Kinetic Theory of Gases Thermodynamics for M.Sc. Entrance ItT-JAM | JNU | TIFR | JEST | BHU | ISM | NCASR |.DU: First Edition : November. 2045: Second Edition : duly 2017. CAREER ENDEAVOUR PUBLICATIONS has taken due care in collecting the data and providing the solutions, before publishing this book. inspite ofthis, if any inaccuracy or printing errors are there, CAREER ENDEAVOUR PUBLICATIONS owes no responsibilty. CAREER ENDEAVOUR PUBLICATIONS will be grateful if you could point out any such error Your ‘suggestions wll be highly appreciated, © All right reserved by CAREER ENDEAVOUR PUBLICATIONS. No par of this book may be reproduced or utilized in any form without the waitten permission from the publisher. ees Regd. Office: 28-A/11, Jia Sarai, New Delhi-16, Ph: 011-26851008, 26861009 E: info@careerendeavour.in, W: www.careerendeavour.inTABLE OF CONTENTS CHAPTER 01: KINETIC THEORY OF GASES Postulates of Kinetic Theory Pressure Exerted by a Gas Molecular Speeds Distribution The Maxwell-Boltzmann Distribution Degree of Freedom Law of Equipartition of Energy Mean Free Path Problems to be Played 01-21 OL 02 07 07 14 15 18 20 CHAPTER 02: THE GAS LAWS & THE FIRST LAW OF THERMODYNAMICS The Gas Laws Different Types of Temperature in Thermodynamics Terms in Thermodynamics ‘Types of Walls Zeroth Law of Thermodynamics Intemal Energy Work Heat Sign Convention First Law of Thermodynamics Application of First Law of Thermodynamies Bulk Modulus or Incompressibility Isothermal Compressibility Coefficient of Volume Expansion Problems to be played CuapTeR 03: THE CARNOT ENGINE The Camot Engine ‘The Heat Engine Refrigerator and Heat Pump ‘Negative Temperature Camot Theorem Problems to be Played 22-52 22 28 29 30 31 31 31 32 33 33 36 47 47 47 49 53-64 33 55 59 60 61 63Chapter 04: THE ENTROPY & THE SECOND LAW OF THERMODYNAMICS Entropy Change in Entropy in Some Processes Change in Entropy in Conversion Processes ‘Temperature-Entropy Diagram The Second Law of Thermodynamics The Third Law of Thermodynamics Problems to be Played Change in Entropy in Terms of Different Parameters 65-82 65 67 72 74 16 8 B 79 CHAPTER 0S: THERMODYNAMICS POTENTIALS & MAXWELL RELATIONS «Thermodynamic Potentials © Maxwell Equations * Problems to be Played ‘CHAPTER 06 : THE PHASE TRANSITION ‘© Clausius Clapeyron Equation © Phase Transition © Triple Point * Problems to be Played Cuaprer 07: STATISTICAL MECHANICS Fundamental Concepts and Theorems Micto-canonical Ensemble The Canonical Ensemble Classical and Quantum Statistics Problems to be Played APPENDIX-I: SPECIFIC & LATENT HEATS APPENDIX-IT: THERMAL EXPANSION APPENDIX-II]: THERMAL CONDUCTION APPENDIX-IV: BLACKBODY RADIATION APPENDIX-V: JOULE THOMSON EXPERIMENT 81-96 81 87 95 97-105 97 99 103 105 106-135 106 ML 114 126 134 136 137 140 142 144Kinetic Theory of Gases Suppose a container with volume V containsa very large number N of identical molecules, each with mss m. ‘Then, the kinetic theory postulates the following, (1) The molecules behaveas point particles that are srrall compared to the size of the container and to the average distance between molecules. (2) The molecules are in constant motion. Each molecule collides occasionally with a wall ofthe container. These collisions are perfectly elastic, (3) Theres no force of attraction among the gas molecules and between the gas molecules and walls ofthe container. (4) The container walls are rigid and infinitely massive and do not move. (5) The molecules. obey Newton's ‘slawofmotion. - 7 Meaning of elastic collision Ifa molecule with velocity eens ane tamaee ‘+ Velocity component parallel to wall (component) does not change, ie., ¥, = *+ Velocity component perpendicular to wall (x-component) reverses direction, ie., v, =—u, Ha. Note : We will follow these notations throughout the book. N=Number of molecules in the gas, n= Number of moles in the gas 1, =Avagadro number where [W=aN, + Speed v does not change, ie,Kinetic Theory of Gases ted by a C During collisions, the molecules exert forces on the walls of the container, this is the origin of the pressure that the gas exerts on the wall of the container. +} v.41 Total number of motecules tht elie, with ine interval dt = Number of molecules with 1a A during ti base area Aand length |v,|dr wack aeee GIDE where volume ofcylinder= A[v,|d¢ Assuming uniform distribution of molecules, number of molecules in this cylinder = (E) able On the average, half of these molecules are moving towards the wall (that causes pressure) and halfare moving away from it. ‘=> Number of collision with A during dt = HE) Aly,|at) (2) Due to all molecules inthe gas, the total momentum change during dt is dp, = (No.of collisions)x 2m|y,| 1(N ~3( Flee) amt | PY = 3, (9) ‘Comparing will deal ges equation PV =nRT which is based on experimental studies of gas behavior, we have K,=3nRT |; T= absolute temperature (10)Kinetic Theory of Gases “This is average translational kinetic energy of n’ moles of ideal gas which clearly shows that translational Kinetic energy depends only on the temperature of the gas. Now, average translational kinetic energy of a’ single molecule @ K,,_3nkT “Non ay where n= nN, (12) K,_3(R So, Ha3(A)r 3) R Theratio Fy, occurs requently in molecular theory. Is called Boltzmann's constant ky. 8.314 J/mol-K R es 381K 10™ Sh a Wy, 6102210” molecules/mol /molecules-K => k= So, average kinetic translational energy ofamolecule= vie Molecular Speeds The average translational kinetic energy is equals to 1 the average translational kinetic energymust also be equals to am Va So, where, Mis the molar mass ofthe gas and is equal to mN,. Problem: Why there is hardly any hydrogen gas (H,) in the earth’s atmosphere, despite its being the most common element in the universe? Soln. Molar mass ofhydrogen gas, M =2%107 kg BRT _ [3x8.314%300 io * Yams. = a7 ee '=300 K (room temperature)] = 1.934 km/sec sizeable fraction of H, molecule in the atmosphere would have speeds greater than the earth’s escape of 11.2 km’sec. On the other hand, the heavier, slowly moving gases, can't escape so easily which is why they predominate in ‘our atmosphere,Kinetic Theory of Gases Soin. Soin. Soln. @ Problem: At room temperature, the rms speed of the molccules ofa certain diatomic gas is found to be 1930 ms, The gas is @H, ®F, (0, @a, [NT-JEE : 1984] BRT Vs foe m= VM Room temperature 7 = 300 K 3x 8.31x 10" x300 M M=2.0 g/molor the gas is H,. Correct option is (a) 1934 Problem: What is the average translational kinetic energy ofa molecule in I mole ofa gas at 27°C? (@) 6.21x10"F (621K 107J ©) 6.10PM =—(d) 6.21 x 10) Given: T= 27°C =300K Avgerage K, permolecule = kgT =Zxr3ex10 300 =6.21x107 5 Correct option is (a) Problem: Five gas molecules chosen at random are found to have speeds of 500, 600, 700, 800 and 900 m/s? What is the rms speed and average speed? @) »,,=700 ms and v,=714 m/s (©) v,.771.4 as and v,= 70.4 m/s © Vpq7714 ms and v,, = 700 m/s © M4y570.4 mls and v,= 71.4 m/s Given: 4 = 500 mvs, vp =600 mvs, v5 =700 mV/s, vg =800 m/s, vs =900 m/s & = 700 m/s, FADE 500 +.600-+- 700800900 2 2 2 2 yo yu and Yona =| 2 (Sense toe oor) =714.14ms Correct option is (c) Problem: Assuming that the hydrogen molecules have a root-mean-square speed of 1270 m/s at 300 K, calculate the rms at 600 K. @ 179.6mis (©) 1796 ms © 2796 mis © 279.6 mis Given: (Yzme)1 =1270 m/s, 7; =300K and (Yems.)2 =? T= 600K = Yims) -£ smal VE Since, rms.Soin. Soin. Kinetic Theory of Gases Vena. dt = V2 x 1270 =1796 m/s. = Cems d2 i Correct option is (b) Problem: One grammole of oxygen at 27°C and one atmospheric pressure is enclosed ina vessel. (@) Assuming the molecules to be moving with v,. find the number of collisions per second which the mol- coules make with one sqaure metre area ofthe vessel wall. (b) The vessel is next thermally insulated and moved with a constant speedy, Itis then suddenly stopped. The process results in arise of the temperature of the gas by 1°C. Calculate the speed v,, [IIT-JEE : 1983] BRT _ [3x83ix300 = REX [BX 831 300 | 493.4 més vm = Vg 32x10" re Given, P, = 1.01 x 10° Nim? =Foree per unit area, Let n molecules of oxygen strike the wall per second per 1m? and recoil with same speed. Change in momentum is (2am, ‘The change in momentum per unit time is the force. Hence, P, = 27mg xa = vee =1,96 «10"7/s ‘ms tae (483.4) 0) 5 (Og. = NCAT (2) (n=) & x 831) @ an, AT 2 =36 m/s can () G2107) Problem: A cubical box of side 1 m contains helium gas (atomic weight 4) ata pressure of 100 Nin?. During, an observation time of | s, an atom travelling with the root mean square speed parallel to one of the edges