KTG_AND_THERMODYNAMICS. pdf ow a Kinetic Theory Of Gases The Anidealgasis collection of small, hard, randomly movingatoms that occasionally collide and bounce off each other but otherwise donot interact, Never the less, gases if two condition are met cI ) 1. The density is low (ce, the atomsoccupy a volume much smaller that of the container), and 2. The temperature is well above the condensation point. Ifthe density gets two high, or the temperature too low, then the attractive forces between the atoms ccame interaction. These ae the forces thatare responsible underthe right condition into a liquid forthe gas condensing Ideal-Gas Law Experiments shown that there isa specific relationship between the state variables, (P,V,T) ‘There isa very clear proportionality between the quantity PV and the quantity nT. If we designate the slope of the line in this graph asR, then we PV=Rx (nT) -an write relationship as The graph of PV against nT Isa straight line with slope R=831J/mol K Pv) nT(mol K) A graph of PV versus nT for an ideal gas. Itiscustomary to write the relationship ina slightly different form, namely PV=nRT (ideal-gas law) (i) ‘equation (i) is ideal gas law. The constant R, which determined experimentally the slope of the graph in figure i called the universal ‘gasconstant, Its value in SI units is R=8.31 J-molK ally in state i, characterizes buy the state variables P, V, and’T, andat some later time in Ifth a final ina final state f, the state variables for these two statesare related by PY, _ BN, TT (ideal gas ina scaled container) ‘The mathematical relation between the state variables of a system is called the equation of state. deal ‘gas will always follow ideal yas equation,2 Symbols and constants : P=Pressure ofgas; V=Volumeof gas; T="Temperature of gas n=no.ofmoles; M=mol. wt of gas: __m,=mass ofeach atom ormolecule N-=total no, of molecule; N, ~Avogadro no, K =Boltzmann gasconstant = 1.38 « 10 JK! R=Universal gas constant R M 11= Specific gas constant = m=massof gas Different forms of Ideal gas of equation (a) () ©) «@) * PV=nRT aRT Ty isdensity ofgas) PV=NKT _ (permolecule) PV=muT Mlustration : Sol Tivo closed vessels of equal volume contain air at P, pressure, T, temperature and are connected through a narrow tube. If one of the vessels is now maintained at T,, and other at T, what will be the pressure in the vessels? Lets say volume of each vessel be V,, valve closed ots y n moles where prese asse {ets say nitallyn moles where presentin each vessel Pa <7 fh Ty th n=, 2PV5 5 f mo e system = pe thus to1al no. of moles in the system = “per Finally lets say n, moles where present in lefi vessel and n, moles where present in right vessel. PY, Phy Rp © RI valve Oponed here Pis the pressure in vessel 4 a nm, + My (no. of moles is constant) Py, By, Pr, PU, _ 2B 7h T 7 RT” RT, ~ RY,2 Symbols and constants : P=Pressure ofgas; V=Volumeof gas; T="Temperature of gas n=no.ofmoles; M=mol. wt of gas: __m,=mass ofeach atom ormolecule N-=total no, of molecule; N, ~Avogadro no, K =Boltzmann gasconstant = 1.38 « 10 JK! R=Universal gas constant R M 11= Specific gas constant = m=massof gas Different forms of Ideal gas of equation (a) () ©) «@) * PV=nRT aRT Ty isdensity ofgas) PV=NKT _ (permolecule) PV=muT Mlustration : Sol Tivo closed vessels of equal volume contain air at P, pressure, T, temperature and are connected through a narrow tube. If one of the vessels is now maintained at T,, and other at T, what will be the pressure in the vessels? Lets say volume of each vessel be V,, valve closed ots y n moles where prese asse {ets say nitallyn moles where presentin each vessel Pa <7 fh Ty th n=, 2PV5 5 f mo e system = pe thus to1al no. of moles in the system = “per Finally lets say n, moles where present in lefi vessel and n, moles where present in right vessel. PY, Phy Rp © RI valve Oponed here Pis the pressure in vessel 4 a nm, + My (no. of moles is constant) Py, By, Pr, PU, _ 2B 7h T 7 RT” RT, ~ RY,Boyle's Law : Relation Between Pressure and volume of a Gas At constant temperature, volume of a fixed mass of a gas is inversely proportional to its pressure, Isotherms P v log P TW TP constant constamt log V , (o)P= ov (a) PV ~ constant Pay (Over (4) log P= constant ~ Ing vel P PV=constant P,V,=P.V, (7, nare constant) Charles’ Law: Relation Between Temperature and volume of a Gas When « gas is heated at constant pressure, its volumeis a linear function of the temperature and can be expressed by the equation for a straight line V=mt+C Where is the temperature in °Cand mand C are constants. The intercept on the vertical axis,C, is V, AV which is the volume at t= 0°C. The slope of the line is m= —~ Thus (a, pare constant) -ase in volume per degree Slope = Var ° om 1K ‘Thus V, at = V, (+a) cris called coefficient of expansion. Itis