. which are also denoted B2. regardless of the sign of B. . C. The most important additional term on the right in eqn 1. whatever that may be. in place of B. 1. 1. hydrogen shows positive deviations at all pressures (at this temperature). The word ‘virial’ comes from the Latin word for force.32 CHAPTER 1: THE PROPERTIES OF GASES 1.15 The variation of the compression factor. are called virial coeGcients. The values of the virial coeAcients for many gases are known from measurements of Z over a range of Compression factor. p/atm 600 800 Fig. Z = 1. and ammonia (so that for them Z < 1). 2 the positive term C/V m becomes large for highly 2 compressed gases (when V m is very small) and the right-hand side of eqn 1. 1. Of the gases shown. some gases (methane. ethane. the attractive interactions are so weak that the repulsive interactions dominate even at low pressures. for the temperature to which the data apply. the attractive interactions are dominant. of taking a limiting expression (in this case. Z= Vm Vm pVm = = o V m RT/p RT V o = RT/p m (1. their molar volumes are smaller than that of a perfect gas. The virial coeAcients. we suppose that. C. and the additional terms progressively take into account the secondary effects that the limiting expression ignores. it follows that. etc. just as in the curves for the other gases in Fig.12 The virial equation of state We can use the deviation of Z from its ‘perfect’ value of 1 to construct an empirical (observation-based) equation of state. the third. which is the ratio of the actual molar volume of a gas to the molar volume of a perfect gas under the same conditions: Z= Vm o Vm Molar volume of the gas Molar volume of a perfect gas (1. B must be positive for hydrogen (so that Z > 1) but negative for methane. which applies to gases at very large molar volumes) and supposing that it is the ﬁrst term of a more complicated expression.21 is the one proportional to B (because under 2 2 most conditions C/V m << B/Vm and C/V m can be neglected).. suggesting that the molecules are pulled together slightly. At low pressures. For a perfect gas. However. Vm V m (1. the unwritten A = 1 is the ﬁrst. Z . 1.3). B is the second virial coeAcient.. A perfect gas has Z = 1 at all pressures. the relation Z = 1 is only the ﬁrst term of a lengthier expression. We can conclude that for these molecules and these conditions.

1). (This slowing does not mean that the gas is cooler close to the walls: the simple relation between T and mean speed in eqn 1. n/V. It is always a good plan to verify that an equation reduces to a known form when a plausible physical approximation is made. We can model the effect by supposing that the attraction experienced by a given molecule is proportional to the concentration. is only an approximate equation of state but it has the advantage of showing how the intermolecular interactions contribute to the deviations of a gas from the perfect gas law. so b ≈ 4VmoleculeNA. the perfect gas equation of state changes from p = nRT/V to p= nRT V − nb This equation of state—it is not yet the full van der Waals equation—should describe a gas in which repulsions are important. RT Vm V m We then multiply both sides by RT/Vm we obtain p= RT Vm ⎛ ⎞ B C + 2 + . the equation of state approaches that of a perfect gas. of molecules in the container. Figure 1.21 into an equation of state. 3 Therefore.⎟ ⎜1 + ⎜ ⎟ Vm V m ⎝ ⎠ r 2r Excluded volume Fig. We can view the van der Waals equation as another example of taking a soundly based qualitative idea and building up a mathematical expression that can be tested quantitatively.16). Equation 1. When the molar volume is very large.. which gives pVm B C = 1+ + 2 + .22 is the virial equation of state. volumeexcluding forces by changing V in the perfect gas equation to V − nb. the molecules strike the walls less frequently and strike it with a weaker impact. The effect of the attractive interactions between molecules is to reduce the pressure that the gas exerts. 1.1 (1. or 3 3 8Vmolecule. Note that when the pressure is low. the centre of one of them 3 cannot penetrate into a sphere of radius 2r and therefore volume 8Vmol surrounding the other molecule.⎞ + 2 + ⎟ ⎜1 + ⎜ ⎟ V V ⎝ ⎠ Derivation 1. the terms B/Vm and 2 C/V m are both very small. Therefore. and T: p= nRT V ⎛ nB n2C . The nb can then be ignored in the denominator and the equation reduces to the perfect gas equation of state. We can therefore model the effect of the repulsive. The volume excluded per molecule is one-half this volume. 