of the cube, was found to make 500 hits with a particular, wall, without any. collision with other atoms. Take, i= R= 25 nab K a Ren [ESE : 2002] 38 x TOP SK, (a) Evaluate the temperature of the gas. (b) Evaluate the average kinetic energy per atom. (©) Evaluate the total mass of helium gasin the box. Volume of the box = I m? Pressure of the gas= 100 Nim? Let Te the temperature ofthe gas. Then, (a) Time between two consecutive collisions with one wall = a .This time should be equal to 74, where isthe side of the cube. 7 => VY, =1000 mvs (as/=1 m) => 1000 Tr (1000)? _ (10)° (4 x10) 2 160K 3R 3(25/3) (1.38 x 10) (160) J= 3.312 x 10°" 3 (b) Average kinetic energy per atom => sT (©) From PY =nkT = RT M Wess massfilam sin tbo, m= 2 ‘Substituting the values, we get (400) (1) (4) (25/3) (160) COS TT ‘The molecules ina gas don’t have the same speed. We will study a function /(v) that will help us to know how a particular number of molecules possess a certain amount of speed. This function s called distribution function. Ifwe observe total N molecules, the number dNV having speeds in the range between v and v + dv is given by aN=N f(v)dv (17) intervalvto v+dy is Probability that a random chosen molecule will have a speed in F(a Mu Hence f(v) isthe probability per unit speed interval. Itisnot equal to the probability that a molecule has speed exactly equals to v. Since probability is pure number, (v) has units of reciprocal speed (s/m). = (18) PE ‘The function f(v) describing the actual distribution of molecular speeds is called the Maxwell-Boltemann distribution. Deriving from the statistical mechanics. itis equal to a S(»)= 4a Osv (sts) [ne m 4 2 = (ey) aesInetic Theory of Gases Either v=0 2k,T m ‘The speeds of the molecule can neither be zero nor infinite (as per as the assumption of the kinetic theory as the molecules are in constant motion with finite speed). So (22) (3) The rms speed (»,,,) Its the speed observed during the experiments and is given by (23) .. (24) ‘The graph representing ViqcsVayg» Yup | #0) Problem: A quantity of gas containing N molecules has a speed distribution function f (v). How many mol- ecules have speeds between v, and v, > v,? @ LFe)4-f Fo)ar wN[ FO)4-[ F0)e] (ar] Of Fo)a-[ rar aol frOe-fKinetic Theory of Gases Soln, Required number "NS (v)dr= af? Soar F0)4] Correct option is (b) Problem: Which of the inequality is valid for molecular distribution of gas? (@) Yong 2 F> Yip, (BY Vane > ¥en FC) Vg > Fra >¥ (A) Mang, > F > Ys y= BRE sy = [ART Soln. We know that, Yems. =z} Ymp. = yay NE =1.732:1.414:1.596 Vnp, =1-732:1.596:1.414 eer nM Clearly, ¥:ens.?¥mp. => Yems.* So, Yams. > 7 > Ymp, Correct option is (a) Another forms of Maxwellian distribution Itisgiven by S(v)ar= of =| ve ay (25) (@) Energy form Since cody =v ‘Using this in equation (25), roan) Bh = of 1 y le 2nkgr ~ 26) @) Momentum form Now, p=mv orv=2 m Using this in (25), Foyan=aa - ) 27) (2) Onk,F en T,, the qualitative temperature dependence of the probability distribution F() of the speed v of a molecule in three dimensions is correctly represented by the following figure: ti z E @ ti wn | g| + a eS E : © ©Soin, Kinetic Theory of Gases For N-particles system in thermal equilibrium, the number of molecules having speed between v to v-+dv - is given by m_)" Ba Po) F)dv = ar ‘(vy aos) e Tydy 2? * = Fv)=4nn| ey? and [Fodv=N T= constact 2nk,T ® and 9 = SEE y, = PEE PPT Tho 7 7m m m If we increase temperature, then ¥, V, and V,,. all will increase and particles have more values of velocities, More particles will distribute in large velocity region but total number of particles in the system will be constant (N). In F(v)Vs.v plot area under the curve remain constant. So on increasing the temperature, peak will decrease and shifted towards higher velocity side, ‘Correct answer is (a) Problem: Let 7, V, andy,,,, fespectively denote the mean speed, root mean square speed and most prob- able speed of the molecules in an ideal monoatomic gas at absolute temperature T. The mass ofa molecule is m. Then, (@) no molecule can have a speed greater than V2 v,,, (b) no molecule can have a speed less than v,/V2 (©) ¥, <7 < Vows 3 (d) the average kinetic energy of amolecule is qm ae __ [RORT_ [SRE faRT ee = RE ye [RRP A [PERE and y= M az M M a M From these expressions we can see that, V, ky?Soin. Soln. om . S Kinetic Theory of Gases This is the law of equipartition of energy + Average energy per molecule £, o=Lir (28) + Average energy per mole Ler [or R=kN,] ce u-n,2eT sia Problem: A system of N non-interacting classical point particles constrained to move on the two-dimensional surface of'asphere, The intemal energy ofthe system is 3 1 5 @ ghar ® ghar (c) Nk,T @ Nar Since, particle is moving on two-dimensional surface its degree of freedom=2 Hence, for N non-interacting particle total degree of freedom=2N ‘The energy per degree of freedom=1/2.k,T Hence, total energy U =2NxLk,7 2 => U=MkT Hence, the correct option is (¢). Problem: A system of N classical non-interacting particles, each of mass m, is at a temperature T and is 1 confined by the external potential ”(r) = Ar? (where A is a constant) in three dimensions. The internal energy ofthe system is 3 @ 3NK,T (5 Mar : mn genie Anya deal: a ie inyfdn( (© N(QmAy? kT b ini EON a ‘The contribution of thermal energy with each quadratic term in Hamiltonian is digr E 2 ‘The Hamiltonian of a classical particle H = 1 In 3-D, hamiltonian has 6 quadratic term. So, the intemal energy of a particle is 6% ky? = 3knT ‘The internal energy of a system of N particles = 3N,7. Correet answer is (a) Problem: A vessel contains a mixture of one mole of oxygen and two moles of nitrogen at 300 K. The ratio of the average rotational kinetic energy per O, molecule to per N, molecule is 7 @l:1 (b) 1:2 (2:1 (@) depends on the moment of inertia of the two molecules [ITE-JEE : 1998]inetic Theory of Gases Soln. soln, Average kinetic energy per molecule per degree of freedom = 1/24, Since, both the gases are diatomic and at same temperature (300 K), both will have the same number of rotational degree of freedom ie., two. Therefore, both the gases will have the same average rotational kinetic energy per molecule =2 x 1/2 k,Tor kT. Thus ratio will be 1: 1. Correct option is (a). Problem: A gas mixture consists of 2 moles of oxygen and 4 moles of argon at temperature T. Neglecting all vibrational modes, the total internal energy of the system is, (@)4Rr (6) 15 RT (ORT (@URT [IT-JEE : 1999] Internal energy ofn moles ofan ideal gas at temperature T is given by u= (Lar) legree of freedom. for O, and 3 for Ar where, Hence, U=Us, +0, -2{3zr) +-4{3er)=11Rr. Correct option is (d) Problem: Atagiven temperature, T, the average energy per particle ofa non-interacting gas of two-dimensional classical harmonic oscillator is AT. According to two-dimensional harmonic oscillator, we consider the vibration of molecules in two dimensions, Vibrational mode in one dimension provides k,7 energy. Intwo dimension, total energy is vibrational mol- ecules. Hence, 2 is correct answer=2 x (&,7') energy. Specific Heat Capacity + The “molar” specific heat at constant volume is (3), -P°CAREER ENDEAVOUR ~© + Also, the molar specific heat at constant pressure is Ig v en6+n-(Lae 30) + Also, the ratio of C, and C, is cG 2 ¥ ay o« 31) (1) Formonoatomic gas, (f =3) 3 3 sar; c,=2R; URDRT; Gp =5R Cy 2) For diatomic gas ( f = 5)Soln. Soln. Kinetic Theory of Gases 3) For triatomic non-linear gas (f = hi 6 6 24. Us2RT; C,=2R; C= SR yalte 1.33 2 2 6 3 (4) For triatomic linear gas (f = 7) 7 7 2_9 u=>. yasR C= oR =1+= 1.28 il CG z = y= lee a Problem: Consider oxygen gas at room temperature and pressure and assume that only translational and rotational motions of the molecules contribute to the specific heat. IC, and C, denote respectively, specific heats at constant pressure and volume, then the ratio C/C, is 2 3 a? Se : 2006} )3 OF @5 [11Sc : 2006} 2 Lf when is degree of freedom ‘There are two degree of freedom associated with rotational motion and three degree of freedom associated with translational motion, So, total number of degree of freedom associated with motion of diatomic molecule, f = 5 4 Hence, correct option is (a) 2 yalts So, ¥ 3 Problem: Keeping density and sound speed constant, doubling the pressure implies that the ratio of specific heatsC,/C, [ise : 2009] (a) doubles (hates (©remainsconstant (4) quadruples Velocity, v= 3 = 2 ) Keeping pand vs same and doubing pressure wilhalves 7 Hence, correct option is (b) ra In the assumption of kinetic theory of gases, we assumed that the molecules