1 Behaviour of Gases

CHAPTER OBJECTIVES
1.1 Introduction 1.2 Gas Laws 1.3 Kinetic Theory of Gases 1.4 Derivation of Kinetic Gas Equation 1.5 Derivation of Gas Laws from Kinetic Equation 1.6 Ideal and Real Gases 1.7 Deviations of Real Gases from Gas Laws 1.8 Causes of the Derivations from Ideal Behaviour 1.9 van der Waals Equation (Reduced Equation of State) (Equation of State for Real Gases) 1.10 Explanation of Behaviour of Real Gases on the Basis of van der Waals Equation 1.11 Isotherms of Carbon Dioxide-Critical Phenomenon 1.12 Principle of Continuity of States 1.13 Critical Constants 1.14 Law of Corresponding States 1.15 Limitations of van der Waals Equation

A vacuum is nothing and what is nothing cannot exist Thomas Hobbes

As the pressure increased, the volume of the gas decreased. Robert Boyle

1.1 INTRODUCTION
All matter exists in one of the three states of aggregation: solids, liquids or gases. A solid has definite shape and volume due to strong intermolecular attractive forces. A substance will be a solid if it melts at a temperature higher than room temperature under atmospheric pressure. In the liquid state, the attractive forces are relatively weak and it has a definite volume but no definite shape. A substance will be a liquid if its freezing point (i.e., melting point) is below the room temperature under atmospheric pressure. In the gaseous state, the molecular forces are much weaker. Hence, due to possible random motion in all directions, gases have no bounding surface and lend to fill completely any available space. The gases thus have neither definite shape nor definite volume. A substance will be a gas if its boiling point is below room temperature under atmospheric pressure. Out of the three states of matter, i.e., solid, liquid and gases in which the different substances exist, the gases show the most uniform behaviour irrespective of the nature of the gas. Some common properties of gases are given below:
i. ii. iii. iv. v. vi. They expand indefinitely and fill up the whole vessel in which they are placed. They can be compressed by the application of pressure. They can be liquefied by cooling and applying pressure. They possess low densities under ordinary conditions of temperature and pressure. They intermix spontaneously, i.e., they show the property of diffusion. They exert pressure on the walls of the vessel in which they are contained.

In addition to the above general properties of gases, another important feature of all gases is that they obey certain gas laws such as Boyles law and Charles law which are briefly outlines below. A gas which obeys the gas laws under all conditions of temperature and pressure is known as an ideal gas. However, gases deviate from behaviour especially at low temperature and high pressure. The concept of ideal gases is only hypothetical. Gases obey gas laws at high temperature and low pressure usually and are called real gases. In this chapter, we will discuss the deal gas behaviour in terms of kinetic theory of gases and also the deviation of real gases from ideal behaviour.

1.2 GAS LAWS

1.2.1 Boyles Law

This law was proposed by Robert Boyle in 1662 based on his experimental study of the variation of volume of a gas with change of pressure at constant temperature. The law states as follow: Temperature remaining constant, the volume of a given mass of a gas is inversely proportional to its pressure. Mathematically, if V is the volume of a gas at pressure P, then

In other words, if at constant temperature, V1 is the volume of a gas at pressure P1 and on changing the pressure to P2, the volume changes to V2, then P1 V1 = P2 V2

1.2.2 Charles Law

Charles in 1787 observed that at constant pressure, the volume of every gas increased by the same amount when heated from 0 C to a particular temperature. Gay-Lussac in 1802 found the exact increase in volume for every degree rise of temperature. Based on their study, they put forward the following generalization. Pressure remaining constant, the volume of a given mass of a gas increases or decreases by 1/273 of its volume at 0 C for one degree rise or fall of temperature. Thus, if V0 is the volume of a gas at 0 C and Vt is the volume at t C, then mathematically, the law may be proposed as

This means that at 273 C, the volume of the gas is reduced to zero i.e., the gas ceases to exist; in fact, the gas gets liquefied. This temperature (273 C) at which the gas ceases to exist is called absolute zero. It is represented by 0 A or 0 K (K stands for kelvin. Kelvin is the SI unit of temperature. According to SI unit, it should be written without putting the symbol of degree i.e., we should write 0 K; 273 K etc.). Thus, 273C = 0 K or 0 C = 273 K

This means that to convert t C into K, we should add 273

Substituting 273 + t C = T K in Eq. (1.1), we get

This implies that

if pressure remains constant or simply VT if pressure constant pressure.