1. the actual volume in which the molecules can travel is reduced to an extent proportional to the number of molecules present and the volume they each exclude (Fig. Next. To convert eqn 1. we combine it with eqn 1. instead of being free to travel anywhere in a volume V... The repulsive interaction between two molecules implies that they cannot come closer than a certain distance. and only the 1 inside the parentheses survives.20b (Z = pVm /RT ). the virial equation does not give us much immediate insight into the behaviour of gases and their condensation to liquids.21 by varying the coeAcients until a good match is obtained.16 When two molecules. In this limit..22) The molar volume of a gas described by the van der Waals equation The volume of a sphere of radius R is 4 pR 3.. and volume Vmolecule = 4 pr 3. is 2r. or 4Vmolecule.15 . the volume is large compared with the volume excluded by the molecules (which we write V >> nb).16 3 shows that the closest distance of two hard-sphere molecules of radius r. Because the attractions slow the molecules down.. the excluded volume is 4 p(2r)3 = 8 × (4 pr 3). So far. which was proposed in 1873 by the Dutch physicist Johannes van der Waals.REAL GASES 33 molar volumes and using mathematical software to ﬁt the data to eqn 1. V. we replace Vm by V/n throughout to get p as a function of n. 1.13 The van der Waals equation of state Although it is the most reliable equation of state. each of radius r and volume Vmol = 4 pr 3 approach each other. where b is the proportionality constant between the reduction in volume and the amount of molecules present in the container (see Derivation 1. The van der Waals equation.

N2 Oxygen.5 were found by ﬁtting the calculated curves to experimental isotherms. are unrealistic because they suggest that under some conditions compression results in a decrease of pressure.16 .137 b/(10−2 dm3 mol−1) 0.23a) This expression is the van der Waals equation of state.82 2.610 5.29 6.17. the molar volume is so large that V − nb can be replaced by V. The loops are therefore trimmed away and replaced by horizontal lines (Fig.5).4 4. C2H4 Helium. one factor of n/V reﬂecting the reduction in frequency of collisions and the other factor the reduction in the strength of their impulse.337 3. The derivation also has the advantage of keeping imprecise the signiﬁcance of the van der Waals parameters.23a is sometimes rearranged by bringing the term proportional to a to the left and multiplying throughout by V − nb: ⎛ an2 ⎞ ⎜ p + 2 ⎟ (V − nb) = nRT ⎜ V ⎟ ⎠ ⎝ (1.2. Apart from the waves below the critical temperature they do resemble experimental isotherms quite well. 1.23b) We have built the van der Waals equation by using physical arguments about the volumes of molecules and the effects of forces between them.65 3. but the present method has the advantage of showing how to derive the form of an equation out of general ideas.18).38 2. CO2 Ethane. and as shown in Derivation 1.5 van der Waals parameters of gases Substance Air Ammonia. Ar Carbon dioxide.23a greatly exceeds the second. To show the resemblance of this equation to the perfect gas equation pV = nRT. with the experimental isotherms already shown in Fig. The van der Waals parameters depend on the gas. H2 Nitrogen.71 3. the constants a and b: they are much better regarded as empirical parameters than as precisely deﬁned molecular properties. which are shown in Fig. eqn 1. If the constant of proportionality is written a. we need to note that when the temperature is high. The van der Waals parameters in Table 1. Furthermore. First. He Hydrogen.2420 1. O2 Xenon. 1.20 4. We can judge the reliability of the van der Waals equation by comparing the isotherms it predicts. whereas b (the parameter representing the role of repulsions) can be expected to be large when the molecules are large.225 1. To conﬁrm this remark.364 4. eqn 1.51 5.23a reduces to p = nRT/V. Two important features of the van der Waals equation should be noted. Xe a/(atm dm6 mol−2) 1. under these conditions (of high temperature and low pressure). Second. NH3 Argon. which are called van der Waals’ loops. the critical constants are related to the van der Waals coeAcients as follows: Table 1. the perfect gas equation.19 5.552 0.507 4. It follows from the way we have constructed the equation that a (the parameter representing the role of attractions) can be expected to be large when the molecules attract each other strongly. but are taken as independent of temperature (Table 1.13. C2H6 Ethene. RT may be so large that the ﬁrst term on the right in eqn 1. 1. at low pressures. we can write ⎛ n⎞ Reduction in pressure = a × ⎜ ⎟ ⎝V ⎠ 2 It follows that the equation of state allowing for both repulsions and attractions is p= ⎛ n⎞ nRT −a⎜ ⎟ V − nb ⎝V ⎠ 2 (1.039 3. so the latter may be ignored. It can be derived in other ways.0341 0.87 3. The waves. perfect-gas isotherms are obtained from the van der Waals equation at high temperatures and low pressures. Hence.34 CHAPTER 1: THE PROPERTIES OF GASES is valid only in the absence of intermolecular forces.) We can therefore expect the reduction in pressure to be proportional to the square of the molar concentration.352 1.