of gas are moving with very high velocity, which means, that molecules of gas contained in vessel should disappear in no time which i contrary to actual observation, because of absence of force to restrain their motion. Thus there was a serious objection against the assumption that the molecules ofa gas move with large rectilinear velocities. This difficulty was solved by the Clausius who assumed that the molecules ofa gas have a small, bt finite size. These molecule collide with one another after short intervals resulting in a change in both the magnitude and direction of the velocities ofthe molecules. Since there isno force acting on the molecules except during collision, they move in straight lines with constant speeds between two successive collision, Thus the paths of diffierent molecules is a series of short zig-zag paths of different length. These paths of different length are called the free paths ofthe molecule and their mean is called mean free path. ‘+ The mean free path is defined as the average distance travelled by a molecule between two successive collision. + Itisgivenby 1 + a ere w= (32) ‘where dis the diameter of the molecule and n isthe particle density ie, number of molecules per unit volume.Kinetic Theory of Gases Soin. Soin. Soln. 7 open Linsey . andy ~~ 33) kT + ae o where we have used PV = Nk,T’ * The collision time is defined as the time between two successive collision. It is equals to Al bt ie Vind Pv 2nd nv G5) where ¥ isthe average speed of the molecules + The collision frequency is defined as the number of collisions in one second. Itis equals to = V2 nd? nv + Note: The ¥ is usually taken to be v,,.- Problem: At what pressure will the mean free path be 50 cm for spherical molecules of radius 3 « 10m? ‘Assume an ideal gas at 20°C. From the expression for the mean free path we obtain, EEE Vala ——Wherd a =mean fee path Combining this with the ideal gas law in the form PV = Nk,T gi kel __(1.38x107S/.K)(293K) p=—sl _. = 5.1mP¢ 4nJ2B 4ny2G.0x 107 m)?(0.50m) i ( \ i Problem: A: what pressure will the mean free path be 50 cm for spherical molecules of radius 3 * 10-"*m? ‘Assume an ideal gas at 20°C. From the expression for the mean frée path we obtain. 1 N 1 fat mm € i Bee, wide REE fai Combining this with the ideel ges law in the form PV =Nk,T gives = Kel (1.381079 / KY(293K) te 4nJ2B — 4nV/2(3.0x10" my? 0.50m) Problem: Estimate the mean free path of molecule of airt 27°C and | atm, Model the molecules as sphere with radius r= 2.0 * 10° m, (@) 5.8 x 10m (6) 5.8 x 10*m (6) 5.8 10-"m, @5.8* 10" =27°C=300K, P=latm=1.013%10° Nim?, r=2.0x107° m kT V2na®P =5.8x10% m Given: ‘The mean fice path is A= » where d is the diameter of the molecules = 2r kgT alone P Correct option is (b) heTheory of Gases PROBLEMS For polyatomic gases such as hydrogen the corresponding degree of freedom would be (a) Two, three () Five, six (©) Three, nine (@) Three, four The ratio oftwo specific heats ofa diatomic gas is~ (a) 1.66 (b) 1.33 (© 1.40 (@) 1.52 If the degree of freedom of agasis, then the ratio of C, and C, is— 2 1 1 2n (i+ Ie Ola, Onn Ina gas the expression for the average speed of molecule is given by- w of o fe ‘Which ofthe following curves represents Maxwell's distribution law of speed of molecules? F F EX Speed. —> t 8 i Ors z No. of Molecules —> s No. of Moleenles —> | : ns Speed—> Speed—> ‘The gas exerts pressure on the walls of the container because the gas molecules (a) Have finite size (b) Obey Boyle's law (©Have momentum (@ Collide with one another The most probable speed v,, and the root mean square speed 'c are related by- eo: The speed of sound V, ina gas, nm.s. speed of the molecule ofa gas V,,,, and the ratio of specific heats y of the gas is related by @V,= Vous O)V,=VX TY OV, = Vint @V,= Vuinetic Theory of Gases ‘a 2 ‘The mean fice path is (2) Inversely proportionalto the pressure(P) _(b) directly proportional to the pressure (©) proportional to P? (@) proportional to P* ‘The correct expression for the most probable velocity of the molecules ofa gas in a steady state isgiven by @ @ rm.s. speed (b) equal to rms. speed 3y © ems speed @ @) rms. speed According to the kinetic theory of gases, pressure exerted by a perfect gas is equal to @ fmt , where vis average velocity (b)mgh © 3E, where E is the mean kinetic energy per unit volume of gas @allofthese Assuming the Maxwellian distribution of speeds for molecules of liquid also, at temperature below the normal boiling point ofa liquid 1. molecules with higher speeds escape from the surface ofthe liquid, 2. molecules with lower speeds escape from the surface 3. average kinetic enegy of the molecules is the liquid increases as evaporation proceeds 4, average kinetic energy decreases with evaporation (a) 2 and3 (b) Land 4 (oc) 2and4 (@ Land3 ‘Maxwell's law of distribution of speed show that the number of molecules with average speed is (@) Very small () large (©)zero @ exactly equal to 1. ‘The root-mean square speed of a particle of mass min the kinetic theory is given by yt Bk T BkyT eye oe oft oye Specific heats ofa gas at constant volume (C,) and at constant pressre (Cy arerelated as “Ag * Pye! 4a c R R MQry @Cr-Cy a Ifmolar C, = 4,97 cal/mole, then (@)C,=2.97 (0) C, = 1.97 @C,=0.97 1. @) 2 © 3. @) 4. 5. @ 3) 7. (b) 8 (@) 9% (a) 10. (a) 11. @) 12. (b) 13. (b) 14, (0) 15. (b) 16. (a)The Gas Laws & the First Law of Thermodynamics Sola. (1) Boyle’s Law: + “At constant temperature, the pressure of'a fixed amount (i.e. number of moles n) of gas varies inversely with its volume, Mathematically, Poe 7 (at constant T and n) ny = — [PY= Constant «= @) => RY=PY, -Q) where constant depends upon the amount of gas, temperatue of the gas and the units in which P and Vare expressed. + The variation ofpressure with volume and its inverse is, Each graph is called isotherm as temperature is constant in + Equation) => P= Constant; p> density of gas p = P=px Constant At constant temperature, pressure is directly proportional to the density of a fixed mass ofthe gas. Problem: A balloon is filled with hydrogen at room temperature. It will burst ifpressure exceeds 0.2 bar. [fat 1 per pressure the gas occupies 2.27 L volume, upto what volume can the baloon be expanded? Given: R=1bar, ¥/=2.27L and P,=2bar, Y=? Using Boylston, AY, = FAY > Ma = 2K = x 2a7 Lats Correct option is (a) Q) Charle’s Law: : + “For afixed mass of a gas at constant pressure, volume of gas is directly related to the absolute tempera- ture.”The Gas Laws & the First Law of Thermodynamics Soln. Mathematically, Vel 4) v or Constant 6) + Thevariation of volume with temperature in Kelvin and Celsius is (8) (1) Each Graphis called isobar as pressure is constant inall graphs. Q) Allthe lines meet the temperature aries at -273,15°C. Problem: On a ship sailing in Pacific Ocean where temperature is 23.4 °C, a balloon is filled with 2 L air. What willbe the volume ofthe balloon when the ship reaches Indian Ocean where temperature is 26.1 °C? @ 2018L (b) 20.18 © 0.20181 @ 2018L Given: Fj =23.4°C =(23.4+273)K =296.4K W=2L Ty =26.1°C = (26.14273)K = 299.1K =? Since the pressure during the sailing remains constant due to the atmosphere. pressure remains constant. So using Charle’s law, we have Kun ZB Tt 299.1 Vy = By, 299) APE 964 Correct option is (4) @)Avagadro Law + “Equal volume ofall gases under the same conditions of temperature and pressure contain the equal num- ber of molecules” Mathematically, Voc =>Von — [- N=nNn,] 6) Or, constant mO} ‘here number ofmoles = 7 where, w=Given mass W=Molar massThe Gas Laws & the First Law of Thermodynamics (4) Gas-Lussac’s Law: + “Atconstant volume, pressure ofa fixed amount of gas varies directly with the temperature.” Mathematically, — Pac T 3) P Or Constant =) + The variation of pressure with temperature is + Each graph is called isockore as volume is constant in all graphs, ‘The Ideal-Gas Equation: The three gas-laws are Ne P Boyle’slaw) V oc (Charle’s law) V on (Avagadro’s law) Combining, we have aT Vo _ Ral =e where R = Universal Gas constant => [PV=nRT This is called an ideal gas equation’, ARE a & Problem: A balloon will carry a total load of 175 kg when the température and pressure are normal. What load will the balloon carry on rising to a height at which the barometric pressure is 50 cm of mereury and the temperature is~10 °C, assuming the envelope maintains a constant volume ? @ 1195.0kg () 119.5kg (© 1195kg @ 1.195 kg Soln. Using 2 = constant, we have BT, y, 50,273 PM yy, = 29,23 says =1195 RE | 16263" keThe Gas Laws & the First Law of Thermodynamics Sola. GS Problem: A monoatomic gas is