KINETIC THEORY OF GAS CHAPTER-13, KINETIC THEORY OF GASES All matter is made up of molecules. The molecules of a gas are in state of rapid and continuous motion. Using this molecular motion, the macroscopic Properties of a gas such as pressure, volume, temperature, energy etc, can be explained. Hence this theory is called kinetic theory of gases. ASSUMPTIONS OR POSTULATES OF KINETIC THEORY OF GASE: 1. The size of the gas molecules is extremely small as compared to the intermolecular distance. 2. All the molecules of a gas are identical as regards their shape and mass. They differ from molecules of other gases. 3. The molecules of a gas are rigid, perfectly elastic and hard spheres. 4. The molecules are in a state of continuous random motion, moving in all direction with all possible velocities. 5. During random motion, the molecules collide with one another and with the walls of the vessel 6. The collisions are perfectly elastic and there are no forces of attraction or repulsion between the molecules. So, molecules possess only kinetic energy. 7. The path travelled by a molecule with a uniform velocity between two successive collisions is called free path and the average distance by a molecule between two successive collisions is called mean free path 8. The collisions are almost instantaneous i.e., the time during collision is small compared to the free path between the molecule. 9. The effect of gravity on the motion of molecules is negligible. i.e. Density remains same throughout the gas. GAS LAWS: 1. Boyle’s la It states that “the volume of a given mass of a gas is inversely proportional to its pressure, provided the temperature remains constant”, Mathematically, 1 K Vas Or V=_ Or PV=K Where K is a constant, its value depends ‘on the mass and temperature of the gas. If P, and V, are the initial values and P, and Vp are the final values of pressure and volume of the gas respectively then from Boyle's law, PLM, = PoVe The variation of pressure P with volume V at constant temperature is as shown in fig.1. The variation of pressure P with - at constant temperature is as shown in fig.2 1 T=constant — Vv Figure.2 Figure.t 2. CHARLES’ LAW: It states that “if the pressure remains constant, then the volume of a given mass of a gas increases or decreases °Y Faas 1°C each rise or fall of temperature”. If V and Vo are the volumes of a given mass of gas at te and 0% respectively at a constant pressure then, times of its volume at 0°C for V=V(1t«t) V=W(1+a975) 27315 tog a= aag")KINETIC THEORY OF GAS 273.15 +0 v= v(Fa) T = 273.15 +t and Ty = 273.15 Vewe or Hae or ha Vo T T To constant ie.,V «1 It can also be states that “at constant pressure, the volume of a given mass of gas is directly proportional to its absolute temperature” The variation of volume Vofagas f with its absolute T temperature T must Peconstant be a straight line as shown in fig. vo 3. GAY LUSSAC’S LAW: It states that “if the volume remains constant, then the pressure of a given mass of a gas increases or decreases by Saiz times of its pressure at 0°C for 1°C each rise or fall of temperature”. If P and Po are the pressure of a given mass of gas at t and 0°c respectively at a constant volume then, P= R(+«t) Pe (1 +a7338) 1 oe-1 mse’) 273.15 + P »( 273.15 T = 273.15 + tand Ty = 273.15 pap or eae op Ph APaRe or aa ona a P ors T It can also be states that “at constant volume, the pressure of a given mass of gas is directly proportional to its absolute temperature”. constant i.e.,P«T IDEAL GAS EQUATION: The equation which relates the pressure (P) volume (V) and temperature (1) of the given state of an ideal gas is known as ideal gas equation or equation of state. Derivation: ‘According to Boyle’s law, for a given mass of a gas at constant temperature, vas sesssstseessnee (1) ‘According to Charles’ law, for a given mass of a gas at constant pressure, VaT (2) Combining the above two laws, Vo V = constant x = = orV= a pe constant x 5 -- (3) For one mole of a gas, the constant has same value for all the gases and is called universal gas constant (R). Equation (3) becomes, Pv= For n moles of a gas, PV =nRT (4) This is perfect or Ideal gas equation. If vis the volume of m gram and Mo is the molecular mass, then n = =. Py, = = constant. Equation (4) becomes, Pu=7-RT Herer = 57 For 1 gram mass of a gas, Pu=rT (5) 7 is gas constant for 1 gram mass of a gas. If Nis the total number of molecules in a mass m gram of the gas, the number Ny of molesis n= Equation (4) becomes, pv ="Rrr Na Here,kp = on is called Boltzmann’s constant. Or PV = kpNT (6) NOTE: Value of R = 8.31) mole? K*. Ani ky = 1.38x107)K7.KINETIC THEORY OF GAS PRESSURE OF AN IDEAL GAS: The force exerted by the gas molecules per unit area of the walls is called the pressure of the gas. A gas exerts pressure due to the continuous collisions of its molecules with the walls of the container. EXPRESSION FOR THE PRESSURE OF AN IDEAL GAS: Consider an ideal gas enclosed in a cubical vessel of side I. Suppose the sides of the cube are parallel to the co-ordinate axes, as shown in the figure. Let_n be the number of gas molecules per unit volume and m be the mass of each molecule. A molecule moving with velocity v hits the wall of area A and rebounds with same velocity. If vy, ¥y and v, are the components of velocity along X, Y and Z-axes respectively. Then, Vi = vp + up + uF The change in momentum of the molecule along X~ axis = —my, — mv, = -2mv, The momentum imparted to the wall in each collision = 2mvy. In small time interval dt, all those molecules which lie within the distance v,dt from the wall of area A will hit this wall. That is the molecules which lie in the volume Av,dt only will hit the wall in time dt. On average, half of such molecules are moving towards the wall and other half away from the wall. + The number of molecules hitting the wall in time dt 1 Av,dt xn 2 The total momentum transferred to the wall in time dt is, 1 dp = 2mv, x 5n Av,dt = nmvgAde Force exerted on the wall is, dp dt Pressure on the wall, nmvA Force _ nmvzA Area A As the molecules different velocities, so we replace v2 by its = nmv move with average value v# in the above equation. a P=nmve Inside the vessel the molecules are in random motion. So the molecular velocities are almost equally distributed in different directions. By symmetry, 1 zg gz y= VE Where V7? is the mean square velocity of the molecules. Hence, This gives the pressure exerted by the gas in any direction. NOTE: Density of gas, mass Then, we write 1 P=zpeKINETIC THEORY OF GAS KINETIC INTERPRETATION OF TEMPERATURE: Consider one mole of a gas. Let P, V, T and M be the pressure, volume, temperature and molecular weight of the gas respectively. According to kinetic theory the pressure exerted by the gas is, 14, 1M P=apR=— gh 37" 1 PV gue From the ideal gas equation, PV = RT 1. o RT = yMi? = BRT = Mi? A Kee = 2Mé? =d3R7 = Ser + Average K.E,E = 5Mi? = >3RT => This gives the mean kinetic energy of one mole of the gas. If Nq is the Avogadro number, then the mean kinetic energy per molecule is given by, Where kg is Boltzmann's constant. Bor Thus, the mean kinetic energy per molecule is proportional to the absolute temperature of the gas. It is independent on pressure, volume and nature of the gas. When gas absorbs heat, the K.E of the molecule increases and hence temperature of gas increases. When gas loses heat, the K.E of the molecule decreases and hence temperature of gas decreases. Thus, temperature of a gas is a measure of the mean translational K.E per molecule of the gas. ‘At the absolute zero temperature the velocities of the gas molecules become zero. DALTON’S LAW OF PARTIAL PRESSURE: It states that, “The total pressure exerted by a mixture of non-reacting gases occupying a vessel is equal to the sum of the individual pressures which each gas exert if it alone occupied the same volume at a given temperature”, For n gases, P=R+P,+P+ Where P = Pressure exerted by mixture and 1, Pp,Py are Partial pressure of component gases. ROOT MEAN SQUARE VELOCITY OF A GAS: It is defined as the square root of the mean of the squares of the speeds of the individual molecules of a gas. If M4, Vp, Bg, ws, Vp are the speeds of the n gas molecules, then the r.m.s speed for the gas is given by pe + vd toh + te Vrms 1 7 We have, Pressure Clearly, Vrms & NT Thus, the r.m.s speed of the gas molecule is directly proportional to the square root of the absolute temperature of the gas. Ata given temperature, 1 Vrms © Hence for lighter gases, the r.m.s speed is comparatively high, as it depends inversely upon the square root of its molecular mass.KINETIC THEORY OF GAS DEGREES OF