interActivity (a) Show that the van der Waals equa2 tion may be written as p = RT/(Vm − b) − a /V m.5 1. and each one passes through a minimum followed by a maximum. First. . we find the expression for pc given there too.8 0 0. Reduced pressure. The axes are labelled with the ‘reduced pressure’.23a as p= RT a − 2 Vm − b V m 1 0.24) The ﬁrst of these relations shows that the critical volume is about three times the volume occupied by the molecules themselves.2 1. the calculated isotherms oscillate. For gases with very low boiling points (such as oxygen and nitrogen. chlorine at 1 atm can be liqueﬁed by cooling it to below −34°C in a bath cooled with dry ice (solid carbon dioxide). For example. at −183°C and −186°C.5 Reduced pressure. V/Vc 10 Fig. (c) Calculate the percentage difference between the value you calculated in part (b) and the value predicted by the perfect gas equation. we use Vm = V/n to write eqn 1.1 1 Reduced volume. the isotherms strongly resemble the observed isotherms.17 that. The isotherm labelled 1 is the critical isotherm (the isotherm at the critical temperature). V/Vc.17 Isotherms calculated by using the van der Waals equation of state.5 0. at the critical point the curve has a flat inflexion (1).5 The first and second derivatives of p with respect to Vm are. we know that an inflexion of this type occurs when both the first and second derivatives are zero. The individual isotherms are labelled with the ‘reduced temperature’. such a simple technique is not practicable unless an even colder bath is available. and both derivatives are equal to zero: − RTc 2a + 3 =0 (Vc − b)2 V c 2RTc 6a − 4 =0 (Vc − b)3 V c Solving this pair of equations gives (as you should verify) the expressions for Vc and Tc in eqn 1.15). p/pc 1 Relating the critical constants to the van der Waals parameters We see from Fig. 1.18 The unphysical van der Waals loops are eliminated by drawing straight lines that divide the loops into areas of equal size. where pc = a /27b 2 and Vc = 3b.1 1 Reduced volume. Vm = Vc. where Tc = 8a/27Rb. (b) Use your result to show that the van der Waals equation may 3 2 also be written as V m − (b + RT/p)V m + (a/p)Vm − ab/p = 0. T/Tc. If the speed of the molecules can be 0 0. 1. p/pc 1 0. Vc = 3b Tc = 8a 27Rb pc = a 27b2 (1. From the properties of curves. We saw earlier that the rms speed of molecules in a gas is proportional to the square root of the temperature (eqn 1. for T < Tc. One alternative and widely used commercial technique makes use of the forces that act between molecules.14 The liquefaction of gases A gas may be liqueﬁed by cooling it below its boiling point at the pressure of the experiment. 1. It follows that reducing the rms speed of the molecules is equivalent to cooling the gas. and ‘reduced volume’. respectively).24. These extrema converge as T → Tc and coincide at T = Tc.5 Derivation 1. V/Vc 10 Fig.REAL GASES 35 1. Hence. With this procedure. (c) Calculate the molar volume of carbon dioxide gas at 500 K and 150 kPa by using mathematical software to find the physically acceptable roots of the equation from part (b). p/pc. we can find the critical temperature by calculating these derivatives and setting them equal to zero. 1. respectively: dp RT 2a =− + 3 dVm (Vm − b)2 V m d2p 2RT 6a = − 4 2 dV m (Vm − b)3 V m At the critical point T = Tc. When they are inserted in the van der Waals equation itself.