described by the equation of state P(V — bn) = nRT, where b and R are constants and other quantities have their usual meanings. The maximum density (in moles per unit volime to which this gas can be compressed is, ot > @: ©) infty Given : P(V —bn) = nRT Pv =Pbn=nRT => n=———_ = PV Pbn=nRT > => n_ P So density, p = Vo Pbh+aT Formaximumof p, dp _(Ph+nT)i- PO) aP (Pb+ nT) =P! ae Correct options (c) => nT =0 Problem: An ideal gas expands in a process in which its pressure depends on the volume as p = pye"™” , where p, and care two positive constants. Inv is the number of moles in the gas, the maximum temperature ‘that it will attain in this process is (R is the universal gas constant) @) poleanR * ©) pylan?R © ep,lanR @ pilanR [JNU : 2009) pape" so, r= PL re mR RR § oS ‘To maximise 7, take its derivative and make it equals 6 zero Plo ave" }=0 a Hence, correct option is (a)Soin. The Gas Laws & the First Law of Thermodynamics Deviation from ideal gas behavior: ‘A gas which obeys the gas laws and the gas equation PY= nRT strictly at all temperature and pressure is said to bean ideal gas. The molecules of ideal gases are assumed to be volume less points with no attractive forces between one another. But no real gas strictly obeys the gas equation at all temperatures and pressures. Devia- tion from ideal behavior are observed particularly at high pressures or low temperatures. The deviation from ideal behavior is expressed by introducing a factor Z known as compressibility factor in the ideal gas equation. Z may be expressedas z = 2% nRT + Incase ofideal gas, PY =nRT. +. Z=1 + Incase ofreal gas, PY # nRT. “Zeal CH, ' He i Ideal gas P + When Z 1, ‘behavior. Causes of Deviation from Ideal Behavior 1. The volume occupied by gas molecules is not negligible as compared to the volume occupied by the gas 2. The forces of traction between gas molecules are negligible. Problem: One mole of SO, occupies a volume of 350 mL at 300 K and $0 atm pressure. Calculate the compressibility factor of the gas. za PY _50%1.01 x10" 0,350 x10 RT 18.314 x 300 ‘Thus, SO, is more compressibility than expected from ideal behavior. is a positive deviation. It shows that the gasis less compressible than expected from ideal 0.71 Different forms of van der Waals’ equation 1, At very low pressure : V becomes so large that both b and a/V become negligible and the van der Waals’ equation reduces to (eS )o-o-ar= PV =RT Gases approach ideal behavior at very low pressure. 2. At low pressure : Vis large and ‘b"is negligible in comparison with V. Therefore, (peSlr=ar= pr += Rr = pyeRT—2 or ei —% or Pet v RT RIV RT ‘This accounts for the dip in isotherm at low pressure.“he Gas Laws & the First Law of Thermodynamics oin, 3. At fairly high pressure : He may be neglected in comparison with P, PV Pb Therefore, P(V —b) = RT > —=1+——>1 0 ~b)= RE = eal ep This accounts for the rising parts ofthe isotherm at high pressure. Hydrogen and Helium aretwo lightest gases known, Their molecules have very small masses. The attractive forces between such molecules will be extensively small So a/V? isnegligible even at ordinary pressure. Thus, 24 > 1, evenat low pressure. aT One litre of a gas at 300 atm and 473 K is compressed to a pressure of 600 atm and 273 K. The /compress- ibility factors found are 1.072 and 1.375 respectively at initial and final states. Calculate the final volume. RV, =2,nRT, and PV; = Z,nRT, PY By BV ZaTs 2 20%, * RAK 300 1375, 273 51 = 370.9 mL. 600 1.072 473 =r vander Waal Gas (The Real Gas) (1) Correction in pressure : Due to the presence of molecular attraction the molecule striking the wall of container is pulled back by the other molecules, and hence the observed pressure on the face of wall is less than the actual pressure within the body ofthe gas. The decrease in pressure p is proportional to + Number of attracting molecules / Volume. + Number of molecules striking per unit area of the wall ofthe container per second. Desreascingresure, pete os pack Real pressure =ptp= P+ 2) Correetion in Volume: Since the particles have finite size the volume left for the particles for their free movernent is less than actual volume ¥. If} isthe volume occupied by the size ofthe particle, then free volume =V —b So, from ideal gas equation PV= RT, we have (pS )y—o)=er Hai Form mole, (2S ern) = ner 02) Equations (11) and (12) are called vander Waal gas equation for one mole and n moles respectively.The Gas Laws & the First Law of Thermodynamics Problem: Areal gas behaves like an ideal gas ifits {@) pressure and temperature are both high (b) pressure and temperature are both low (©)pressure is high and temperature is low (@ pressure is low and temperature is high [MIT-JEE : 2010} Soin. A real gas behaves like an ideal gas at low pressure and high temperature, Henee, correct option is (4). pe (A) Boyle’s Temperature (T,) Itisa temperature at which vander Waal gas behave like an ideal gas. Ifat T =, , the Vander Waal’s equation i.e. PY = RT then Since b<< V, so (2) Critical temperature (Te) Its the temperature above which a gas can't be liquified by the application of pressure alone. ‘According to vander Waal gas equation (pe&)y—e)=ar => P= (¢) =e RT Now (av)... (V.—b) wy va (14) Again differentiating ap 2RT, 6a _ 9 AV Jaa Ve=b) Ve =a 2RT. = ee sy Ve Ve _ Ven Using 14), = 4=* = Ve=3d (15) ; a 2a-4b* ‘Using (15) in (14), To" TPR => (16) Using (16) in vander Waal’s equation reo ae where the critical pressure of a substance is the pressure required to liquefy a gas at itscritical temperature 3R Roam 2)The Gas Laws & the First Law of Thermodynamics > Problem: The equation of state fora gas is events [vo ( 8) Jo-o =NkpT, where, V, T,Nand kp respectively represent pressure, volume, temperature, number of atoms and the Boltzmann constant, respectively, while a and fare constants specific to the gas. Ifthe ertical point C corresponds to a point of inflexion ofthe p-V curve, then the critical volume V, and the critical pressure p,, for this gas are given by 2 @ a (@ %=3N, Pema Be (b) % =3BN, Pom ge B® ¥.=30N, p. = (© %e=3BN, pe ne @ %=3B: Pe ee Soln. Given [>+( 7 J Je -tor-angr ‘Comparing with vander Waals’ equation (oS) nby=ner or interms of number of molecules (N), (2:2 Jon) -igr wetwea=c?, bof So V, =3Nb=3NB pnw i { 276? 27p7 Correct option is (c) remem ms in Thermodynamics - Thermodynamies : It isthe branch of physics that deals with the concepts of heat and temperature and the inter conversion of heat and other forms of energy. + Itisa macroscopic science. It deals with bulk systems and doesnot go into the molecular constitution of matter, 2. System: According to Oxford dictionary, a system is defined as complex whole set of connected things or parts. ‘Thermodynamic systems: A definite quantities of substance bounded by some closed surface is known asa system. A system always interacts with the environment surrounding the system. Thus, surrounding has toplaya considerable/significant role in affecting the working ofthe system, 4. State ofa system: The quantities which are used to determine the characteristic of a systemare said to be the state of system,(a 30. aa The Gas Laws & the First Law of Thermodynamics “The equation connecting the pressure, volume and the absolute temperature of gas is called the equation ofstate of that gas. Mathematically the equation of state is represented as, F(PV,T) 5, Equilibrium : Ifthe macroscopic variables (P, V, T) that characterise the system do not change in time, the system is said to be in an equilibirium. (IFT isnot changing with time —> Thermal Equilibrium (ii IfP is not changing with time — Mechanical Equilibrium i Ifeomposition isnot changing with time -> Chemical Equilibrium 6. Quasi-statie process: A quasi-static process is defined as the process in which the deviation from thermodyanmic equilibriumis infinitesimal and all the state through which the system passes may beconsid- cred as the succession of equilbrium states ¢ g. ifa turbine is moved at infinitesimally slow rate, the system. is ata time in quiescent equilibrium state and then process can be considered quasi-static. 