approximately =~ forall the gases, 2713 1+ 0223)Thus, an increases the temperature ofa fixed volume of a gas at constant pressure increases the volume at O°C, bby 373 of the volum constant T consiant P constant V MoT, (n, Pareconstants) Gay-Lussac's Law When the temperature ofa gas is changed keeping the volume constant, the pressure of the gas changes. Similarto volume, the pressure changes by 1/273. (isothermal) constant P constant T or (a, Vare constants) Dalton's Law of partial Pressures This law states that the total pressure exerted by @ mixture ofnon-reacting gases is equal to the sum of nt would exert if placed independently in the container the pressure which each compon Pig o Py bP, 4 Py4 oa (I, Vare constants) = =P, Where the symbol 2 stands for the summation over al the components present in the mixture. The partial pressure P, of component iis defined as the pressure that the gas would exert ifit were presentalong inthe same volume and the same temperature.ART Po _ aT Py ‘The total pressure of the system can be written as RTS ong RI ve Vv When | is the mole fraction of the respective component Equation of State : ‘The equation of state for an ideal gas : PV=nRT Inthis expression, known as the ideal gas law, R isa universal constant that is the same forall gasesand T is the absolute temperature in kelvins. Experiments on numerous gases show that as the pressure approaches zero, the quantity PV/nT approaches the same value R for all gases. Forthe reason, Ris called the universal gas constant. In SI units, in which pressure is expressed in pascals (1 Pa = 1 N/m?) and volume in cubie meters, the product PV has units of newton meters, or joules, and R has the value R=8.315 Jimol K Ifthe pressure is expressed in atmospheres and the volume in liters (1L=10°= 10m), then R has the value R=0.08214 L atm/mol K Using this value of R we find that the volume occupied by 1 mol of any gas at atmospheric pressure and at O°C (273K ) is 2.4L. Mlustration : A big container having ideal gas at pressure P and of volume V, ix being evacuated by using vacuum pump of cylinder volume V. Find pressure in the big container after n strokes. Assume the s to be isothermal, LL essure becomes P, whole proces For first stroke, pr PV,=P,,+V) PY, i> (4+) Pfor 2~ stroke, pressure becomes P. PY,=P,U, +1) PY, Ps- 7 4Y) PY; P,= 7 ap? Va t¥) for n® stroke, pressure becomes P, Pv; Po Wav Mustration : Consider the lung capacity to be 500 cm? and the pressure thereing to be equivalent of 761 mm of Hg; estimate the number of molecules per breath. Sol From ideal gas equation, PV = MKT. Normal body temperature is 98.6°F = 37 °C = 310 K. Py AT (101.46)(500x 10° ) © 1.3807 10° 310) = 1.19 * 10 molecules Altustration : A gas is enclosed in a cylinder with a freely movable piston. The load on the piston is gradually decreased. The temperature of the gas can be changed by placing the cylinder on hot and cold heat reservoirs. The figure shown P-V graph of such a cylinder. What inference can be drawn the nature of change in the temperature of the gas ? P 1 y ° (a) (b) Sol We draw two isotherms representing constant temperatures T, and T., such that T,passes through initial and final points I and 2, and T, passes through certain intermediate point 3. The curve closer to origin represents lower temperature. Hence the gas is heated in the section 1 cooled in the section 1-2. SandMlustration : Figure (a) shows P-T curve of a ideal gas during a process. Does compression or expansion takes place when the gas in heated ? P —— oO 0 @ () Sol. We draw constant volume lines (isochores) through the initial and final points ample 71). The volume V, is gmeater than V,, Hence during heating of the g place. Land 2 expansion took (see ex- Mlustration = A certain mass of a gas was heated in a constant volume vessel; its P-T curve 3 is another mass of the gas was heated in the same vessel ; its P-T curveis2. If tan is the ratio of masses of gas in the two experiments ? imilarly Iss 2tana, what Sol. From ideal gas equation, rR _ (mR \p Ly) ar The constant volume curves are straight lines with slope mR/MY. The slope of lines is propor tional to the mass of the gas. From ideal gas equation, °F) Gry The cons of the mass of the gas. fant volume curves are straight line with slope mR/MV. The slope of line is proportional (slope, _m, tana _ 1 (slope), m, ~ tan 2 Hence the mass m, is twice ofm,8 Mlustration : Figure shown a cylindrical tube of radius rand length 1, fited witha cork. The friction coefficient between the cork and the tube is 4. The tube contains an ideal gas at temperature T, and atmospheric pressure P,. The tube is slowly heated ; the cork pipe out when temperature is doubled. What is normal force per unit length exerted by the cork on the periphery of tube ? Assume uniform temperature throughout gas any instant. — Sol. Since volume of the gas is constant, The forces acting on the cork are shown in the figure in equilibrium. Pix A+ UN =2P,A By H Nis the total normal force exerted by the tube on the cork; hence contact force unit length is aN dl Assuption of kinetic theory of gases 1. All gasesare made of molecule moving randomly in all directions. 