FREEDOM: The degrees of freedom of a system can be defined as the total number of independent ways in which the particles of the system can absorb energy. The number of degrees of freedom of a system is equal to the total number of coordinates required t specify the positions of the constituent particles of the system minus the number of independent relations existing between the particles, Le. f=3N-k Where N = number of particles in the system, k = number of independent relations between the particles. a) Degrees of freedom of a mono-atomic gas: The molecule of a mono-atomic gas like He, Ne, Ar etc., consists of a single atom, it is capable of translatory motion only. So it has THREE degrees of freedom. b) Degrees of freedom of a diatomic gas: The molecule of a diatomic gas like No, 2, He, CO etc., consists of two atoms, separated by a fixed —_ distance. Corresponding to translatory motion, the molecule has 3 degrees of freedom. The molecule has two additional degrees of freedom due to rotational motion. The total degrees of freedom are FIVE. c) Degrees of freedom of a tri-atomic gas: Anon-linear tri-atomic molecule has SIX degrees of freedom. And a linear tri-atomic molecule has SEVEN degrees of freedom. LAW OF EQUIPARTION OF ENERGY: It states that, “In any dynamical system in thermal equilibrium, the energy is equally distributed amongst its various degrees of freedom and energy associated with each degree of freedom per molecule is$kgT, where kg Boltzmann's constant and T is is the absolute temperature of the system”. Consider one mole of a mono- atomic gas in thermal equilibrium at temperature T. A mono-atomic gas molecule has 3 degrees of freedom due to translatory motion. According to kinetic theory of gases, the average translational kinetic energy of a gas molecule is given by, gm? pheT if 02, UB, and ve are the components of mean square velocity of the gas molecules along the three coordinate axes, then Bakr e+e diet + mod + ima -3 2 pmol + 5 mij + 5mvp = FkyT As the molecular motion is random, there is no preferred direction of motion. So average kinetic energy of each molecule along a direction is same. 1 1 2 “2 =We write 1, 1-41-41 jmvd = 5mvy = mip = phe Thus, the average kinetic energy per 1 molecule per degree of freedom is = kg T 3, op = Kinetic energy of mono-atomic isp ksT. = Kinetic energy of diatomic is 5 kpT. oe Kinetic energy of tri-atomic is > kT" (non linear) and tke? (linear),KINETIC THEORY OF GAS ‘SPECIFIC HEAT CAPACITY OF GASES: In an ideal gas, the total energy of the gas or internal energy of the gas is equal to the total kinetic energy of all the molecules in the gas. a) Mono-atomic gas: The total energy is 3 3 U = ZNakeT = 5RT The specific heat at constant volume is ow _ 4 y= p= Since, C, — Cy The specific heat at constant pressure is 3 5 Cy = Cy +R=SR+R=2R ” 2 2 The ratio of the specific heat at constant pressure to that of the constant volume is C5 2 = =2=167 Yrar3 b) Di-atomic gas: The total energy is u= ink =2 = 3 Nake? = RT. 2 The specific heat at constant volume is qu 4 Gar) Sp 6 =f as ° "ar dr Since, Cy —Cy =R The specific heat at constant pressure is 2 5 7 Gy =G +R=FR+R=5R The ratio of the specific heat at constant pressure to that of the constant volume is (For non-linear tri-atomic) The total energy is U = 3NgkgT = 3RT The specific heat at constant volume is qd Co = Gp = gp GR Since, Cy - Cy =R The specific heat at constant pressure is yp = Cy, F+R=3R+R=4R The ratio of the specific heat at constant pressure to that of the constant volume is & 4 _ yang 133 (For linear tri-atomic) The total energy is Tet = RP U =D Nake? = ZR The specific heat at constant volume is Since, Cy — Cy = R The specific heat at constant pressure is 7 9 p= G+R=ZR+R=5 The ratio of the specific heat at constant pressure to that of the constant volume is d) Polyatomic gas: (f is total degrees of freedom of each molecule ) The total energy is Li U=ZNake? = 5 RT The specific heat at constant volume is dae f ¢, = = (Crt) =oR °F al; ) 2 Since, Cy — Cy =R The specific heat at constant pressure is & c+rafere=(+1)e 2 The ratio of the specific heat at constant pressure to that of the constant volume is =o. G*) 2 Or yeastKINETIC THEORY OF GAS ‘SPECIFIC HEAT CAPACITY OF SOLIDS: In a solid, the atom has only vibrational modes along three mutually