7. Reversible process : A reversible process is one which can be reversed in such a way that all changes taking place in the direct process are exactly repeated in the opposite order and sense and no changes are left in any of the bodies taking part in the process or in the surrounding, ‘The condition for reversibility : ‘A process can be reversible only when it satisfy two conditions () Process must be quasistatic (Ifthe process is performed in such a way that at any instant during the process the systemis very nearly in the thermodynamic equilibrium). ‘A quasistatic process is an idealised process in which all changes take place infinitely and slowly. Gi) Process must be non-dissipiative (dissipiative force such as friction, resistance, hysteresis etc must be ‘completely absent). Irreversible Process: Any process inevitably isan irreversible process because we always have some departure from initial system in carrying out the process again. Thus, those processes which producea permanent change in the thermodynamic state of the system and cannot be retraced in the opposite order are known as irreversible process. (1) Adiabatic Wall : [tis an insulating wall (can be movable) that does not allow flow of energy (heat) from one systemto another, Allpossible pairs (P,, V.) and (P,, Y») arein equilibrium. (2 Diathermal Wall :Itisa conducting wall that allows energy (heat) from system to another. After the exchange of heat, a new equilibrium state is achieved ie. (Pip Va)>(Fas¥a) => (Pie¥a) and (F5.%5)he Gas Laws & the First Law of Thermodynamics Zc er “It states that two systems in thermal equilibrium with a third system separately re in thermal equilibrium with each other.” ‘Suppose there are three systems A, B and C. Ifinitially, there is an adiabatic wall between A and Banda Glathermal wall between both A and C, and B and Cas shown in the figure. Then after some time, thesystems Aand B both willbe in thermal equilibrium with system C individually. Now, we have interchanged the adia batic and diathermal wall as shown in the figure below. Then, we observed that A and B are already in thermal equilibrium, c c ithermal > Adiabatic Wall A B Mie A B + Diathermal Adiabatic Wall atl + This law gives the definition of temperature, + Mathematically, if 7, = 7 and T, =Ty > 1,=T, ice, systemA and system B are also in thermal equilibrium + Temperature isthe marker of the hotness and coldness ofa body. + Heat flows ftom a body at high temperature to a body at low temperature. The flow stops when the temperature equalise ie. bodies come in thermal equilibrium. * _Itisthesum ofmolecular KE and PE in the frame of reference relative to which the centre of massof the system is at rest, * _ Itisastate variable ie, its value depends only on the state of the system and not on the path taken to arrive that state. For example, ifyouchange the volume first and then pressure through the path A or charge the pressure first and then volume through the path B, the change in internal energy between initial and final states remains same, UPD ue ¥) VAP, ¥9 wie %) AU, 2 = AU, + Itis defined as , 7 x w=|" Pav + Itisapath variable ic., depends on the path taken and given by the area in the PV-curve. ¥ wmThe Gas Laws & the First Law of Thermodynamics ee ee Vv v () Work done in anti-clockwise direction is positive and done by the system. @ Work done in clockwise direction is negative and done onthe system. Problem: A piston containing an ideal gas is originally in the state X (see figure). The gas is taken through a Pi thermal cycle X—> Y->Xas shown: t | * ve “The work done by the gas is positive if the direction of the thermal cycle is: @ clockwise (b) counter - clockwise (¢) neither clockwise nor counter-clockwise @ clockwise from.X->¥ and counter-clockwise from YX. Soin. Since work done = Area between P-V curve and volume axis For clockwise cycle, work done is W=area of shaded portion (in clockwise sense) area of XYBAX area of YXABY= positive Hence correct option is (a). a ‘+ tis thedefined as the flow of energy by virtue ofthe temperature difference, + Itisalso apath function. + IfAQ>0, heat is given to the system If AQ.< 0, heat is taken from the system.“he Gas Laws & the First Law of Thetmodynamics ~_ Se Wore w) = [*¥8 bY the system ork (W) = ve, on the system ++ve, given to the system Heat(Q) = (Q) ~ve, taken away from the system TALE oln, ain, + Itissimply the principle of conservation of energy applied to the system. + If AQ = Heat supplied to the system by the surroundings AW = Work done by the system on the surroundings Al ‘Change in internal energy of the system. then AQ=AU+AW (18) or dQ=dU+aw (19) where AW = PAV +» (20) => AQ=AU+PAr el) Problem: A thermos bottle containing cofive is vigorously shaken and thereby the temperature of coffee rises. considering the coffee as the system, which of the following is CORRECT: (@) AQ=0, AW <0;AU >0 (b) AQ=0;AW > 0;aU >0 (©) AQ=0; AW <0;AU <0 @ AQ=0;A7 >0,aU <0 Since no heat is given, AQ = 0. Also, the bottelis shaken and hence work is done on the bottle. => Aw0 [- aw L, dQ, =dU, + 47%, = Sar, = Ty) +160%10°(0.1- 0.03) Inprocess L — M, 3 dQ, = dU, + dW, = FRU -T)+0 Inprocess,M— J, dQ, = 3Rq, ~Ty)+80%10%(-0.07) = -8400 - 5600 =-140003The Gas Laws & the First Law of Thermodynamics Soin, Soln. Heat absorbed, dQ* = dO, +dO, =316007 Heat rejected, dQ = dQ, + dQ, =-26000F : Total work done _ 5600 _14 Efficiency= Total heat absorbed ~ 31600 79 Problem: When a system s taken from the state A to the state B along the path ACB, 80 Joules of heat flows into the system and the system does 30 Joules of work. (® How much heat flows into the system along the path ADB if work done is 10 J? (i)’The system is returned from state B to state A along the curved path. The work done on the system is 20 Joule. Does the system absorb or liberate heat and how much? (iil) HU, = 0, U,, = 40J. Find the heat absorbed in the process AD & DB Along thepath ACB, AU=AQ-AW = —U,-U,=80-30~50 @ Along the path ACD, AQ=AU+AW =(Ug~U,)+ AW =50 + 10 = 605 Gi) Along the curved path fromB to A, AQ=AU+AW =(U,—-Uy)+AW =(-50) + (20) So, liberated heat is 70 J ! (ii) Given: U, = 0,U, = 407 { Since, Ug—-U,=50 = Up = 50S Now, for the path DB, AW = PAV =0 | So, AQ=AU =U, Up =50-40=10F Now, forthe path AD, i A f AQ=AU+AW =(Up-U, FAW =(40'= 0) 10507 AW =10J (Given)] Problem: A vessel contains an ideal monoatomic gas, which expands at constant pressure when heat Q is supplied to it. Then work done in the expansion internal energy is a state function) 3 2 2 @Q ) 32 @52 @ 372 ‘The internal energy is au=car-Lrar=2Rar=3pav 2 2 2 where f=3 for monoatomic gas. Now from ist law of thermodynamic, Q=AU+ Pav PV =RT] > O=3 Pav + Par = Pav = ~2, Q=> Wao Correct option is (c)(1) Isothermal Process (AT = 0) Itis the process in which the temperature ofthe system is kept fixed throughout, E.g. () Melting oficeat meling point (ii) Vaporization of water at 100°C. + Ideal gas equation PY= constant += (22) + The graphs are P tT Tr a v ‘a + First Law of Thermodynamics says => dQ=dU+dW =C,dT+dW (23) where dU =C,dT (24) Since dT =0, dQ=dWw => Aitheat supplied to the system gets converted into the work. + Work done % %, aRT w=[opay=("™ ay frrar= [4 W = nRT tnt i = WankT tn | (25) or wenat of 2) ; (26) B + Iso thermal process are generally slo : (2) Isochorie process (AV = 0): ; Itisthe process in which volume remains constant. P Ideal gas equation => “7 = constant. The graphs are P v| P v T First law of thermodynamics gives dQ = dU + PdV Since dV =0, dQ => dQ=dU=CaT [: GQ (2)] v= (27)‘he Gas Laws & the First Law of Thermodynamics => Allheat given to the system is converted to the increase in internal energy. + Work done w=[" Pav =0 28) (3) Isobarie Process (AP = 0) + Itisthe process for which pressure of the gas remains constant. + Ideal gasequation => V eT or ce constant w= Q9) + The graphs are . Sori rentieaatiara dQ= ae += 30) where dO=C,dT 4 G1) + Work done, 17 = f Pav = ler P(W-K) 14 Problem: Figure fides Aueascktnet alta The net heat given to the system during the process is wo sfna(S)- np orfsn(i)-a-m] ——eoaea(}en-n] Jn. Since change in internal energy in a cyclic process is zero, the net heat given to the system is thetotal work. ie, AQ=aW = AO= Wig + Wayce + Wosy (isochore process) (Jothermal process) (Isobar process) oven i) Py %) = eto Zen —7 T= -#[no(%)-(n-n)] Correct option is (d).The Gas Laws & the First Law of Thermodynamics (4) Adiabatic Process (AQ=0): + Whena gas expands or contracts without exchanging heat with the surrounding, the process is called adiabatic process. + For this process, the system is insulated from the surrounding, + Mathematically, AQ=0 32) Equation govering is PY" =Constant (for ideal gas) + G3) ‘Also, nT yx Constant (PY =nRT) => TV" =Constant 84) Also, from equation (33), () = Constant => ~~ PT’ =Constant ++ 35) where 7=S2 2142 Gf + The graphs are eS = + First Law of Thermodynamics: dQ = dU + dW Since dQ=0, dW = = The workdoneby the gasisat the orpelos dits inset + Workdone we’ Say XE) nv l-y 1-y where K = RV; = P,V;)~constant of proportionality