UNIT

HEAT

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1.1 KINETIC THEORY OF GASES
1.1.1 Introduction
Molecules have a diameter of the order of 2 Å and the distance between them in a gas is 20 Å while the interaction distance in solids is very small. R. Clausius and J. C. Maxwell developed the mathematical concept of the random motion of the gas molecules in a gas which helped to explain not only the properties of gases but also that of free electrons in metals.

1.1.2 Postulates of Kinetic Theory of Gases
1. A gas consists of a large number of minute particles known as molecules of the same size and mass. 2. The interaction between molecules is negligible unlike solids. 3. The molecules in a gas are in a state of random motion in all directions with different velocities ranging from zero to infinity. 4. The size of the molecules is negligible in comparison with the volume of a gas. 5. During the motion, molecules collide with each other which is perfectly elastic. 6. The impact of molecules on the walls of the container exerts a pressure. Pressure of a gas is the average force per unit area of the molecules on the walls of the container during impact. Larger the number of impacts, greater will be the pressure. 7. Due to random motion of molecules in gas, the molecules have kinetic energy. The average kinetic energy of a gas molecule varies as absolute temperature. According to kinetic theory of gases, the molecules of a gas are in random motion. So, the average velocity of the molecules is zero. Hence we find the rms velocity of a molecule.

c3. Hence root mean square n velocity of a molecule is c rm = 2 2 2 2 c1 +c2 +c3 + . y and z.. Momentum of the molecule D before collision is mv and the momentum of the molecule after collision is equal to −mv. . Let m be the mass of the molecule and n be the total number of molecules in this cubical vessel of volume 1 m3..3 Pressure Exerted by a Gas Let us enclose a gas in a cubical box of dimension 1 metre. It hits the wall B with a velocity v and rebounds with the same velocity v as the collision is perfectly elastic.. c = 2 2 2 c1 +c2 +c3 + . the mean square 2 velocity of the molecules of the gas is. Since there are only three independent directions x.2 Engineering Physics Vol. For v metre it will undergo v = mv 2. Thus force exerted by the single molecule on the wall B = change in momentum × time = 2m v × A D B Fig. Thus change in momentum of the molecule on the wall B due to a single collision of the molecule D is mv − (−mv) = 2mv. All the n molecules in the cubical vessel are not moving along the x-axis between the walls B and A. 2 2 collisions v (in a sec)... c n n 1.1. II If c1. Consider a molecule D moving in the x-direction with a velocity v towards the wall B. 1. c2. . cn are the velocities of the molecules of a gas at any instant.1 We shall now consider the combined effect of collisions of all molecules on the wall B.. In 2 metres the molecule undergo 1 collision. it is reasonable .

Being the area of the surface B is 1 sq...Heat 3 to assume that. there may be tween walls B and A. ⎛1⎞ P = ⎜ ⎟ m nc 2 ⎝3⎠ Since m is the mass of the molecule and n is the number of molecules per unit volume of the gas. P= Further discussion is possible by choosing unit volume or molar volume (Vm). then 2 2 2 2 c 2 = c1 +c2 +c3 + . force exerted by the molecules on the walls B = m nv 2 . m.. at any instant.. n molecules moving along the x-axis be3 1 3 Therefore. Hence it is reasonable to substitute c 2 . cn are the velocities of the molecules at any instant. NA . c2.e. If c1. for v2. the pressure exerted on the wall B is P= 1 m nv 2 3 But all molecules are not moving with the same velocity.. where R is universal gas constant. the mean square velocity of the molecule. c n Therefore. Let us consider one mole of a gas which occupies a volume Vm. Thus 3 mc 2 = 3RT = 3k BT NA as Boltzmann constant k B = R . then ρ= mn 1 1 2 ρc 3 i. The pressure exerted by the gas is P= PVm = 1 m N Ac 2 3 Vm 1 m N A c 2 = RT . . c3. .

E . µ T. of the gas is proportional to the absolute temperature.4 Engineering Physics Vol. Hence. PV µ T.E.. it is obvious that at constant temperature PV = constant or V µ 1 ..E. If M is the mass of a given gas with V as the volume.. Let P. This is Boyle’s law. 2 1 2 1 2 M c 2 = × M c 2 = × K . V. 2 Conclusion: Let us consider any amount of a gas. K. Conclusions (a) At constant pressure [from Eqns. temperature and number of the molecules of the gas.(3) or PV = nk BT . average kinetic energy of one mole of the gas is 1 3 3 m c 2 N A = N A k BT = RT 2 2 2 . of the gas = then PV = = 3 nk BT . II or 1 3 m c 2 = k BT 2 2 . of the gas 3 3 2 3 2 3 × nk BT 3 2 ..1.E.. P (ii) Since K. of a molecule of the gas is 3 K. of a molecule of a gas = k BT 2 Hence.E. This is Charles second law. This is Charles first law (b) At constant volume P µ T. T and n be the pressure..4 Boyle’s Law and Charles Law (i) Kinetic energy of a gas is directly proportional to the absolute temperature. Hence from equations (1) and (2). ...(4) 1.E. It is now evident that K.(2) 3 k BT or K. 3 and 4] V µ T. from equations (3) and (4). volume.(1) This is kinetic energy of a molecule.