It is very easy to move molecules apart from each other: we simply allow the gas to expand. 1. The procedure works only for real gases in which the attractive interactions are dominant. the Joule– Thomson effect results in the gas becoming warmer. 1. the gas is now cooler than before the expansion. 1 An equation of state is an equation relating pressure. 8 Diffusion is the spreading of one substance through another. 1. . then they should slow. like a ball rising from a planet. and amount of a substance. The expanding gas cools still further. but the effect is the same). In practice. the molecules move apart to ﬁll the available volume. As it does so.8 and 1. 3 Dalton’s law states that the total pressure of a mixture of perfect gases is the sum of the pressures that each gas would exert if it were alone in the container at the same temperature. Checklist of key ideas You should now be familiar with the following concepts. This process of cooling a real gas by expansion through a narrow opening called a ‘throttle’ is called the Joule–Thomson effect. After several successive expansions. To slow the gas molecules. The gas is recirculated and cools the gas that is about to undergo expansion through the throttle. 7 The properties of the Maxwell distribution of speeds are summarized in Figs. struggling as they do so against the attraction of their neighbours. Charles’ law (V ∝ T ). which increases the average separation of the molecules. and Avogadro’s principle (V ∝ n). Kelvin). To cool a gas. then the cooled gas will condense to a liquid. Eventually. Because some kinetic energy must be converted into potential energy to reach greater separations. 5 The kinetic model of gases expresses the properties of a perfect gas in terms of a collection of mass points in ceaseless random motion. effusion is the escape of a gas through a small hole. Therefore. 4 The partial pressure of any gas is defined as pJ = xJp. the latter is cooled further. For molecules under conditions when repulsions are dominant (corresponding to Z > 1). the molecules travel more slowly as their separation increases. we make use of an effect similar to that seen when a ball is thrown into the air: as it rises it slows in response to the gravitational attraction of the Earth and its kinetic energy is converted into potential energy. because the average speed of the molecules has been reduced. volume.9. Molecules attract each other. On each successive expansion the gas becomes cooler. and if we can cause them to move apart from each other. therefore. 6 The mean speed and root-mean-square speed of molecules is proportional to the square root of the (absolute) temperature and inversely proportional to the square root of the molar mass. 10 The Joule–Thomson effect is the cooling of gas that occurs when it expands through a throttle without the influx of heat. and as it ﬂows past the incoming gas. 9 Graham’s law states that the rate of effusion is inversely proportional to the square root of the molar mass. liquefied gas drips from the throttle.19).19 The principle of the Linde refrigerator. where xJ is its mole fraction in a mixture and p is the total pressure. because the molecules have to climb apart against the attractive force in order for them to travel more slowly. the gas is allowed to expand several times by recirculating it through a device called a Linde refrigerator (Fig. the gas becomes so cold that it condenses to a liquid. 2 The perfect-gas equation of state is based on Boyle’s law (p ∝ 1/V ). we allow it to expand without allowing any heat to enter from outside. temperature.36 CHAPTER 1: THE PROPERTIES OF GASES reduced to the point that neighbours can capture each other by their intermolecular attractions. The effect was ﬁrst observed and analysed by James Joule (whose name is commemorated in the unit of energy) and William Thomson (who later became Lord Cold gas Heat exchanger Throttle Compressor Liquid Fig. as we have seen (the attraction is not gravitational.