eR -R l-y = we Biz. A Bh yt Or + Adiabatic process are generally very fast e.g, the bursting ofa tyre.The Gas Laws & the First Law of Thermodynamics Soin, Soln. Soln. Problem: A motor car tyre has a pressure of 2 atomsphere at room temperature 27°C. Ifthe tyre suddenly bursts, find the resulting temperature. = 1atomsphere 2 y= 14 forair Py , We opp ys seal a alnet 1 (a Ly (Be =() (i) =(3) (35) Taking log both side, = 0.4 log 0.5 = 1.4 10g 7,~ 1.4 log 300 => — ~0.1204= 1.4 log 7, — 3.4680 => 3.4680 ~ 0.1204 = 3.3476 > 3476/14 = 2.3911 => 46.1 K =~ 26.9°C Problem: A quantity ofair at 27°C and atmospheric pressure is suddenly compressed to halfits original vol- ‘ume. Find the (j) pressure and (i) temperature. Given P,=1 atm, P, Also, TW = Tey wat | =300(2)"* = 395.9K =122.9°C Problem: Air is compressed adiabatically of halfits volume. Calculate the change in its temperature, Let the initial temperature be 7;K and finaltemperature 7;K Initial volume ¥, = Vand final volume V2 = For adiabatic process, 7/7! =7,yJ"1 ny" a ) or 1; =1,(2)"*"The Gas Laws & the First Law of Thermodynamics iD) ‘So change intemperture is T, ~T, =1.3197, -%, =0.3197K 3 Problem: | gm molecule ofa manoatomic (r = 3) perfect gas at 27°C adiabatically compressed in reversible process froman initial pressure 1 atmosphere to a final pressure of 50 atmosphere. Calculate the resulting difference in temperature. 5 join, Given: P= | atm, P,=50 atm, T, = 27°C = 300K, 7 = prt prt (RY (ny Us A oy |) a) sing or | ; en z\ 2 (ny poets 3 = (0) = (3) => 50? -(4) 2 5 5 = Flog50=5 log 7, ~5 log 300 = T= 1434K =1161°C Problem: Ifthe equation of state fora gas with intemal energy U's PY —5U then the equation for an adiabatic process is: @ py"? = constant (&) PV? = constant («) PY“? =constant (@) PY* = constant Soln. For adiabatic process, Integrating, log P = 4 log + constant => log PV*® = constant => or — PV*? =constant Hence, correct option is (¢). Problem: An ideal gas expands adiabatically but quasistatically from state i(P,V,T,) toa statef(P,V, 7). What is the change in its internal energy? ‘What would this change be if the expansion were isothermally? Soln. Ifthe process is performed in such a way that at any instant during the process the system is verynearly in the thermodynamic equilibrium, the process is called quasistasti, this means we can specify pressure, volume, temperature uniquely at any instant during such a process. Thusa quasistastic process isan idealised process in which all changes take place infinitely slowly. From first law dQ =dU+ dW But for adiabatic process dQ=0 SodU=-aWThe Gas Laws & the First Law of Thermodynamics Soin. f + tK Total change in internal energy= f, aU ~~ [Pay =— | av (- PVT =K => p=& v So for adiabatic isothermal process, the change in internal energy is zero. Problem: A monoatomic ideal ges, initially at temperature 7, is enclosed in a cylinder fitted witha frictionless piston. The gas is allowed to expand adiabatically to a temperature 7, by releasing the piston suddenly. 1fL, and L, are the lengths of the gas column before and after expansion respectively, then 7./T, is given by @ (L/L? ©) (G/L) (©) L/h, @ (L/L) UPSEE : 2000] During adiabatic expansion, we know Tv?" = constant or TY?" =T,VJ™ For amonoatomic gas, y = 3 (si), i ) (A= Area of cross-section of piston) Problem: P-¥ plots for two gases during adiabatic processes are shown in the figure. Plots 1 and 2 should correspond respectively to P v (@) He ando, (b) O, and He (0) Heand Ar (@) 0, and N, (WIE-JEE : 2001]2) jon. Inadiabatic process, PY? = constant aP Therefore, slope of P-V graph, > The Gas Laws & the First Law of Thermodynamics => slopecy —_(withnegative sign) From the given graph, (slope), > (slope), “Pn Therefore, 1 should correspond to O, (7 = 1.4) and 2 should correspond to He (y = 1.67) Hence, correct option is (b) (5) Cyclic Process + Tnacyelic process, the system retums to its intial state. + Since internalenergy isa state function, AU = 0 + First Law of Thermodynamics = AQ=AU+AW => SQ=AW Problem: Figure shows the process Aand B ona system. Let AQ, and AQ, be the heat given to the system in the process A and B respectively then (a) AQ, > AQ, (b) AQ, = 40, aw (d) AQ, < AQ, P v ‘Since AU is same for both the process and AJ is the amount of work which is represented by the area under the curve and since area under 4 is greater than area under B. AW, > AW, => AW, +AU > AW, +AU So AQ,>AQ, Son, Ifboth the arrow signs are changed then AQ, < AQ, (6) Free expansion + Inasystem say ifa gas expands in such a way that no heat enters or leave the system (adiabatic process) and also no work is done by or on the system, the gas is said to be expanded freely. + For free expansion, d= 0 and dW = PdV =0 (There is no pressure acting on the gas during free expansion) + First Lawof Thermodynamics => dU e.g, Ifinitally the gas is contained in half of the box and the other helfhas vacuum in it. When the separating layer is suddenly removed, the gas expands freely in the whole box. => Vaccum Separating layerhe Gas Laws & the First Law of Thermodynamics Problem: The internal energy of moles ofa gas is given by E font ~ 4 where Vis the volume ofthe gas at temperature T and a is @ positive constant. One mole of the gas in state (J;,%;) is allowed to expand adiabatically into vacuumto a final state (7;, V,). The temperature Ty is: rele 7) ain. Since the process is free expansion process. So the change in intemal energy for free expansion process is zero. => U,-U,=0 2af 1 I T=T+—4|-+ ESCH le i Hence correet options (c). Problem: Two gases separated by a impermeable but movable partition are allowed to freely exchange energy. ‘At equilibrium, the two sides willhave the same (@) pressure and temperature (b) volume and temperature (©) pressure and volume @ volume and energy In. Once the system is released freely, duc to exchange of energy both sides will attain thermal equilibrium by attaining the same temperature. Also, due to unbalanced pressure, both the sides will attain mechanical equilib- rium by balancing the pressure on both sides of the movable wall Hence correct option is (a). Problem: A thermodynamic system is taken through thecycle ABCD as shown in figure (i) Calculate the work done by the gas (system) during the path 4B, BC, CD, DA (i) Find the total heat rejected by the gas during the process ABCDA. PEP.) 200+ + 10+ f 4 ‘V{er’) 100 300 i) W, = PaV =100 kPa x 200 cm? (along 4B)Se : onl The Gas Laws & the First Law of Thermodynamics Soln. =100x1000x 220 74 - 29 y 10° m? Wy = Obecause the change in volume is zero. (along BC) W,=-PxdV -200 kPa x 200. cm* (along CD) == 200% 1000207 Pa 10° =-40s “The negative sign is due to decrease in volume W,, = Obecause the change in volume is zero. (along DA) W HW, +0, + Wy +W, =20-40=—20F (ii) dQ =dU + dw For cyclic process dU= 0 dQ = dW =-20J = Heat rejected by the gas Problem: When a systemis taken froma state ito falong the PKR) path iafas shown in figure. Its found that heat Q absorbed by the systems 50 cal and the work done by the system is 20 cal. Along the path ibf Q = 36 cal. * (@ what i the work done along the path ib?? a Ifthe work done onthe systems equalto 13 cal forthe curved returned path f. Whats the value Q for this path? (ii) Ifinternal energy of the system in inital state is equal to 1 Ocal. What isthe internal energy ofthe system in final state? (jv) Ifinternal energy ofthe system for state b= 22 cal. What are the values Q for the process bfand ib? Given U,=10 cal, Q=50cal_ and: W7=20 cal: for the pathiaf, we o > U, =40 cal So work done along path ibf, As dQ =36 dQ-adU+dw = dW=dQ-dU=36 - (40-10) =6 cal 3 cal for (f > i) Ww: 13 cal dQ-aU+ aw =(U-U)-1 Gi) AU =30 > UU, > U,-10= 0 => U, 40 () —-U,=22 cal, U,= 40 cab So for path bf => U,-U, = 18 cal 30-13 =~ 43 CalThe Gas Laws & the First Law of Thermodynamics Soln, Soln, AS AW =6 {. i> b, AW =0} dQ=18+6=24cal For bath i -» U,=22cal_ U,=10cal AU =l2cal, AW =0, AQ=AU+AW => AQ=12 cal Problem: A given quantity of gas is taken from the state A C reversibly, by two paths, A —> C direetly and A~> BC asshownin the figure below. Pp a a Vv During the 4—>C the work done by the gas is 100 J and the heat absorbed is 150 J. Ifduring the process A> BC the work done by the gas is 30 J, the heat absorbed is: (@203 (b) 80 (©2205 (@) 2803 UsingdQ = dU + d¥V, ForpathaC: 1503=dU+ 1003 = dU = 1503-1003 = 503 For path ABC: dQ = dU + dW,= 503 + 30 = 803 (~- internal energy is a state function) Correct option is (b) Problem: Figure shows a process ABCA performed on an ideal gas. Find the net heat given to the system during the process, Since the process is cyclic so the chainge in internal energydU/=0 SincedU=0 = dQ=dW=PaV For the process 4B change in volume = Zero = W=0 For process BC, temperature is constant Wy» RTL On VY? = Ren 1wo Soln. For process c4,/- T constant Also, PY = RT of 4 aves, 7 Scere TR oh i te nay = jrar Ppt =[RT}}, =R(%,-4) W, = R(T-T) b, Now, Q=W =W,+W,+ W= afnotee(n-n)| i Problem: A gas is carried through a cycle ABCA as shown in the P-V diagram. Determine weather the heat is givento the system or by the system, work is done by the system or on the system, intemal energy of the system increases or decreases in the following process. 