KINETIC THEORY OF GASES

KINETIC THEORY OF GASES

1.1 Introduction:A gas of extremely large number of widely separated minute particles, called molecules, which are in a state of continuous motion. They rush about in all directions, and in all sorts of manner, and frequencies collide with each other. Due to repeated collision of molecules, their velocity and direction get changed at random, as a result of which a molecular change prevails within the gas. While the particles making up a gas are too small to be visible, the jittering motion of pollen grains or dust particles which can be seen under a microscope, known as Brownian motion, results directly from collisions between the particle and gas molecules. As pointed out by Albert Einstein in 1905, this experimental evidence for kinetic theory is generally seen as having confirmed the existence of atoms and molecules. Postulates: The theory for ideal gases makes the following assumptions:

The gas consists of very small particles. This smallness of their size is such that the total volume of the individual gas molecules added up is negligible compared to the volume of the smallest open ball containing all the molecules. This is equivalent to stating that the average distance separating the gas particles is large compared to their size.

These particles have the same mass. The number of molecules is so large that statistical treatment can be applied. These molecules are in constant, random, and rapid motion. The rapidly moving particles constantly collide among themselves and with the walls of the container. All these collisions are perfectly elastic. This means, the molecules are considered to be perfectly spherical in shape, and elastic in nature.

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Except during collisions, the interactions among molecules are negligible. (That is, they exert no forces on one another.) This implies: 1. Relativistic effects are negligible. 2. Quantum-mechanical effects are negligible. This means that the interparticle distance is much larger than the thermal de Broglie wavelength and the molecules are treated as classical objects. 3. Because of the above two, their dynamics can be treated classically. This means, the equations of motion of the molecules are timereversible.

The average kinetic energy of the gas particles depends only on the temperature of the system. The time during collision of molecule with the container's wall is negligible as compared to the time between successive collisions. More modern developments relax these assumptions and are based on

the Boltzmann equation. These can accurately describe the properties of dense gases, because they include the volume of the molecules. The necessary assumptions are the absence of quantum effects, molecular chaos and small gradients in bulk properties. Expansions to higher orders in the density are known as virial expansions. The definitive work is the book by Chapman and Enskog but there have been many modern developments and there is an alternative approach developed by Grad based on moment expansions. In the other limit, for extremely rarefied gases, the gradients in bulk properties are not small compared to the mean free paths. This is known as the Knudsen regime and expansions can be performed in the Knudsen number.

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1.2 Different States of Matter

States of matter are the distinct forms that different phases of matter take on. Three states of matter are known in everyday experience: solid, liquid, and gas. Other states are possible; in scientific work, the plasma state is important. Further states are possible but do not normally occur in our environment: BoseEinstein condensates, neutron stars. Other states, such as quark-gluon plasmas, are believed to be possible. Much of the baryonic matter of the universe is in the form of hot plasma, both as rarefied interstellar medium and as dense stars and quantum spin liquid. Historically, the distinction is made based on qualitative differences in bulk properties. Solid is the state in which matter maintains a fixed volume and shape; liquid is the state in which its volume varies only slightly, but adapts to the shape of its container; and gas is the state in which matter expands to occupy the volume and shape of its container.

This diagram shows the nomenclature for the different phase transitions. The state or phase of a given set of matter can change depending on pressure and temperature conditions, transitioning to other phases as these conditions change to favor their existence; for example, solid transitions to liquid with an increase in temperature. A state of matter is also characterized by phase transitions. A phase transition indicates a change in structure and can be recognized by an abrupt change in properties. A distinct state of matter can be defined as any set of

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states distinguished from any other set of states by a phase transition. Water can be said to have several distinct solid states.[1] The appearance of superconductivity is associated with a phase transition, so there are superconductive states. Likewise, ferromagnetic states are demarcated by phase transitions and have distinctive properties. When the change of state occurs in stages the intermediate steps are called mesophases. Such phases have been exploited by the introduction of liquid crystal technology. More recently, distinctions between states have been based on differences in molecular interrelationships. Solid is the state in which intermolecular attractions keep the molecules in fixed spatial relationships. Liquid is the state in which intermolecular attractions keep molecules in proximity, but do not keep the molecules in fixed relationships. Gas is the state in which molecules are comparatively separated and intermolecular attractions have relatively little effect on their respective motions. Plasma is a highly ionized gas that occurs at high temperatures. The intermolecular forces created by ionic attractions and repulsions give these compositions distinct properties, for which reason plasma is described as a fourth state of matter.