perpendicular directions. Since each vibration mode contributes two vibrational degrees of freedom, the energy in the vibration mode is 2 x Fket = kg. Therefore, in three dimensions the average energy of each atom is 3kgT. For N atoms the total energy is 3NkgT. For one mole of a solid, N= Na, Then, then total vibrational / internal energy is U = 3NgkpT =3RT kg = Ry, At constant pressure, dQ = dU + Pav =~ aU dV is negligible in solids. Specific heat capacity of the solid is, dQ_ dU _d@RT) Oo a at a The specific heat of most of the solids at room temperature at constant volume is 3R or 25 J mole* K* The temperature at which the molar specific heat of a solid at constant volume becomes equal to 3R is called Debye temperature. ‘SPECIFIC HEAT CAPACITY OF WATE! We may treat water as a solid. By the law of equipartition of energy, the average vibrational energy per atom is 3kgT. Water molecule has three atoms, and then the average vibrational energy per water molecule is equal to 3X Bk pT = 9kg? The total vibrational energy of one mole of water molecules, U = Ny X 9kpT = ORT ‘At constant pressure, dQ = dU + Pav = du Specific heat capacity of the water is, dQ_ dU _d(9RT) ar dT aT The specific heat capacity of the water is nearly equal to 75 J mole K7, OR MEAN FREE PATH The mean free path of a gas molecule can be defined as the average distance travelled by the molecule between ‘two successive collisions. DERIVATION: ‘Assume that each molecule of a gas is a sphere of diameter d and except the molecule-A remaining molecules are considered to be at rest. Suppose the molecule-A has average velocity # and it will collide with all those molecules whose centres lie within a distance d from its path. In time t, it will collide with all those molecules in the cylinder of volume md? vt. Let n be the number of molecules per unit volume. The number of collisions suffered by the molecule =n x nd2vt Mean free path of a gas molecule, distance covered in time t number of collisions suf fered _ at 1 = pdt = az D Considering all the molecules of a gas are to be in motion the above equation can be modified to,KINETIC THEORY OF GAS = 1 = (2. V2nnd? ® This is the required expression for mean free path a gas molecule. NOTE: If mis the mass of each gas molecule then, m V2nd?p For one mole of a gas, 4) Factors on which the mean free path depends, (1) Directly proportional to the mass of a gas molecule. (2) Inversely proportional to the density of the gas. (3) Inversely proportional to the square of the molecular diameter of gas. (4) Directly proportional to the absolute temperature of the gas. (5) Inversely proportional to the pressure of the gas. 1/2/3/5 MARKS QUESTION! 1. Mention any one measurable property of gas. 2. On what factor does the internal energy of a gas depend on? 3. On what factors does internal energy of the gas doesn’t depend? 4. Define degrees of freedom, 5. How many degrees of freedom 2 mono atomic and diatomic gas molecule possesses? 6. State the law of equipartition of energy. 10, 11, 12, 13, 14, 15, 16, 17, 18. 19, 20. 21. 22. 23. 24, 25. 26. 27. 28. Mention any one measurable property of gas. What is the value of ratio of specific heats for a mono atomic and di-atomic gas molecule? Write the general formula for ratio of specific heats for poly atomic gases. What is the value of universal gas constant R? Write the equation connecting Cp,Cv & R. Draw P-V curve or diagram for Boyle's law and for Charle's law. Show that specific heat of solids C=3R What are the important characteristics of an ideal gas? State and explain Boyle’s law. State and explain Charle’s law. Write the perfect gas equation and explain the terms. State and explain Dalton’s partial pressures. Write the equation for mean free path and explain the terms. Explain the term free mean free path. Deduce the expression PV=nRT. Determine the specific heat capacity of a mono atomic gas molecule. Determine the specific heat capacity of a diatomic gas molecule treated as a rigid rotator. Apply law of equipartition of energy to a monoatomic gas explain. Mention assumptions of kinetic theory of gases. Derive an expression for pressure of an ideal gas. From kinetic theory of gases explain the kinetic interpretation of temperature. Define mean free path and hence derive the expression for it. law of molecule and