there is a flow of heat from the hot body to the cold body until both attain a common temperature. Specific heat of some substances Substance Water Aluminium Copper J kg−1 K−1 4200 378 924 kJ kg−1 K−1 4. The unit is joule per kg per degree kelvin (J kg−1 K−1). In S.5°C. Since heat is a form of energy it is measured in joule. . Specific heat capacity of a substance (C): It is the quantity of heat required to raise the temperature of the body by one degree kelvin. Calorie is the unit of heat in C. Q=mCθ Method of mixtures: When a hot body is allowed to share its heat with a cold body. if no heat is lost to or gained from the surroundings. Then.1 Measurement of Heat and Unit of Heat Heat is a form of energy. The dimension is L2 T−2 K−1. Heat capacity of a body: It is the quantity of heat required to raise the temperature of the body by one degree kelvin. . i.378 0. Water was taken as the standard substance for defining heat units. then quantity of heat Q required to raise the temperature through θ° is m C θ i. Usually quantities of heat is measured by the effect they produce. It is defined as the quantity of heat required to raise the temperature of one gram of water through 1°C from 14. 1 Calorie = 4. water equivalent (in kg) = Heat capacity of the body .e.924 J gm−1 K−1 4. unit.378 0.924 Water equivalent: Water equivalent of a body is the mass of water having the same heat capacity as the given body.S.2.2 0. then Heat lost by the hot body = Heat gained by the cold body. in the same way as other forms of energy.I.2 0. the unit of heat capacity of a body is joule/kelvin = J/K. C is the specific heat.2 joule.Heat 5 1.e.G.5°C to 15.. Specific heat of water Quantity of heat: If m is the mass of the body.2 SPECIFIC HEAT 1. unit.

6 Engineering Physics Vol.2 . 1. molar specific at constant pressure can be stated. Hence CP > CV. The unit of specific heat is J kg−1 K−1. the heat supplied is utilized only to increase the internal energy of the gas. For the same temperature. the heat supplied is used not only to increase the internal energy but also doing work during expansion. 1. (ii) CP: The specific heat of a gas at constant pressure is the amount of heat required to raise the temperature of unit mass of the gas through one degree kelvin keeping its pressure constant. II 1.2 Specific Heat of a Gas at Constant Volume and at Constant Pressure (i) CV: The specific heat of a gas at constant volume is the amount of heat required to raise the temperature of unit mass of the gas through one degree kelvin keeping its volume constant. Thus the amount of heat required to raise the temperature of one mole of the gas through one degree kelvin at constant volume is called molar specific heat at constant volume (CV). But when it is heated at constant pressure. Why CP > CV?: When a gas is heated at constant volume.2. the increase in internal energy is the same in both cases. As discussed above. dV P V T Fig.2.3 Mayer’s Relations (CP − CV = R) Consider one mole of an ideal gas enclosed inside a non-conducting cylinder with a light smooth piston.

Heat 7 Let P be its pressure. Density of air at STP = 1.e. T = 273 K. CP = CV + external work . W = F × S = P × A × dx = PdV where A is the area of cross-section of the piston and A × dx = dV is the increase in volume of the gas.. . Therefore. let the gas be heated so as to raise its temperature by one degree kelvin. V its volume and T its temperature. ρ = 1.293 × 273 . or PV + PdV − PV = RT + R − RT PdV = R CP = CV + R CP − CV = R This is the well known Mayer’s relation. Gas constant for 1 kg. R= R= PV P M 1 = as ρ = = T ρT V V 1. . Keeping the volume constant. An Example: Let us consider air at constant pressure with CP = 966 J kg−1 K−1. Now. P (V + dV) = R (T + 1) i. The quantity of heat supplied is given by Q′ = CP This amount of heat is partly used to raise the internal energy of the gas as the temperature raises by 1 K and also used to do external work as the gas expands to keep the pressure constant. Hence external work done by the gas. Q = CV This amount of heat is used only to raise.(1) When the gas expands keeping pressure cosntant.. the internal energy of the gas. Thus.e. let us imagine the gas be heated at constant pressure so as to raise the temperature by 1 K.. i.013 × 105 N/m2. equation (1) can be written as CP = CV + PdV . PV = RT After expansion.293 kg/m3.013 × 10 5 1. let the piston be moved through a distance dx. The quantity of heat supplied.(2) For an ideal gas..293 kg/m3. Get the value of R using PV = RT Pressure (STP) = 1.