3 Vv (@) Forthe process AB if AU=+Ve (b) for the process BC if Q= + Ve (c) For process CA (d) Net work dong in the complete cycle. @ AU =+Fe (given) =>50 internal energy of the system increase AW =4Ve (work done by the system because volume increase) AQ=AU + AW = +Ve (Heat given o the system) (i ForBC O~=+ Ve( given) = Heat givento the system AW =0 (W=Pd¥ and Vis constant) AU =+Ve AQ = AU +AW Internal energy of the systemincrease) (iii) For process CA For process ABC AU = positive (“(AU) ye =(AU) yg (AU) go =(4¥) + (+¥€) For CA Process (AU). =—(AU) ,o = negative (AU) 4 =— ve (Internal energy of the system decrease) AW =—ve (-7 volume decrease so work done on the system) AQ=~ve (AQ = AU + AW = —ve, heat is given by the system) (iv) Net workdone in complete eycle = area under the curve a Ex AB BC = 34420 40 Joule.The Gas Laws & the First Law of Thermodynamics Slope of Adiabatic and Isothermal Process (a) Isothermal Process PY =constant > Pd +Vap=0 > (2). P WV 7 (b) Adiabatic Process i Iota a pry F PY? =Constant => PyV "dV 4dP.F? =0 => i aan (PIM Laprar),. (Slope ofadiabatie is y-times than that of isothermal). OE Oy The bulk modulus or incompressibility ofa substance is a measure of how incompressible/resistant to com- Pressibility that substance is. It is defined as the ratio ofthe infinitesimal pressure increase tothe resulting relative decrease of the volume. oP Mathematically, K =-V/ =) - (5 Ib eS otermal Compressibility In thermodynamics and fluid mechanios, compressibility, (also known as coefficient of compressibility or ‘sothermal compressibility) is a measure of the relative volume change of a fluid or solid as.a response to @ pressure (or mean stress) change, Lav Mathematically, B = ~77| 55 OR ICO It isa measure of how easily a substance expands on increasing ils temperature. It is defined as the ratio of the infinitesimally increase in the volume ofthe substance to the infinitesimally increase inthe temperature per unit original volume, Mathematically, cr (2 u ) VAT )y Problem: For a gas under isothermal conditions. its pressure P varies with volume Vas P x V-!. The bulk modulus B is proportional to (@) yo? () ves © ys wy WRT . For isothermal condition, we get dPV + PaV =0 In. According to ideal gas equation, we get PY ae aviv So, P=B A) But giventhat Pa 7° ii)Soln. Soin. (ea ean The Gas Laws & the First Law of Thermodynamics ‘Comparing equations (i) and (ii), we get Bo ¥™°?. Hence correct option is (d). Problem: The isothermal compressibility , x ofan ideal gas.at temperature T, and volume V,, isgiven by Lor| y | 72. Oya), oar), oral, 7 ap Isothermal incompressbility is defined as -— sor mp is arm 1 | @) YP Hence correct option is (a). Problem: Express the isothermal compressibility 1%) ofone mole of vander Waal’s gas asa function I of temperature and volume. Isothermal compressibility is defined as. __ 1 e b=—vap ), (for one mole) ‘The vander Waal gas equation, is (pe) -2)-27‘The change in the internal energy of the gas is directly proportional to- (a) The change in volume (b) Change in pressure (©) Change in temperature (d) None of these The first law of thermodynamics is conservation of- (@) Momentum (b) Energy (0) Both(a)and(b) (4) None of these ‘A thermos bottle containing coffee is vigorously shaken and thereby the temperature of coffee rises. Considering the coffee as the system, which of the following is CORRECT. (2) O=0; 7 (b) O=0; W=+ ve; dl (© O=0;W- (@) 0-0; W=+ ve; a ‘A resistor immersed in running water carries an electric current. Consider the resistor as the system (a) Q=0; W=—ve;dt (b) O=0; (©) O=0; W=+ve: dU @o ‘The quantity remaining constant in the isothermal expansion of an ideal gas is— (a) Heat (b) Internal energy (©) Pressure (4) Temperature and pressure The work done #7 during an isothermal process in which the gas expands from an initial volume V, toa final voluem V, is given by— 1 (R= Gas constant, 7= Temperature) z ‘(4% @RY,-V bog 7 © (F,-T)l08| 7 conrng() ORT bg 7, | Ifa system Ais in thermal equilibrium separately with B and C, then B and C are also in thermal equilibrium with each other. This is the statement of- (@) Zeroth law of thermodynamics |b) First law of thermodynamics (c) Second law of thermodynamics \ @ Third law of thermodynamics Ookdneee CAREER ENDEAVOR (b) Work done by the systemis equal to the quantity of heat given to the: system (©) Work done cies not depend on the quantity of heat given to the system @ The internal energy of the system increases One mole ofa perfect gas expands adiabatically. As a result ofthis, its pressure, temperature and volume change from?,,7,, V, to P,, T, and V, respectively. If molar specific heat at constant volume is C, then the work done by the gas is— - 7 nav —pive (2309 7,7, tog (27, oak ota Cnr) Fora thermodynamic system work done ina process depends upon (@) Thepath (b) State of the system (6) Extemal pressure (a) Nature ofthe system ‘Work done inan isothermal change ina gasis @ W=T tog, 2 ()W=R wee 2) 7, 7, (W=RT vee( ft) @ 7 ~B0-otg( 2) 412. 13. 14 15. 16. The Gas Laws & the First Law of Thermodynamics nan isobaric process work done is (a) W=RT ve) (W=PY,-¥) (@Ww=0 The work done by a gas in adiabatic expansion is represented by the diagram— @ | ) | ©r @)e. ¥ t a Inthe PY diagram below which is the correct statement? (@) Any point on the line abe represents a higher temperature than any point on the line ade (b) The area abcda represents the work done by the system for the process (c) Heat is lost to the surroundings during the process is represented by pathade (@ The path abc and ade represents isothermals Inan isothermal change the internal energy ofmotecules~ (a) May increase or decrease (b) Does not change (©) Increases (@ Decreases ‘Which of the following graph correGtifgppres constant temperature ? mag. AIP fi 2-H with P for an ideal gas at orn Bay 6 @ ) \ ——____P L______.p By B © @ P L____\—,pThe Gas Laws & the First Law of Thermodynamics 17. 18. 19, 20, 2 22. 23. 25. A piston containing an ideal gas is originally in the state X (see fig.). The gas is taken through a thermal cycle X > ¥ > Yas shown. They work done by the gas is positive if the direction of the thermal eycle 8 v— (@) Clockwise (b) Counter clockwise (©)Neither clockwise nor counter clockwise (@) Clockwise from.X —> Yand counter clockwise from Y -> X An ideal gas in a cylinder is compressed adiabatically to one-third ofits initial volume. During this process 20J wworkkis done on the gas by compressing agent. Which ofthe following statements is rue for this case? (@) Change in the internal energy in this process is zero (b) The internal energy increases by 20 J (©) The internal energy decreases by 20 (@) Temperature of the gas decreases The relation connecting pressure and volume in an adiabatic expansion is given by PY” = constant. Ifthe specific heat at constant pressure is / and the specific heat at constant volume is m, then nis given by- m i @Ft oO Ol-m @ m-t ‘The internal energy ofa systemis the eet (@) potential energy of the particle of the system (b) kinetic energy of the particle of the system (c) sum of kinetic and mutual potential energies of the particles of the system (d) difference between the kinetic and mutual potential energies ofthe system A.vessel contains an ideal monoatomic gas, which expands at constant pressure when heat Q is supplied to it. Then work done in the expansion is BCH € @o wih EER EA, ‘The slopes of isothermal and adiabatic curves are related as (a) Isothermal curve slope= Adiabatic curve slope (b) Isothermal curve slope = 7 x Adiabatic curve slope (©) Adiabatic curve slope y'* Isothermal curve slope (@) Adiabatic curve slope = + x Isothermal curve slope ‘Two bodies are said to be in thermal equilibrium when they are equal in (a) temperature (b) heat content (©) heat capacity @) specific heat Ifthe equation of state for a gas with intemal energy Us PY = =U sthenthe equation for anadiabatic process is (@) Py% =constant (b) PY# =constant (©) PY =constant (4) PY = constant ‘When a perfect gas is supposed to expand freely against vacuum ina insulated vessel, the gas has undergone~ (a) An increase in pressure (b)A change in temperature (©) Achange in entropy (@ Achange in phase) = The Gas Laws & the First Law of Thermodynamics 6. A gas obey the equation of state P(V—b) = RT where b is a constant. For this gas a plot of V versus Tat . constant P (isobar) will be- : J Ko (a) (b) i {____ Peet v v © @ _ -___ {___ 27, The general gas equation PY = RT was improved by Vander Waal who introduced a correction factor 77> which is added to P, The term, 77 relates to (a) Volume of the molecules (b) Effective area of the molecules (0) Average velocity of the molecules (@ Force of attraction between the molecules 28, The pressure of a gas filled in a vessel is P, ifthe masses ofall the molecules of the gas are halved and their speeds doubled, the new pressure will be— (a)4P (&)2P (OP @ £ 29. Fora gas obeying Vander Waal's equation the critical constants can be related correctly by RE 8 PY._3 RT 3 @ pry 3 ORs Ors (@none of these 30, Which ofthe following graphs satisfy Boyle's Law? P @ v a 31, Onsuffering adiabatic expansion the internal energy ofa gas— (@) Increases (b) Decreases (©) Remains unchanged (@) May increase or decrease 1 © 2 (b) 3. @) 4. (b) 5. (b) 6. (©) 7 @) 8 (b) 9%. @) 10. (a) 1. @) 12. ©) 13. (a) 14. (b) 15. (b) 16, (a) 17. (a) 18. (©) 19. (b) 20. (©) 21. 22. (¢) 23, (a) 24.(©) 28, (a) 26. (a) 21.(@) 28. (b) 29. (a) 30. (©) 31. (b)The Carnot Engine Suppose we have a hot reservoir at temperature 7, and a cold reservoir at temperature 7; What is the maximum efficiency possible for a heat engine operating between the two reservoir and what cycle ofpro- ‘cesses should be adopted to achieve the maximum efficiency ? Sadi Camot, a French engineer first considered these questions in 1824. A Carnot engine governs by Carnot cycle which is defined as any cyclic process bounded by two reversible ‘sothermals and two reversible adiabatics, It consists ofthe following : 1. Acylinder fitted with piston 2. Asource at higher temperature (71) 3. Asource at lower temperature (7,) 4, Aninsulating stand ‘The Carnot cycle is shown as :The Carnot Engine ‘The various steps in the Camot engine are as follows 5 (a) Step 4 — B : Isothermal expansion of the gas. Since the intemal energy of an idcal gas is a function of ts temperature only, the internal energyis constant in the isothermal process 4—+ B and the heat flow Q, into the gas in this process is equal to the work done by the gas WV,, So we have =m =nenn( 2) Q 4 where V, and V, are the volumes in states A and B, respectively. () Step B—» C: Adiabatic expansion of the gas. To expand adiabatically, the gas needs to perform work WW, which it does at the expense of its internal energy and hence fall in its temperature. So, we have y= ne iD wQ) (0) Step CD : Isothermal compression of the gas. ‘The gas is compressed isothermally from the volume V, to V, This requires work W/, need to be done on the gas. This is the amount of heat 0, released by the gas to the reservoir. This gives Op =Ws = nT In| % = @) y (@ Step D> A: Adiabatic compression of the gas. The gas in the systems further compressed adiabatically. The necessary energy required to performthis. task increases the internal energy of the gas resulting in the rise of temperature of the system. The work done involves in the process is given by W, =nr BD 4) So the total workdone by the gas in one complete cycle is WW Wyte = no 22) y 2 = gi 2 nary ‘Now from equations (1) and (3), Q _ nRT IIH) _T In(a/K) 6) Q, ~ nRIz In Vl) Ty WV4I%>) Since states B and Clie on the same adiabatic and hence qv =hyy* (D Similarly, since states A and D lie on the same adiabatic, Ty l=nVy! (8) + 5) Now dividing equation (7) by (8), we have 2 = a -@) 1 V4The Carnot Engine ‘Now using equation (9) in (6), we get 7 moyv.) (10) Ao Be 1 (1D) Roa So the magnitude is B38 (12) i TThus for an “ideal gas”, the ratio Qp/Q, depends only on the temperature of the source (7}) and of the sink (Z,) and independent of the nature of the working substance. Itisa device by which a system is made to undergo a cyclic process that results in conversion ofheat to work. Since the process is cyclic, the net flow of heat Q into the gas or the system, in any complete cycle, is equal to the work done by the engine per cycle. ie Q=W (13) ‘The Schematic representation ofa heat engine is 7 rf whe a Here Q, isthe amount of heat given to the working substance from the hot reservoir at temperature 7; Apart ofthis Q, amount of heat is used to perform work FV by the system and the rest ofthe heat Qp is rejected to the sink at temperature 7; . So by the conservation of energy Q=7+2, (14) = W=0,-Q, (1S) ‘The efficiency (n) is defined as = hat You get. ‘what you pay For the heat engine, we have given Q, amount ofheat to the system and as a result, it performs Wamount of work. So the thermal efficiency is (16) = neo (17) (Using (15)] 7 ) IsingSoin. Soin, Soin, The Carnot Engine > w= (18) [Using (12)] ‘The definition in equation (17) is valid for every type of heat engine whereas equation (18) is valid only when, the working substance is an ideal gas. Clearly, the efficiency of heat engine depends only on the temperatures of the source (7j) and of the sink (1) and independent of the nature of the working substance. For Q, =0 ic, ifno heat gets wasted, the efficiency ofthe heat engine is 1 or 100%. It means that all the heat given to the system is utilized in the work. This is an ideal case and is not practically possible. Moreover, the value of ‘ny’ lies between 0 and 1. Problem: Find the efficiency ofthe Carnot engine working between the steam point and the ice point. Given T,= 100°C = 100+273=373 K (steam point) T,=0C = 0 +273 = 273 K (ice point) 273 _ 373-273 _100 373373838 %Wofefficiency = xt00 = 26.81% Problem: A Carnot engine whose temperature of the source is 400 K takes 200 calories of heat at this ‘temperature and reject 150 calories ofheat to the sink. What is temperature ofthe sink. Also calculate the efficiency of the engine? Q, =200 Cal, Q,=150Cal, 7,= 400K, 7, ne 1-2: 2 150 Using B= 2 = 7, = Buz = 2x 400=300K sing Gh = L 500 r, i =l- 20 Lo, nolo gal Zo =05 % of efficiency = 0.25x100=25%. Problem: A Camot engine is operated between two reservoirs at temperature of 450 K and 350K. Ifthe engine receives 1000 calories of heat from the source in each cycle. Calculate the amount of heat re- jected to the sink in each eyele. Calculate the efficiency of the engine & the work done by the engine in each cycle (I calorie = 4.23) 7, = 450K, 7,=350K, Q,~1000cel, 2, — Qh x9, =358, nF P= PHO = 751000 = 777.77 eal ry 250,100 _ ge Ta 1n ad T= gq 02002 So, % ofefficiency =22.22% Also, work done in each eycle= Q, ~ Q, 1000 777.77) cal = 222.23 cal = 222.23 x 4.2 J= 933.336}The Carnot Engine Soln, Soln. Sols. Problem: A Carnot engine whose low temperature reservoir is at *C has an efficiency of 50%, Its desired to increase the efficiency to 70%, By how many degrees should the temperature of the high temperature reservoir be increased? Inthe Case-I: 1=50%=0.5, T,=273 +7 = 280K, T=? So, 2800.5 = 7 = 280. 2800 _ 60x i os. 5 Inthe Case-II: 1=10% = 0.7 T, = 280K, %=? So,n = 30,7 = 1-280, 280 9.3 7 280 _ 280 _ 95545 ¢ ih 03. 3 So increase in temperature = 933.33 — 560 = 373,33 K Problem: In a Carnot cycle isothermal expansion of an ideal gas take place at 400 K and the isothermal compression at 300K during the expansion 500 cal of heat energy are transfered to the gas, Determine (1) The work performed by the gas during isothermal expansion. (2) The heat rejected from the gas during an isothermal compression (3) The work done in isothermal compression of gas? (i) The work performed by the gas during the isothermal expansion is equivalent to heat Q, absorbed by the gas Here Q,=500cal= Wi=9 W =500 x 4.18 = 2090 Joule, (ii) Let Q, be the amount of heat rejected. Then, Qt h 300 Lot s2x = 500x—— =375 cal a 7 27, *% 400 (iii) The work done on the gas during isothermal ‘compression is equivalent to the heat rejected. W =Q, =375 cal =375x 4,18 =1567.5 Joule Problem: A reversible engine works between two ‘temperature whose difference is 100°C. 1f 746 J ofheat fromthe source is taken and 546 J heat is given to the sink by working substance. Calculate the temperature of the source and sink. Given T, ~I,= 100°C, Q, = 746 J, O,= 546 QF, 746 _ 373 Using 2 Q T 0, 346 27 DFAT _, 200 100 346x100 yyy = 2 % 346% 8 200 Now, T\~I,=100=7,=T, + 100 =273 + 100 = 373°C.