2. The size ofa molecule is much smaller than the average separation between the molecules. 3. The molecules exertno force on each other or on the walls of the container except during collision. 4. All collisions between twomolecules or between a molecule and a wall are perfectly elastic. Also, the ‘time spent during collision isnegligibly small 5. The molecules obey Newion’s laws of motion. ty and the distribution of 6, When a gas is lefi for sufficient time, it comes to a steady state. The dk position, direction and time. This assumption may be justified if the number of molecules is very large. 4)Calculation of the pressure of an ideal gas A, Consider an ideal gas enclosed ina cubical vessel of edge L.Takea comerof he vessel asthe origin O and the X-, Y-, Z-axes along the edges. Let A, and A. be the parallel faces perpendicular to the X-axis Consider a molecule moving with velocity ij. The components of the velocity along the axes are v,,v, and v,. When the molecule collides with the force A,, the x-component of the velocity is reversed whereas the y- and the z-components remain unchanged. This follows from ourassumption that the collisions of the molecules with the wall are perfectly elastic. The change in momentum of the molecule is Ap=(-mo,)— (mv,)=—2mv, the momentum remains conserved ina collision, the change in momentum of the wall is, Ap’=2mv, (i) After rebound, this molecule travels towards A, with the x-component of velocity equal to—v,. Any collision of the molecule with any other face (except for A.) does not change the value of v,.So, ittravels, As betw A, and A, with a constant x-component of velocity which is equal to v,.. Note that we ean neglectany collision with the other molecules in view ofthe last assumption discussed in the previous section. The distance travelled parallel to the x-direction between A, and A, = L. Thus, the time taken by the molecule to go from A, toA, = L/v,. The molecule rebounds from A,, travels towards a, and collides with itafteranothertime interval Lio, Thus, the time between two consecutive collisions this molecule with A, is At=2 Lv. The number of collisions ofthis molecule with A, in unit time is lv, "at 2b oO The momentum imparted per unit time to the wall by this molecule is, from (i) and (ii), ‘The momentum imparted per unit time to the wall by this molecule is from (i) and (ii), AF = np’ v © 2b x2mo, This is also the force exerted on the wall A, due to this molecule. The total force on the wall, due toll themokecules is (ii) Asall directions are equivalent, we have Ep! = Dv; = Iv?10 Im, 5 Thus, from (iii), F= > 20" hus, from (ii) F= 5 5 IfNis the total number of moleculesin the sample, we ean write _ I mN 2v? plan ze “3LN ‘The pressure is force per unit area so that where M isthe total mass ofthe gas taken and p is its density. Also Ev°/Nis the average of the speeds squared, Itis written as u? and iscalled mean square speed. Thus, the pressure is 1 po ape ol) Lae or pV= Mv" (2) or, 3) RMS Speed The square root of mean square speed is called root-square speed or rms speed. It is denoted by the symbol, Thus, y Equation (1) may be writtenas or, v=(v, tv! 3P Pom so that v, (M— molecular weight)4 8KT _ | \ xm, Avg. speed Pass = Most probable speed ¥, Translational kinetic energy of gas : Kinetic energy of any molecule isk, Total KE. of all molecularis k k= = Smv? KE. / volume = Mlustration + Calculate the rms speed of nitrogen at STP (pressure = 1 atm and temperature = 0°C). The density of nitrogen in these conditions is 1.25 kg/m’. Sol, At STP, the pressure is 1.0 * 10° N/m? The rms speed is _ BP On = | =p [aaoTN ime \1.25ke/m = 490 m/s42 Translational Kinetic Energy of a Gas The total translational kinetic energy of ail the molecules of the gas is a Mlustration : Assume that the temperature remains essentially constant in the upper part of the atmosphere. Obtain an expression for the variation pressure in the upper atmosphere with height. The mean molecular weight of air is M. Sol Suppose the pressure at height h is p and the at h + dh is p + dp. Then dp =~ pg dh @ Now considering any small volume AV of air mass, Am, av = ner = “™ gr pa = aRT= 5 Am RT _ pRT on, P= AVM M Putting in (i) dp= fap » p__Mgh on, ne RT. Where p, is the pressure ath =0 Thus. p =p, ©13 Mlustration: A barometer tube contains a mixture of air and saturated water vapour in the space above the mercury