Thus, the Charles Gay-Lussacs law may also be defined as follows: Pressure remaining constant, the volume of a given mass of a gas is directly proportional to its absolute temperature Mathematically, the law may also written as: V T. (at constant pressure)

where V1, is the volume of the gas at pressure P1 and V2 is the volume at pressure P2. Absolute scale/Kelvin scale of temperature: Taking 273 C as 0 K, the scale of temperature obtained is called absolute scale or Kelvin scale. On this scale, the temperature in degrees kelvin is obtained by adding 273 to the temperature in degrees centigrade.

1.2.3 Avogadros Law

Avogadro, in 1811, put forward the following hypothesis. Under similar conditions of temperature and pressure, equal volumes of all gases contain the same number of molecules. In other words, if temperature and pressure are kept constant, the volume (V) of a gas is directly proportional to the number of molecules (N) present in the gas. Mathematically,

However, the number of molecules present in 1 mole of the substance (solid, liquid or gas) has been determined experimentally. It has been found that one mole of every gas (i.e., 22.4 litre at N.T.P.) contains 6.023 1023 molecules. This number is known as Avogadros number and is usually represented by N0.

Thus, what was originally known as hypothesis is now known as Avogadros law. Obviously, the number of moles (n) of a gas may be calculated as follows:

As N0 is a constant quantity, we can say that

Hence, the equation V N may also be written as

where n is the number of moles of the gas.

1.2.4 The Combined Gas Law Equation or the Gas Equation

The above three gas laws may be combined to give a general equation, called the gas equation. This may be done as follows: According to Boyles law

According to Charles law

According to Avogadros law

Combining Eqs (1.5), (1.6) and (1.7), we get

where R is constant of proportionality and is called gas constant.

This equation is known as gas equation (or more correctly, ideal gas equation), which will be explained later.

Standard Temperature and Pressure or Normal Temperature and Pressure (N.T.P.)

As discussed above, volume of a given mass of gas changes with temperature and pressure. Hence, to compare the volume of different gases, they have to be taken or converted to same condition of temperature and pressure using gas equation. The conditions most commonly chosen are P = 1 atm and T = 0 C or 273 K. Nature/significance of gas constant, R: From the gas equation, PV = nRT, we have

Numerical Values of the Gas Constant, R

i. At N.T.P. conditions, for 1 mole of the gas

ii.

In C.G.S. units, 1 mole of gas at N.T.P.

iii.

For expressing in SI units, put 107 erg = 1 J

iv.

Further putting 4.184 J = 1 calorie, we have

1.2.5 Grahams Law of Diffusion

It states that: Under similar conditions of temperature and pressure, the rates of diffusion of different gases are inversely proportional to the square root of their densities. Mathematically,

As molecular weight = 2 vapour density, weight can also be written as

1.2.6 Daltons Law of Partial Pressure

If states that: If a number of gases which do not react chemically with one another are enclosed together in the same vessel, the total pressure exerted by the mixture of gases is the sum of their partial pressures, i.e., the pressures which each gas would exert if present alone in the same vessel. Mathematically,

where P is the total pressure and p1, p2, p3 etc. are partial pressures.

1.3 KINETIC THEORY OF GASES

It was observed that the gas laws were based on experimental observations. The theoretical foundation or mathematical representation was missing. However, several workers studied the properties of gases and found that the gases are essentially composed of freely moving molecules. To explain the behaviour of gases, they put forward a theory called kinetic theory of gases. This theory succeeded to attain a rigid mathematical form. Theassumptions made in this theory are given below.

1.3.1 Postulates (Assumptions) of Kinetic Theory

i. ii. A gas consists of a large number of very small spherical tiny particles called molecules. The volume occupied by the molecules is negligible in comparison to the total volume of the gas.