1.3 Assumptions in the kinetic theory of gases:The kinetic theory of gases is based on the following assumptions:
1. The volume of gas consists of large number of minute particles called

molecules. It has been experimentally found that there are about 26.8 x 1018 molecules in *1ml of gas at N.T.P
2. The molecules are mere mass points. In other words, the size of the

molecule is assumed to be negligible, as compared to the distance between the molecules. 3. The gas molecules are perfectly elastic spheres and exert negligible force of attraction or repulsion on one other, or on the walls of the containing vessels. Hence in a direct impact, the molecules rebound with the same velocity after each collision.

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4. The molecules are continuously colliding against each other, and with the walls of the containing vessel. Between two collisions a molecule moves in a straight line. This distance is called the free path of the molecule. 5. The time during which a collision takes place is negligible as compared to the time required to transverse the free path, i.e., collisions are instantaneous
6. The molecules are continuously in motion. They have velocities in all

directions ranging from zero to infinity. The velocity of molecules increases with the increase in temperature. For simplicity, it is assumed that 1/3rd of the molecules move parallel to the x-axis, 1/3rd parallel to the y-axis and 1/3rd parallel to the z-axis. *
Since 1 ml = 10-6 m3, therefore 1m3 of any gas at N.T.P will contain 26.8 x 1018/10-6 = 26.8 x1024 molecule. Since the volume of 1kg molecule of any gas at N.T.P is 22.4 m3, therefore 1kg molecule of any gas will contain 26.8 x 1024 x 22.4 = 6.02 x 1026

1.4 Velocity of molecule:We already discussed that molecules of a gas move in haphazard manner in all directions and have different velocities. The following three velocities are important from the subject point of view: 1. Mean or average velocity, 2. Route mean square velocity, 3. Most probable velocity 1. Mean or average velocity: Consider a gas containing n molecules, having actual velocities of individual as C1, C2, C3 Cn Therefore mean or average velocity = C1, C2, C3 Cn / n = (8kT/ m) = 1.5959kT/m)

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2. Root mean square (r.m.s) velocity: The root mean square velocity, C = [(C21, C22, C23 C2n)/n] The value of r.m.s. velocity of may also be obtained from the following relations: (i) (ii) C = (3p/ ) = 1.732 (p/ ) C = (3kT/m) = 1.732 (kT/m) Since the velocity of molecule changes with temperature, the root mean square velocity of the molecules remains constant so long as the temperature remains constant. 3. Most probable velocity: The Maxwells distribution of molecular velocities and percentage of molecules is shown in figure

Fig 1.1 Most probable velocity.

We see that the maximum percentage of molecules (AB) at any temperature move with the velocity of OA. The velocity is known as most probable velocity.

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The most probable velocity may, therefore, be defined as the velocity with which the largest percentage of molecules in a gas is found to move at any given temperature. Note:1. The value of most probable velocity is given by: (2kT/m) = 1.414 (kT/m). Where k = Boltzmanns constant, its value is small for all gases and may be taken as 1.38 x 10-26KJ / K. T = absolute temperature m = mass of one molecule 2. Due to non-symmetrical shape of the curve, the mean velocity is larger than the most probable velocity, and the r.m.s. velocity is little larger than either one of them. 3. From above we see that Mean average velocity = 0.9209 x r.m.s velocity and Most probable velocity = 0.8164 x r.m.s velocity

1.5 Perfect Gas:A perfect gas or ideal gas may be defined as a state of a substance, whose evaporation from its liquid state is complete*, and strictly obeys all the gas laws under al conditions of temperature and pressure. In actual practice, there is no real or actual gas which strictly obeys the gas laws over the entire range of temperature and pressure. But, the real gases which are ordinarily difficult to liquefy, such as oxygen, nitrogen, hydrogen and air, with in certain temperature and pressure limits, may be regarded as perfect gases. * If its evaporation is partial, the substance is called vapour. A vapour, therefore, contains
some particles of liquid in suspension. It is thus obvious, that steam, carbon dioxide, sulphur dioxide and ammonia are regarded as vapours. It may be noted that a vapour becomes dry,

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when it is completely evaporated. If the dry vapour is further heated, the process is called super heating and the vapour is called super-heated vapour. The behavior of superheated vapour is similar to that of a perfect gas

1.6 Pressure exerted by an ideal gas:The pressure exerted by a gas is due to the continuous bombardment on the walls of the containing vessel by the rapidly moving gas molecules.