Slow expansion of a gas enclosed in a perfectly conducting cylinder fitted with a perfectly conducting position.. then the total work done is V2 W = V1 V2 ∫ Pd V .303 × log ⎜ 1 ⎝ P2 ⎞ ⎟. Thus W = RT log e V2 . ⎠ Adiabatic transformation: The process that takes place in a system under thermal isolation. W can also be written as ⎛P W = RT × 2. 1. II R = 287 J kg K . V V V ∫ 1 Hence in an isothermal change R and T are constants. At constant temperature. ∫ but PV = RT or P = V2 RT V Thus. .e. The total work done in an isothermal expansion from volume V1 to V2 under the same conditions is W = P (V2 − V1). W = V1 RT dV d V = RT . V1 i.e. The expansion or compression of a gas enclosed in a perfectly non-conducting cylinder filled with a perfectly non-conducting frictionless piston. Since the system is thermally insulated no heat can enter or leave the system i. such that heat is not transferred from the system to outside or from outside to a system is called an adiabatic process.2. It means that there is no exchange of heat between the system and surroundings. If the pressure changes during the expansion. suppose a certain mass of a perfect gas undergoes an isothermal expansion by dV. then the total external work done is dW = PdV. dQ = 0.8 Engineering Physics Vol.4 Isothermal and Adiabatic Changes Isothermal Process: The process in which temperature is kept constant either by adding heat or taking heat away from a system is called isothermal process.303log ⎜ 2 ⎟ ⎝ V1 ⎠ P1V1 = P2V2 or P1 V2 = P2 V1 But Hence. ⎛V ⎞ W = RT × 2. .

W = V1 ∫ (k V2 V γ )d V W = k V − γd V = V1 ∫ k 1−γ 1−γ ⎡ ⎣V2 − V1 ⎤ ⎦ 1− γ Again. Thus. Since perfect isolation is not practically possible. PdV + VdP = 0 Pd V = −Vd P dP P =− dV V . then P1V1 = RT1 and P2V2 = RT2 W = R (T1 − T2 ) γ −1 Conclusion: The simple relation of isothermal change is PV = k Differentiating this equation we get. the physical changes should take place very rapidly so that heat produced during compression does not have enough time to leave the system and similarly during expansion heat does not have enough time to enter the system. the total work done when the volume changes from V1 and V2 is V2 W = V1 ∫ Pd V k Vγ For adiabatic change PV γ = constant or P = V2 Thus. When a certain mass of a perfect gas undergoes adiabatic changes. P1V1γ = P2V2γ = PV γ = constant = k W = W = 1 γ 1−γ γ 1−γ ⎡ ⎣ P2V2 − V2 = P1V1 V1 ⎤ ⎦ 1− γ 1 1 ( P1V1 − P2V2 ) [ P2V2 − P1V1 ] = 1− γ γ −1 If the temperature of the gas changes from T1 to T2 during the operation.Heat 9 Hence dU + PdV = 0.

What is Mayer’s relation? Dependence of K.1 1. the slope of adiabatic = −γ P V That is under same conditions of pressure and volume. of a molecule with temperature.2 1.7 State two important postulates of kinetic theory of gases.3 1.4 1.6* 1.E. .2 1. Explain Charles’ Law. II Thus the slope of the isothermal equation is − P dP = V dV The adiabatic relation is PV γ = constant. Give the unit of specific heat. we get Vd P + P γ d V = 0 or dP P = −γ dV V Hence.5 1. V γdP + P γV γ−1d V = 0 If V = 1.10 Engineering Physics Vol.1* 1. Explain. Explain why CP > CV. Differentiating this equation. Find the relation between PV and the kinetic energy of the gas. Two kilogram of water is heated to raise the temperature from 30° C to 40°C.6 Give the dependence of root mean square velocity on absolute temperature. the slope of adiabatic curve is γ-times that of isothermal formation. 2 Mark Questions 1. State Boyle’s Law. Boltzmann constant and absolute temperature. SHORT QUESTIONS 1 Mark Questions 1. Discuss the principle of method of mixtures.4* 1. Compute the heat energy supplied in joule.3 1. The quantities required to measure the amount of heat in an experiment.5 1. Write down the relation connecting kinetic energy of a molecule.