NOTEWORTHY POINTS
1. Air is dense at sea level, because it is compressed by the mass of air above it. However, the density and pressure decrease with altitude. The atmospheric pressure at Mount Everest is only 0.5 atm. 2. Pressure of a pure gas is measured by manometer while that of a mixture of gases by a

barometer. 3. 1 Bar = 0.9862 atm = 1.0 atm.

1 atm = 1.03125 105 Pa 4. At 4.58 mm Hg pressure and at 0.0098 C, ice (solid), water (liquid) and vapour (gas) may be

present simultaneously and all are stable. Ice/water/vapour The corresponding temperature at which all the three states coexist is called triple point. 5. 6. 7. Centigrade scale and Fahrenheit scale of temperature were related as C = 5/9 (F32) Charles law is not applicable to liquids. Gas constant per molecule is known as Boltzmann constant (K).

K = R/N = 1.38 1010 erg/K/molecule or 1.38 1023 JK1 mol1. 8. Numerical value of R = 0.0821 litre atm K1 mol1 = 8.314 JK1 mol1 = 1.987 cal K1 mol1 iii. The molecules are in a state of constant rapid motion which is completely random. During their motion, they collide into one another and with the walls of the vessel. iv. v. The pressure of a gas is due to the collisions of the molecules with the walls of the vessel. The molecules are perfectly elastic, i.e., there is no loss of energy when they collide with one another or with the walls of the vessel. vi. vii. viii. There is no force of attraction or repulsion amongst the molecules. The average kinetic energy of a molecule is directly proportional to the absolute temperature of gas. The laws of the mechanics in particular Newtons second law of motion are applicable to the molecules in motion.

1.4 DERIVATION OF KINETIC GAS EQUATION

Based on the above postulates of the kinetic theory, we can calculate the pressure of a gas in terms of molecular quantities. Suppose a volume of gas is enclosed in a cubical vessel (Fig. 1.1) of side of l centimetres. Suppose the number of molecules present in it be n and the mass of each molecule bem.

Figure 1.1 Gas contained in a cubical vessel

The molecules move with different velocities in different directions colliding with each other and with the walls of the containing vessel. Suppose u is the velocity of a molecule at any instant. This velocity may be resolved in three rectangular components, ux, uy and uz, along the three axes x, y and zof the cube. Then, we have

Now, consider the molecule moving with a velocity ux along x-axis striking the walls A and A. Since the collisions are perfectly elastic, the molecule after colliding with the wall A would rebound with exactly the same velocity but in opposite direction. The momentum of the molecule before it strikes

The momentum of the molecule after it strikes

Therefore, the change of momentum due to one impact

After colliding with the wall A, it will travel a distance of l centimetres to strike the face A (i.e., opposite to A) and then returns to face A again. Hence, after traversing a distance of l every time, it will make one impact on the wall. The total number of impacts the molecule makes on the two walls A and A per unit time would thus be ux/l. Therefore, the change of momentum per molecule along x-axis per second

Similarly, the change of momentum per molecule along y- and z-axes per second would be and respectively.

Therefore, the total change of momentum along all the three axes per second per molecule

Now, we consider all the molecules having different velocities u1, u2, u3,etc. The change of momentum per second of all the molecules on all the walls of the cube:

where u is the root mean square velocity. Based on the kinetic theory of gases, we have three types of velocities, viz. average velocity, root mean square velocity and most probable velocity. Suppose in a gas, there are n1, n2, n3,molecules possessing velocities n1, n2, n3,, respectively. The average velocity (v) is then given by,

The root mean square velocity (u) is defined as the square root of the mean of squares of all the velocities and is given by

Most probable velocity ( molecules of the gas. We have

) is defined as the velocity possessed by the maximum number of

According to Newtons second law of motion, the change of momentum per unit time is the force (F) exerted by the molecules on the walls of the cube.

Since, pressure is the force per unit area (A), we have

If d be the density of the gas, then from Eq. (1.12), we have

For 1 mole of a gas, n can be replaced by N (Avogadro number). Therefore, kinetic equation (1.12) then becomes,

Expressions (1.12), (1.13) and (1.14) are different forms of kinetic equation of gases.