Fig. 1.2 Pressure exerted by an ideal gas

Consider a hollow cubical vessel of each side equal to l, having perfectly elastic walls as shown in the above figure. Let it contain a perfect gas having a large number of molecules, say, n. out of these n/3 molecules are travelling back and forth parallel to each of the co-ordinate axis i.e., x-axis. Yaxis, z-axis with velocity C (r.m.s velocity) Let us first consider the pressure exerted by one molecule, travelling back and forth parallel to the x-axis. The molecule strikes the face ABCD of the containing vessel and rebounds with the same velocity in reverse direction, since the collision is perfectly elastic. Let C = velocity of molecule before collision and -C = velocity of molecule after collision Therefore momentum before collision = mC Momentum after collision = -mC Hence, change in momentum per collision per molecule = mC (- mC) = 2mC The molecule now travels from face ABCD to face ABCD and travels back again to face ABCD. It is thus obvious that the distance travelled by the molecule between the two successive impacts on the face ABCD is 2l.

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Therefore number of collisions per second

= C / 2l

and change in momentum per collision per second = 2mC x C / 2l = mC2 / l and total change in momentum per second due to collisions of n/3 molecules = (n / 3) x (mC2 / l) = (mn / 3l) x C2 Since the change in momentum per second = impressed force, therefore, Total force on face ABCD = (mn / 3l) x C2 = [mn / (3l x l2)] x C2 = (mn / 3v) x C2 Now, Therefore Pressure exerted by an ideal gas, p = 1/3 x M/v x C2 = 1/3 C2 Note: the above equation may also be written as: P = 2/3 x 1/2 C2 = 2/3 x K. E per molecule = 2/3 E Therefore the pressure exerted by an ideal gas is equal to 2/3rd of the kinetic energy of all the molecules contained in a unit volume of gas. Example 1 Calculate the root mean square velocity of air at NTP. The density of air at NTP is 1.29KG/m3. Density of mercury is 13,600kg/m3 and g 9.81m/s2 Solution: Given: p = 760 mm of Hg; = 1.29 kg/m3; We know that, p = 0.76 m of Hg = 0.76 x 13600 x 9.81 = 101396 N/m2
m

Pressure exerted on the face ABCD = force / area

mn = M molecular mass of gas

[M/v = ]

= 13600 kg/m3

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We also know that, P = 1/3 x C2 C = (3p/ ) = (3 x 101396 / 1.29) = 485.6 m/s

1.7 Kinetic Energy per kg Molecule of a Gas

We know that the pressure exerted by an ideal gas, p = 1/3x M/v x C2 Or p v = 1/3 x M C2 Now, according to perfect gas equation, we have p v = Ru T where Ru = Universal gas constant From equation (i) and (ii), we get 1/3 x M C2 = Ru T Or 1/2 x M C2 = 3/2 x Ru T Hence, the kinetic energy per kg molecule of any gas at absolute temperature Tis equal to 3/2 x Ru T. .. (ii) v = Volume of gas per kg molecule, and .. (i)

1.8 Kinetic Interpretation of Temperature:We know that the pressure exerted by an ideal gas, p = 1/3 x M/v C2 Or p v = Ru T we also know that 1/3 x MC2 = Ru T 1/3 x mNC2 = Ru T Where m = Molecular mass of gas per molecule, and N = Avogadros number representing the number of molecules

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KINETIC THEORY OF GASES

per kg molecule of a gas. Its value is same for all gases and may be taken as 6.02 x 1026 From the above equation , we have 1/3 x mC2 = (Ru / N) x T Or 1/2 x mC2 = 3/2 x (Ru / N) x T = 3/2 x kT Where k = Ru / N = Boltzmanns constant. Hence, kinetic energy of translation of molecule 3/2 x kT In other words, the kinetic energy of translation of molecule is proportional to the absolute temperature. This is known as kinetic interpretation of temperature. Note: 1. The K.E. of translation of a molecule at a given absolute temperature is same for all the gases. 2. From equation 1/3 x mNC2 = Ru T C = (3kT/mN) = (3kT/m)
... Because, Ru/N = k ..(i) ..(ii)

= (3RT) ..Because, mN = m & Ru/M = R R = Characteristic gas constant. Where In other words, C T 3. Since C T or C2 T, therefore when T = 0, the velocity C = 0

Hence , the absolute Zero of temperature is that temperature at which the velocities of the molecules of gas becomes Zero.