1.2 ( a ) Discuss the pressure exerted by a gas and obtain an expression for the pressure using kinetic theory of gases. ( b ) Derive the expression for kinetic energy of a gas.4 ( a) Explain isothermal expansion and obtain the expression for the work done during this process. 1.1 ( a ) Bring out the important postulates of kinetic theory of gases.E. This is Charles’ second law. Similarly at constant volume P µ T. REVIEW QUESTIONS 10 Marks Questions 1. (ii) Due to random motion of the molecules in a gas.4* Since K.V µ T. ( c) At STP. PV µ T i. What is the percentage change in pressure? . At constant pressure. ( b ) Obtain the expression for the pressure exerted by a gas in a cubical box in terms of the density of the gas and root mean square velocity. In this case m = 2 kg.3 ( a ) Explain specific heat of a gas at constant volume and constant pressure ( b ) Obtain Mayer’s relation. Thus. This is Charles’ first law. ( c) Explain why Cp > CV ? 1. ( b ) Show that for an adiabatic change in a perfect gas.1* (i) The molecules in a gas are in a state of random motion in all directions with different velocities ranging from zero to infinity. The average kinetic energy of a gas molecule varies as absolute temperature. calculate the value of R using the equation PV = RT. 1. Q = m s θ = 2 × 4200 × 10 J Q = 84000 joule.Heat 11 ANSWERS TO STARRED QUESTIONS 1. ( c) A quantity of dry air at 27°C is compressed slowly to (1/3) of its original volume. PV γ = constant. ( c) Deduce Boyle’s law and Charles’ laws. s = 4200 joule kg−1 K−1 and θ = (40 − 30)°C. the molecules have kinetic energy.e.. of the gas is proportional to the absolute temperature.6* The general formula for heat lost or heat gained is ms θ. 1.

1 The ratio of specific heat capacity of helium is 1. pressure remaining constant.32 × 300 32 × 10 −3 c = 4. Solution: C P − CV = R CP = 1. 1 3 m c 2 = k BT 2 2 or 1 3 3 m N A c 2 = N A k BT = RT 2 2 2 where NA is Avogadro’s number and R is universal gas constant mN A = M A = 32 × 10 −3 1 3 M A c 2 = RT 2 2 c = 3RT = MA 3 × 8.29 = = 12. Given: R = 8.12 Engineering Physics Vol.29 J/K/mol.66 C V − C V = R = C V ( 1.66 − 1) = R CV = R 8. 1.32 J/mol-K.5 JK −1mol −1 0. Given: 8.66 0..66 or C P = 1. Let C1 and C2 be the velocities corresponding to T1 and T2.66.2 Calculate the RMS velocity of a molecule of oxygen at 300 K.83 × 10 2 m s Answer.66 C V = 12. the RMS velocity becomes double its value at T1 = 273 K.3 At what temperature. II PROBLEMS AND SOLUTIONS 1. 1. Calculate the specific heat capacity at constant volume and at constant pressure. Solution: The mean K.66C V CV Thus 1. .E.5 JK −1mol −1 Answer.

1.3 × 323 4 E = 2010. 1.02 × 1026 is the Avogadro’s number.00831 kJ/ mol-K. .4 Calculate the molecular energy of one gram of hydrogen gas at 323 K.Heat 13 Solution: c2 T = 2 c1 T1 2c 1 T = 2 c1 T1 or T2 =4 T1 T2 = 4 × 273 = 1092 K T2 = 1092 K Answer.02 × 1026 molecules. Find CV for hydrogen.e.5 Given CP = 24. R = 0.6 J Answer.3 J/mol-K. Solution: 2 × 10−3 kg of hydrogen will have 6. C V = 16.31 i. Given that the molecular weight of hydrogen is 2 × 10−3 kg and R = 8. The molecular energy is 1 3 3 N A × k 3T = RT 2 2 4 = 3 × 8.34 J mol-K Answer. 2 where NA = 6. 10-3 will have NA molecules. . Solution: C P − CV = R C V = C P − R = 24.65 J/mol-K for hydrogen.65 − 8.

V1 = V. .9 K Answer. Solution: m = 1 mol.e. V2 = V . the process is adiabatic P1V1γ = P2V2γ ⎡V ⎤ P2 = P1 ⎢ 1 ⎥ ⎣ V2 ⎦ γ = 1( 2 ) 1.7 Calculate the work done if one mole of an ideal gas expands isothermally at 127°C until its volume is doubled [R = 8. 1. V2 = 2V.13 J mol−1 K−1].31 × 400 × 2.30 × 10 3 J W = 2.4 × 10 3 calorie Answer. II 1. Express the answer in calorie. .4 −1 = 300 [ 2] 0. Solution: (i) P1 = P2 = 1 = atmospheric pressure V1 = V and V2 = V 2 During sudden compression.4 P2 = 2. Work done = RT log e (V2 V1 ) = 8. or W = 2. Find the final pressure and temperature.6 A quantity of air at 300 K and atmospheric pressure is suddenly compressed to half its original volume.4 T2 = 395.636 atmosphere.54 × 10 3 calorie 4⋅2 W = 5. T1 = 300 K and T2 = ? 2 T1V1γ−1 = T2V2γ−1 T2 = T1 [ 2] 1.30 × 10 3 = 0. (ii) V1 = V .303 × log 10 2 i.14 Engineering Physics Vol. T = 400 K.

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