1.5 DERIVATION OF GAS LAWS FROM KINETIC EQUATION

(i) Boyles law: According to it, at constant temperature, the volume of a given mass of a gas is inversely proportional to pressure, i.e.,

or

PV = constant, at constant T From kinetic equation, we have

The kinetic energy of the gas

At constant temperature, the kinetic energy (E) of the gas is constant. Therefore, at constant temperature PV = constant [This is Boyles law.]

(ii) Charles law: According to it, at constant pressure, the volume of a given mass of a gas is directly proportional to its absolute temperature, i.e.,

As already derived, from Eq. (1.15), we have

At constant pressure,

However, we know that E T, where T is absolute temperature.

(iii) Avogadros hypothesis: According to it, equal volumes of all gases under similar conditions of temperature and pressure contain equal number of molecules. For any two gases, the kinetic equation can be written as:

When pressures and volumes of the gases are the same, i.e., P1 = P2 and V1 = V2, it follows that

When the temperatures of the gases are the same, their mean kinetic energy will also be the same, i.e.,

Dividing Eq. (1.16) by Eq. (1.17), we get, n1 = n2

[This is Avogadros hypothesis.]

(iv) Grahams law of diffusion: According to it, the rate of diffusion (r) of a gas is inversely proportional to the square root of the density (d) of the gas, at constant pressure, i.e.,

From kinetic equation, we have

Therefore, at constant pressure, The rate of diffusion (r) of the gas is directly proportional to the mean velocity (u) of the molecules, i.e.,

(v) Daltons law of partial pressures: Suppose n1 molecules, each of mass m1, of a gas, A, are contained in a vessel of volume V. Then, according to the kinetic theory, the pressure, pA, of the gas A will be given by:

Now, suppose n2 molecules, each of mass m2, of another gas, B, are contained in the same vessel at the same temperature and there is no other gas present at that time. The pressure, pB, of the gas B is then given by,

If both gases are present in the same vessel at the same time, the total pressure, P, is given by,

Similarly, if three, four or more gases are present in the same vessel, the total pressure is given by,

(vi) Derivation of ideal gas equation:

It is combined gas equation. If then PV = RT (for one mole of gas) PV = n RT (for n moles of gas) which is the required ideal gas equation. k = R, (gas constant),

1.5.1 Some Useful Deductions from Kinetic Theory of Gases 1.5.1.1 Calculation of Molecular Velocities
According to kinetic gas equation

If 1 mole of the gas is taken, M will be equal to the molecular weight of the gas.

Further, for one mole of the gas (assuming it is ideal) PV = RT

Knowing that

is the density of the gas, equation

can also be written as

Depending upon the conditions given, any one of the Eqs (1.18), (1.19) and (1.20) can be used for the calculation of the root mean square velocity.

Numerical Problems
Example 1 Calculate the root mean square velocity of CO2 molecule at 1,000 C.

Solution: We know that

Example 2 Calculate the RMS velocity of chlorine molecules at 12 C and 78 cm pressure. Solution: At given condition: At STP

Example 3 Calculate the average velocity of nitrogen molecule at STP. Solution: Substituting the given values in this equation

Example 4 Oxygen at 1 atmosphere pressure and 0 C has density of 1.4290 grams per litre. Find the RMS velocity of oxygen molecules. Solution: We have

1.5.1.2 Calculation of the Kinetic Energy of the Molecules

For 1 mole of the gas containing n molecules, each of the mass m, the kinetic energy will be

According to kinetic gas equation

Further, for 1 mole of the ideal gas,

From the equation, we observe that the kinetic energy of an ideal gas is independent of the nature or pressure of the gas and it depends only on the absolute temperature, being directly proportional to it. The average kinetic energy per molecule can be obtained from the above equation by dividing with the Avogadros number N. Thus, average K.E. per molecule

where

is called Boltzmann constant.

Example 5 Calculate the total and average kinetic energy of 32 g methane molecules at 27 C (R = 8.314 JK
1

mol

).

Solution: Total (molar mass of CH4 = 16 g mol1)

Example 6 Calculate the root mean square speed of methane molecules at 27 C. Solution:

Example 7 The average kinetic energy of a gas molecule at 0 C is 5.621 1021 J. Calculate Boltzmann constant. In addition, calculate the number of molecules present in one mole of the gas.