1.9 Application of Kinetic Theory to Laws of Perfect Gases:

1. Boyles law We know that pressure exerted by a perfect gas, P = 1/3*M/v*C2 or

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KINETIC THEORY OF GASES

pv = 1/3*MC

Since C depends on T (because C T), therefore, when T is constant, the right hand side of the above expression is also constant. Therefore pv = constant 2. Charles law We know that pressure exerted by a perfect gas, P = 1/3*M/v*C2 or pv = 1/3*MC2 Since C T or C2 T, Therefore pv T When p is kept constant, then v T or v/T = Constant 3. Gay-Lussac law We have already seen in the above equation that pv T When v is kept constant, then P T or p/T= Constant 4. Perfect gas equation We have already seen in the above equation that pv T pv/T =Constant or pv= RuT 5. Avogadros law .(General gas equation) (when This constant)

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KINETIC THEORY OF GASES

It states, Equal volumes of all gases under the same conditions of temperature and pressure, contain the same number of molecules. Let m1, n1 and C1 represent the mass per molecule, number of molecules per m3 and root mean square velocity respectively for one gas and m2, n2 and C2 the corresponding values for the other gas. If the two gases exert the same pressure p, then p=1/3m1n1C12=1/3m2n2C22 molecule in the two gases is equal. In other words 1/2 m1 C12=1/2 m2 C22 Dividing equation (i) by (ii), n1=n2 Example 1 At what temperature will the velocity (root mean square velocity) of hydrogen be double of its value at N.T.P., if the pressure remains constant? Solution: Given: T0 = 00 = 0 + 273 = 273 K Let C = Root mean square velocity. T = Absolut temperature at which the r.m.s. velocity is 2C. We know that C T Or C2 = T C2/ (2C) 2 = T0 / T Or 1/4 = 273/T Or T = 1092 K = 819 0C .(ii) (i) If two gases are at the same temperature, then the mean kinetic energy per

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KINETIC THEORY OF GASES

Example 2 Calculate the temperature at which root means square velocity of a gas molecule is same as that of a molecule of another gas at 47oC. The molecular masses of first and second gases are 64 and 32 respectively. Solution: Given: T2 = 47oC = 47+273 = 320K; M1 = 64; M2 = 32; Let T1= Temperature of the first gas, and C= Root mean square velocity. We know that pv= RuT=1/3MC2 M1C12/T1= M2C22/T2 Or M1/T1=M2/T2 Therefore T1=T2*M1/M2 = 320*64/32 =640K =367oC Ans. Example 3 The root mean square velocity of the molecules of a fixed mass of a gas is 895m/s. Calculate the root mean of square velocity of the molecules when the gas is compressed adiabatically to half of its original volume. The ratio of specific heats at constant pressure to that of constant volume is 1.4. Solution: Given: C1 = 895 m/s; v2 = 0.5v1; ( because C1=C2)

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KINETIC THEORY OF GASES

= 1.4 Let C2=Root mean square velocity of the molecules when the gas is compressed, T1=initial temperature of the gas, and T2= final temperature of the gas. We know that for adiabatic compression, T1/T2 = (v2/v1) (-1) = (0.5v1/v2) (1.4-1) = (0.5v1/v2) (1.4-1) = (0.5)0.4 =0.758 (i) Since C T Or C2 T, Therefore C12/C22 = T1/T2 or C12/C22 =.758 C2 = (C12/.758) ^1/2 = [(895)2/.758)] ^1/2 = 1028m/s Ans. (From equation (i))

1.10 Degree of Freedom:In order to describe completely the motion of a particle in one plane, only two quantities must be known, say its two rectangular components. Similarly, for a particle moving in space, three independent qualities must be known to describe its motion. A molecule in a rigid body can have three motions of vibration along any of the three co-ordinate axes in addition to its three motions of translation. It is thus obvious that in order to completely describe the state of motion of a particle, six independent quantities must be known.

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KINETIC THEORY OF GASES

In general, the total numbers of independent qualities, which must be known for describing completely the state of the motion body, are called degree of freedom. 1. Monoatomic gas. A molecular of mono atomic gas has only one atom. This atom can rotate about its polar axis, and can also move bodily in the three perpendicular planes as shown in the below fig (a). Hence, such a molecule will have three translational degrees of freedom and one rotational.

2. Diatomic gas. A molecule of diatomic gas is like a dumb-bell. It has two atoms only. Such molecules have appreciable moment of inertia and it is capable of rotational as well as translational motion. Its rotational motion can be resolved into two motions about two axes perpendicular to the line joining the atoms constituting a molecule as shown in fig 5.4. Hence a diatomic possess five degree of freedom, i.e. three translational and two rotational. It can be observed that more the atoms in a molecule, the greater will be the number of degrees of freedom possessed by it.