y-. The x-component of the momentum therefore changes by 2m| vx | on each collision (the y. So we begin with a brief review of velocity. as it takes the concepts set out in the text and turns them into precise expressions. we need to calculate that number.1 37 Table of key equations The following table summarizes the equations that have been developed in this chapter. v. testable.) c = lz p = nRT/(V − nb) − a(n/V )2 ⎛ M ⎞ F (s) = 4p ⎜ ⎜ 2pRT ⎟ ⎟ ⎝ ⎠ 3/2 Comment A limiting law for real gases as p → 0 Definition Perfect gas (kinetic model) a: attractive effects b: repulsive effects 2 / 2RT Maxwell distribution of speeds s 2 e−Ms Perfect gas (kinetic model) Further information 1. in this case a swarm of mass points in ceaseless random motion. Next.|... Now we begin the derivation of eqn 1. v. Many molecules collide with the wall in an interval Δt.. For example.and z-components are unchanged). The velocity. right and is reﬂected. are the components of the vector along the x-. 1. respectively (Fig.20). the change of momentum divided by the interval during which that change occurs. speed. When a particle of mass m that is travelling with a component of velocity vx parallel to the x-axis (vx > 0 corresponding to motion to the right and vx < 0 to motion to the left) collides with the wall on the vz v vx vy Fig. and z-axes. p = (nRT/V )(1 + nB /V + n 2C /V 2 + . Property Perfect gas law Partial pressure Dalton’s law Virial equation of state Mean free path.21. is a vector. then all the particles in a volume A × | vx |Δt will reach the . but each one is motivated by a clear appreciation of the underlying physical picture.FURTHER INFORMATION 1. its value without a sign.1 Kinetic molecular theory One of the essential skills of a physical chemist is the ability to turn simple... all the molecules within a distance |vx |Δt of the wall will strike it if they are travelling towards it. momentum. qualitative ideas into rigid. It follows that if the wall has area A. is denoted |. 1.. of a particle of mass m is the vector p = mv with magnitude p = mv. and collision frequency van der Waals equation of state Equation pV = nRT pJ = xJp p = pA + p B + . Because a molecule with velocity component vx can travel a distance | vx | Δt along the x-axis in an interval Δt.20 A vector v and its three components on a set of perpendicular axes. The key quantitative ingredients we need are the equations of classical mechanics. and y vz. its linear momentum changes from +m| vx | before the collision to −m|vx | after the collision (when it is travelling in the opposite direction at the same speed). As usual in model building.9 by considering the arrangement in Fig. and the total change of momentum is the product of the change in momentum of each molecule multiplied by the number of molecules that reach the wall during the interval. The linear momentum. Newton’s second law of motion states that the force acting on a particle is equal to the rate of change of the momentum. there are a number of steps. a quantity with both magnitude and direction. The kinetic model of gases is an excellent example of this technique. vy. The magnitude of each component. The magnitude of the velocity vector is 2 2 the speed. where vx. quantitative theories. p. and Newton’s second law of motion. |vx | means the magnitude of vx. given by v = (v x + v 2 + v z )1/2. 1.

3 Use the kinetic model of gases to explain why light gases.2 A sample of neon of mass 425 mg occupies 6. is nNA/V (where n is the total amount in moles of molecules in the container of volume V and NA is Avogadro’s constant). Here.5 Explain how the compression factor varies with pressure and temperature and describe how it reveals information about intermolecular interactions in real gases..0 cm3. c. 1. such as O2. because the molecules are moving randomly. is deﬁned as c = 〈v 2 〉1/2 (eqn 1.. At 14. and N2 are abundant. half the particles are moving to the right and half are moving to the left.10). What amount (in moles) of NO has been collected? . the force divided by the area.8 Describe the Joule–Thomson effect and its application to the liquefaction of gases.5 kPa. A | vx|Δt Number of impacts in the interval Dt Momentum change on each impact Momentum change = Will Won’t nN A A | vx | Δt × 2m | vx | 2V 2 2 nmAN A vx Δt nMAv x Δt = V V = M = mNA Next. The number density. for clarity. It follows that c2 = 3〈vx 〉.38 CHAPTER 1: THE PROPERTIES OF GASES Area. Force = 2 2 Change of momentum nMAvx Δt / V nMAvx = = Δt V Time interval It follows that the pressure. nitrogen monoxide (NO) has been found to act as a neurotransmitter. 