Solution: Average Kinetic energy =

1.5.1.3 Concept of Absolute Zero

We know that

Further as derived above,

Combining Eqs (1.21) and (1.22), we get

Thus, the molecular velocity of any gas is directly proportional to the square root of its absolute temperature. Hence, when T = 0, u also becomes zero. This temperature is called absolute zero. Hence, absolute zero is that temperature at which the molecular motion creases. Remember 0 A or 0 K = 273 C

1.5.1.4 Slow Diffusion of Gases

In spite of the fact that the gas molecules move with high speeds, yet their motion is not so fast. For example, it takes quite some time for a smell to spread from one corner of a room to the other. This is obviously due to the fact the molecules of a gas undergo an extremely large number of collisions, per second. In every collision, the path of the molecule is deflected, so much so that sometimes it is even deflected back. Hence, the net linear movement of the molecules in a particular direction is quite slow.

1.11 ISOTHERMS OF CARBON DIOXIDECRITICAL PHENOMENON

The curves representing the variation of volume and pressure at constant temperature are called Isotherms (Greek; iso = equal). In the case of an idea gas, the isotherms would be rectangular hyperbolas.

Figure 1.7 Andrews isotherms of CO2 at different temperatures

In 1869, T. Andrews studied the effect of pressure on volume of CO2 at different temperatures. When the volume readings were plotted against the pressure, a set of curves of the type shown in Fig. 1.7 was obtained. Each curve corresponds to one particular temperature and is, therefore, called isotherm. The curves should be rectangular, hyperbolas like that expected for an ideal gas. It is quite clear that CO2 does not give rectangular hyperbolas although with increasing temperature the curves approximate to one. Let us consider the various isotherms separately. (i) Isotherm at 0 C: The isotherm shows that carbon dioxide is entirely gaseous at low pressures and the volume decreases with increasing pressure in the normal fashion. (ii) Isotherm below 31 C: The isotherm below 31 C is not continuous. For example, in the isotherm of 21 C, the point A corresponds to gaseous CO2 occupying a certain pressure. At low pressures, if the pressure is increased, the volume decrease as indicated by the curve AB. At B liquefaction commences; vapour is converted into liquid of very much greater density and the decreases suddenly as the volume occupied by a liquid is much less than that of BC is approximately parallel to the volume axis indicating the sudden decrease in volume taking place at the same pressure. Liquefaction is complete at C and CD shows the small effect of pressure on a liquid. The steep line CD which is almost vertical represents the compressibility of a liquid and shows that the liquids are much less compressible, i.e., increase in pressure produces a very small decrease in volume. To summarize, along curve AB there is only vapour, along CD only liquid and along BC liquid and vapour co-exists. Since BC is parallel to the volume axis, there can be only one pressure at which liquid and vapour co-exits. This pressure is called vapour pressure of the gas. (iii) Isotherm at 31 C: As the temperature is raised, this horizontal portion becomes less and less till at 31.1 C; it reduces almost to a point F. Above this temperature, there is no trace of horizontal portion, i.e., beyond 31.1 C, there is no indication of liquefaction at all. Point F is the critical point for CO2. The distinction between liquid and vapour state disappears at this point and CO2 exits in a state called the critical state. The isotherm passing through critical point is called the critical isotherm. (iv) Isotherm above 31 C: If the temperature was beyond 31.1 C, CO2 could not be liquefied. Yet Andrews applied a pressure of 300400 atm. However, at 21 C, only a pressure of 75 atm was quite sufficient to liquefy CO2.

From the experiment, Andrews concluded that if the temperature of CO2 is above 31.1 C, it cannot be liquefied no matter how high the pressure may be. This maximum temperature (31.1C) at which liquefaction can be brought about is called critical temperature. The pressure required to liquefy a gas at the critical temperature is known as the critical pressure. If the temperature happens to be below the critical temperature, the gas will liquefy at a somewhat lower pressure. All other gases have been found to behave similarly. The critical phenomenon observed by Andrews for CO2 may be observed for any gas.