1.11 Laws of Equipartition of Energy*

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KINETIC THEORY OF GASES

This law states, The total energy of a molecule is shared equally by the various degrees of freedom possessed by it. In case of monoatomic molecules like argon and helium, the energy possessed by them is only that of translational type, the rotational energy being negligible. =3/2*kT This energy is equally distributed among the three translational degrees of freedom. Therefore energy per molecule per degree of freedom =1/3*3/2kT=1/2kT Hence, the law of Equipartition of energy may be stated as follows: The total energy of any dynamical system in thermal equilibrium is divided equally among all its degrees of freedom and the energy associated with each degree of freedom is 1/2kT.
* This law was devised by Maxwell in 1849 for translation degrees of freedom. But
Boltzmann extended it further to rational and vibration energies.

1.12 Ratio of Molar Specific Heats

The ratio of molar for the following two cases is important from the subject point of view: 1. Monoatomic gas. And 2. Diatomic gas. 1. Monoatomic gas: We know that monoatomic gas has three degrees of freedom of translation and energy per molecule of the gas per degree of freedom is 1/2kT. Therefore Total energy per molecule for 3 degrees of freedom =3*1/2kT =3/2kT And total energy per kg-molecule at temperature TK =3/2kNT =3/2RuT . (N being number of molecules) (because k = Ru / N)

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If the temperature of the gas is raised by 1K, then total energy per kg-molecule at (T+1) K =3/2 Ru (T+1) It may be noted that increase in total energy per kg-molecule per degree rise in temperature is equal to the heat required to raise the temperature of 1kg molecule through 10. This is known as molar specific heat at constant volume, i.e. cvm. Therefore Molar specific heat a constant volume, cvm = 3/2 Ru(T+1)-3/2RuT = 3/2Ru Since cpm-cvm = Ru, therefore c = cvm + Ru = 3/2Ru+Ru = 5/2Ru Therefore Ratio molar specific heats, Gama= cpm/cvm=(5/2*Ru)/(3/2*Ru)=5/3=1.67 2. Diatomic gas: We know that the molecule of a diatomic gas has five freedom. Therefore Total energy per kg-molecule at temperature TK =5/2RuT And total energy per kg-molecule at (T+1) K =5/2 Ru(T+1) Now, molar specific heat at a constant volume, Cvm = 5/2 Ru(T+1)- 5/2RuT= 5/2 Ru Therefore Ratio of molar specific heats, Gama= cpm/cvm=(7/2) Ru /(5/2) Ru=7/5= 1.4 degree of

1.13 Vander Waals Equation of a Real Gas

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KINETIC THEORY OF GASES

Practically there is no real gas which obeys the gas laws perfectly. The deviation is small at ordinary temperatures and pressures, but it is large at high pressure and low temperatures. In deriving the perfect gas laws a on the basis of kinetic theory of gases, the following assumptions were made which do not hold true for the real gases: 1. The molecule of a gas are mere mass-points occupying no space; and 2. There is no attraction or repulsion between the molecules. In actual practice, the molecules of all actual or real gases do occupy some space and do attract each other. Hence no real gas conforms to the perfect gas equation p v= RT. The Dutch physicist J.D.Van der Waals was the first scientist to correct this equation by applying corrections for the above two factors. 1. Correction for the size of molecules: Consider some quantity of gas contained in vessels. We know that molecule of gases have finite size, therefore the space available for the molecules to move about is less than the volume of the gas. Let v= volume of the gas; and b= volume occupied by all the molecules. Therefore space actually available or the effective volume of the gas = v-b Note: This has been experimentally found that b is four times the total volume of the molecules and not equal to the volume occupied by the molecules. 2. Correction for the mutual attraction of molecules: Consider a gas molecule A well within the body of the gas inside the vessel. It is attracted by other molecules in all directions with the same force and the net force on it is zero. But when it strikes the wall of the vessel, it is pulled back by other molecules. Its velocity, and hence the momentum, with which it strikes the wall would be less than the momentum with which it will strikes the absence of the force of attraction. It is obvious that when the pressure of the gas

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KINETIC THEORY OF GASES

drops, the momentum of the molecules also decrease. it is due to this fact, that the decrease in pressure is proportional to: 1. The number of attracting molecules per unit volume, and 2. The number of attracting molecules striking a unit area of walls of the containing vessel per unit time. Each of these factors is proportional to the number of molecules per m3 or the density of the gas. Therefore decrease in pressure, p (density of the gas)2 to 1/v2 or p = a/v2 Where a is constant of proportionality. Therefore Corrected pressure = p + p= p + a/v2 Now with these corrections, of perfect gas equation for the real are actual gas becomes (p + a/v2)(v - b) = RT This is known as Van der Waals equation for a real gas.

BIBILOGRAPHY: Thermodynamics by Khurmi Application of Thermodynamics by R K Guptha Basics of Thermodynamics by B A Srinivas Google Wikipedia Encyclopedia

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