2 The total momentum change in the interval Δt is the product of the number we have just calculated and the change 2m| vx |: To write an expression of the pressure in terms of the root mean square speed. the average number of collisions with the wall during the interval Δt is 1 nNAA|vx | Δt/V. a sample was collected in a container of volume 300. as v 2 = v x + v 2 + v z . 1. we calculate the rate of change of momentum: x Fig.5°C its pressure is found to be 34. v. p.6 What is the significance of the critical constants? 1.4 Provide a molecular interpretation for the variation of the rates of diffusion and effusion of gases with temperature.055 g in a container of volume 3. Therefore. and Avogadro led to the formulation of the perfect gas equation of state. At any instant. we begin by writing the speed of a 2 2 single molecule. CO2.1 Explain how the experiments of Boyle. c.1 What pressure is exerted by a sample of nitrogen gas of mass 3.3 Much to everyone’s surprise. so the detected pressure. so the number of molecules in the volume A|vx | Δt is (nNA/V) × A|vx | Δt. are rare in the Earth’s atmosphere but heavier gases. What pressure does it exert? 1. Because the rooty mean-square speed. to ﬁnd the force.9 now follows by substituting 〈v x 〉 = 3 c into 2 p = nM〈vx 〉/V. such as H2 and He. 1. Charles.2 Explain the term ‘partial pressure’ and why Dalton’s law is a limiting law. 1. All molecules within the shaded area will reach the wall in an interval Dt provided they are moving towards it. 1. is Pressure = 2 2 nMAvx / V nMvx = A V Not all the molecules travel with the same velocity. 1.00 dm3 at 32°C? 1.21 The model used for calculating the pressure of a perfect gas according to the kinetic molecular theory. 1. all 2 three averages are the same. To prepare to study its effect. is the average (denoted 〈.00 dm3 at 77 K. 1 2 2 Equation 1.7 Describe the formulation of the van der Waals equation of state. 1. we show only the x-component of the velocity (the other two components are not changed when the molecule collides with the wall). the number of particles divided by the total volume. Questions and exercises Discussion questions 1.〉) of the quantity just calculated: p= 2 nM 〈vx 〉 V wall (if they are travelling towards it). Exercises Treat all gases as perfect unless instructed otherwise. it follows that 2 2 2 c 2 = 〈v 2 〉 = 〈v x 〉 + 〈v y 〉 + 〈v z 〉 However.

we have to carry it with us to inhospitable places.0 dm3 of argon under the same conditions as in Exercise 1. (c) 1.29 How does the mean free path in a sample of a gas vary with temperature in a constant-volume container? . What is the molar mass of the compound? 1. 1. what volume of gas is emitted? 1. The gas in an aerosol container exerts a pressure of 125 kPa at 18°C. (iii) 1500 K.0 atm. The latter depends on how far a molecule can travel before colliding with another molecule. If this gas is emitted at 800°C and 1.0°C.2 kPa. −5.5 kPa.0 mol N2 at 273. (b) the root-mean-square speeds of the molecules.27 How many collisions per second does an N2 molecule make at an altitude of 20 km? (See Exercise 1. and do so in compressed form in tanks.15 K.19 A vessel of volume 22.21 dm3. In 1782. Calculate the mean free path of diatomic molecules in air using s = 0. Calculate the final pressure of the gas. To what temperature should you heat a sample of air. What is the pressure of gas in the cylinder at 20°C? 1. The pressure was 152 Torr at 298 K and the mass of the gas was 33.0 s when the temperature is 25°C and the pressure is (a) 10 bar. and 225 mg of nitrogen.23 g dm−3 at 330 K and 25. 1.24 When we are studying the photochemical processes that can occur in the upper atmosphere.36 nm2. What is the volume of the air space when the bell has been lowered to a depth of 50 m? Take the mean density of sea water to be 1. 1.24 for data.0 dm3 that contains it? Take s = 0.43 nm2.00 dm3 at 25°C and 1.00 dm3 to 100 cm3? 1.0 m3. What is the mean free path of N2 molecules? Take s = 0.74 kg when empty. where the pressure was 104 kPa and the temperature 21. What is the pressure at this temperature? 1.6 You are warned not to dispose of pressurized cans by throwing them on to a fire. we need to know how often atoms and molecules collide.25 How many collisions does a single Ar atom make in 1.11 A diving bell has an air space of 3.25. 1.050 atm. 1.0 Pa? 1. 1.15 A gas mixture being used to simulate the atmosphere of another planet consists of 320 mg of methane.18 In an experiment to measure the molar mass of a gas. including humans.9 Hot-air balloons gain their lift from the lowering of density of air that occurs when the air in the envelope is heated. 250 cm3 of the gas was confined in a glass vessel.5 The effect of high pressure on organisms. 1.20 dm3 to 4. Calculate (a) their partial pressures and (b) the total pressure.43 nm2 at 25°C and (a) 10 bar.22 At what pressure does the mean free path of argon at 25°C become comparable to the diameter of a spherical vessel of volume 1. (b) 880 Pa. however. 1.0°C? 1. (b) 100 kPa. The partial pressure of nitrogen at 300 K is 15. neglecting the mass of the balloon? 1.0 dm3 glass bulb contains 1. initially at 315 K. and its temperature rises to 700°C. (ii) 315 K.8 To what temperature must a sample of helium gas be cooled from 22.0 m3 when on the deck of a boat. What is the mass density of hydrogen relative to air at the same temperature and pressure? What mass of payload can be lifted by 10 kg of hydrogen.1°C. The Kilauea volcano in Hawaii emits 200–300 t of SO2 per day.00 atm. what is (a) the temperature of the gas.4 dm3 contains 2. Jacques Charles used a hydrogen-filled balloon to fly from Paris 25 km into the French countryside.10 At sea level. is studied to gain information about deep-sea diving and anaesthesia.36 nm2.0 × 1023 H2 molecules. (c) Would the temperature be different if they were O2 molecules? 1. What pressure is needed to compress it to 100 cm3 at this temperature? 1.5 m when released at sea level at 20°C and expanded to a radius of 3.21 A 1.26 Calculate the total number of collisions per second in 1.12 Balloons were used to obtain much of the early information about the atmosphere and continue to be used today to obtain weather information. Volcanic eruptions can be a significant source of air pollution.20 Calculate the mean speed of (a) He atoms.2°C to reduce its volume from 1. If the pressure exerted by the gas is 100 kPa.0 mol H2 and 1.04 kg when full and 0.13 Atmospheric pollution is a problem that has received much attention. What is the pressure inside the balloon at that altitude? 1. is from industrial sources. What is the partial pressure of dry air in our lungs when the total pressure is 760 Torr? 1.7 Until we find an economical way of extracting oxygen from sea-water or lunar rocks. 1. At an altitude of 20 km the temperature is 217 K and the pressure is 0. −52. to increase its volume by 25 per cent? 1. A sample of oxygen at 101 kPa is compressed at constant temperature from 7. (b) CH4 molecules at (i) 79 K. 1.5 m when it had risen to its maximum altitude where the temperature was −25°C.28 The spread of pollutants through the atmosphere is governed partly by the effects of winds but also by the natural tendency of molecules to diffuse.14 A meteorological balloon had a radius of 1.23 At what pressure does the mean free path of argon at 25°C become comparable to 10 times the diameters of the atoms themselves? Take s = 0.QUESTIONS AND EXERCISES 39 1.16 The vapour pressure of water at blood temperature is 47 Torr. The density of a gaseous compound was found to be 1.5 mg.4 A domestic water-carbonating kit uses steel cylinders of carbon dioxide of volume 250 cm3. What is the molar mass of the gas? 1. To what volume will the region expand when it has risen to an altitude where the pressure and temperature are (a) 52 kPa. A sample of air occupies 1. Calculate (a) the volume and (b) the total pressure of the mixture. (c) 1. (b) 103 kPa.) 1. The container is thrown on a fire. a certain mass of air occupied 2.17 A determination of the density of a gas or vapour can provide a quick estimate of its molar mass even though for practical work mass spectrometry is far more precise. Not all pollution. 175 mg of argon.025 g cm−3 and assume that the temperature is the same as on the surface. They weigh 1.0 Pa.

However. and find expressions for the critical constants in terms of the van der Waals parameters. is zero for a van der Waals gas.30 Calculate the pressure exerted by 1.7 cm3 mol−1 and C = 1200 cm6 mol−2 for the virial coefficients at 273 K. 0 (b) Confirm that the root-mean-square speed of molecules of molar mass M at a temperature T is equal to (3RT/M )1/2 and hence confirm eqn 1.40 CHAPTER 1: THE PROPERTIES OF GASES 1. the temperature is 3. Its volume is found to be 5.15 J cm−3).15 K in 22. 1. Calculate the van der Waals parameters of the gas and estimate the radius of the molecules. Waals gas occurs where the isotherm has a flat inflexion. It may seem absurd. such as carbon.36 The critical constants of ethane are pc = 48.32 Express the van der Waals equation of state as a virial expansion in powers of 1/Vm and obtain expressions for B and C in terms of the parameters a and b.32.00 g of carbon dioxide confined to a container of volume 100 cm3 at 25. Hint: You will need an integral of the form ∞ 2 x 4e−ax dx = (3/8a 2)(p /a)1/2. and has a mass density of 1200 kg m−3. (b) Combine the result from part (a) with the expression for the pressure from kinetic model to show that the pressure of the plasma is related to its kinetic energy density rk = E k /V. Series expansions are discussed in Appendix 2.33 A certain gas obeys the van der Waals equation with a = 0. the particles making up the plasma have diameters comparable to those of nuclei. Vc = 148 cm3 mol−1. Using the language of calculus. 1. 0 (c) Find an expression for the most probable speed of molecules of molar mass M at a temperature T.. Assume that half-way to the centre a red giant has a temperature of 3500 K. From this information calculate the van der Waals constant b. the kinetic energy of the molecules in a region divided by the volume of the region.34 Measurements on argon gave B = −21. 2 which is where dp/dVm = 0 (zero slope) and d2p/dV m = 0 (zero curvature). The increased temperature results in an increase in the rates of nuclear reaction..31 How reliable is the perfect gas law in comparison with the van der Waals equation? Calculate the difference in pressure of 10. 1.23b. and calculate its value for carbon dioxide. for instance. (d) Estimate the fraction of N2 molecules at 500 K that have speeds in the range 290 to 300 m s−1.0°C between treating it as a perfect gas and a van der Waals gas. In the Sun. What is the pressure at this point? (e) If the red giant in part (d) consisted of neutral carbon atoms. What are the values of a and b in the corresponding van der Waals equation of state? 1. We can therefore use pV = nRT as the equation of state for the stellar interior. in which the electrons have been stripped from the atoms of hydrogen and helium that make up the bulk of the matter of stars. Hint. 1.20 g cm−3 (slightly higher than the density of water). Use the data in Table 1. which contracts and results in higher temperatures. and Tc = 305. B. we have to realize that the state of matter is that of a plasma. as a consequence. (b) a van der Waals gas when it is confined under the following conditions: (i) at 273.39 The kinetic model of gases is valid when the size of the particles is negligible compared with their mean free path. the density is 150 times that of liquid water at its centre and comparable to that of water about half-way to its surface. to be applicable to the dense matter of stellar interiors.20 atm. Hint: Use the expression for B derived in Exercise 1.38‡ Here we explore the van der Waals equation of state. (d) A star eventually depletes some of the hydrogen in its core. What is the compression factor for this gas at the prevailing temperature and pressure? 1. (a) Calculate the pressure half-way to the centre of the Sun.. a mean free path of only 0. 8 1. Hint: You will need an integral of the ∞ 2 form x 3e−ax dx = n!/2a 2.13. and the mass density is 1.1 pm satisfies the criterion for the validity of the kinetic model and the perfect gas law. 1. The expansion you will need is (1 − x)−1 = 1 + x + x 2 + .35 Show that there is a temperature at which the second virial coefficient. the critical point of a van der . 1. or about 10 fm.5 × 105 J m−3 (corresponding to 0.00 × 10− 4 m3 mol−1 at 273 K and 3.0 MPa. Therefore. assuming that the interior consists of ionized hydrogen atoms. (b) Show that the value of the compression factor at the critical point is 3. The outer part of the star expands and cools to produce a red giant.4 K. (a) Confirm that the mean speed of molecules of molar mass M at a temperature T is equal to (8RT/pM )1/2. some of which result in the formation of heavier nuclei.414 dm3. is composed primarily of fully ionized carbon atoms and electrons.50 m6 Pa mol−2. to expect the kinetic theory and.6 MK.5. the perfect gas law. (a) Evaluate these two expressions using eqn 1. by p = 2 rk 3 (c) What is the kinetic energy density half-way to the centre of the Sun? Compare your result with the (translational) kinetic energy density of the Earth’s atmosphere on a warm day (25°C): 1. Hint: Look for a maximum in the Maxwell distribution (the maximum occurs as dF/ds = 0). what would be the pressure at the same point under the same conditions? Projects The symbol ‡ indicates that calculus is required.0 mol C2H6 behaving as (a) a perfect gas. As a result. therefore.37‡ In the following exercises you will explore the Maxwell distribution of speeds in more detail. (ii) at 1000 K in 100 cm3.