column, It reads 70 cm when the actual atmospheric pressure ts 76 em of mercury. The saturation vapour pressure at room temperature is 1.0.em of mercury. The tube is now lowere the reservoir till space above the mercury column is reduced to half its original volume. Find the reading of the barometer: Assume that the temperature remains constant. Sol, The pressure due to the air+vapour is 76cm ~ 70m = 6m of mercury. The vapour is saturated and the pressure due to it is I cm of mercury: The pressure due to the air is therefore, 5 em of mercury. As the tube is lowered and the volume above the mercury is decreased, some of the vapour will condense. The remaining vapour will again exert a pressure of the volume is halved. Thus, Pau, = 2*5 cm = 10. cm of mercury. The pressure due to the air + vapour reading is 76cm ~Ilem 65 cm. Internal Energy Degree of freedom : Noof waysin which molecule can passes energy is known as degree of freedom. SN Gas Translatory Rotation Vibration Total I Monoatomie 3 0 0 3 2, Diatomic 3 2 0 5 Law of equipartition of energy : as average energy associated with its any molecule for each degree of freedom, Statement : Foran ide: KT is ~(WheretemperatureT in kelvin) KT Letfbe the degree of freedom for a gas. Average energy associated with its any molecule= —> NEKT Total kinetic energy of ga Kineti fs cof fRT Value of internal energy of a gas Internal energy of gas should be sum of K.E. and P.E. of its constitute molecu But forideal gas we has assumed P-E, ~0 (Since force of interaction between molecules is zero) ‘Thus, LE. ofa gas=K.E. of molecules If fis the degree of freedom of a gas molecules than total KF. [Trans +Rotation of each molecule ] £RT foronemole U=— forn mole of gas and having f degree of freedom are at temperature T, kelvin and heated to temperature T, then 4)14 atT, kelvin U, atT, kelvin nfR changein LE, AU= ~~ (T,-T) Change in internal energy of ideal gas is a function of temperature and temperature only. It does not depend on how we carry out this change in temperature. £R 5 istepresentedas C, fR oo U=nC ( —_ Formonoatomic gas (f= 3) _3RT _ n3RAT “2 eT? BR oC (i) Forrigid diatomic molecule (f=5) nSRT gy, DSRAT 2 “ 2 SR Cay Mustration The temperature of an ideal gas consisting of rigid diatomic molecules is T = 300K. Calculate the angular root mean square velocity of a rotating molecules if its moment of inertial is equall to 1=2.1* 10 gen? 1 Sok KE, associated with rotation = > la Degree of freedom associated with rotation = 2 1 5 la = [2KT 1 = 63 * 10" rad S$!15 Calculation of work done by gas: Ifthe piston moves towards right a dx distance then'Work done by this force is dW. dW=F. dx =P(A.dx) dW=Pdv aw- [rav ¥ Graphical interpretation : From above integral it ean be understood that area enclosed by PV-curve and V-axis represents the work done by gas. 0) @ iti) When volume decrease AW is ve Mustration = From the given curves find out the all the three processes PAMBNOP = 800. Sol W W, = PABNOP = 6003 3 4 PCL’ Nm*) w PANOP = 400516 Indirect technique(for quasistatic process) : Work done by gas + work done by all external agents = 0 => Work done by gas =— (work done by all the extemal agents) WT Work done by gas + WD by spring + W.D. by atm press=0 W.D. by gas =—(W. D. by atm press + W.D. by spring) =—(CP,Ax) + 1/2 kx?-0) 1 Axt kx Heat & Thermodynamics Definition : Heat is defined as the amount of energy transfer from one body to another body or from one part of a body to other part of the body by virtue of temperature difference. Important points : (a) When two bodies at different temperature are brought in contact the hotter body cools down and the cooler body warms up due to the transfer of heat from hotter body to cooler body. (b) “Heat is energy in transit due to temperature different between the body” when heat is transferred from one body toanother body then after the transfer this heat becomes part of intemal energ doing work. y or is used for Unit & Dimension : Slunit —> Joule Dimension —> ML” Specific heat of gas : ific heat of gas: fic heat: Unit mass is taken es one mole Units —> J / mole~k (b) Gram specific heat : Unit mass is taken as 1kg or 1 gan, Units —+ J/kg-k or J/ gmk c M17 Definition Amount of heatrequired to raise temperature of one unit amount (mass or mole) by one unit temperature through a given processis known as specific heat of that process. Note : Thus any ges can have infinite specific heats depending on the infinite different processes » AQ= | nCaT where C is the sp. heat for the process through which temperature from T, to T,. i Note : C remains inside the integral because it may be a variable ie. C may be a function of temperature (directly orindirectly) Specific heat at constant volume : (dQ Represented asC, (sar 7 const. volume fR Its experimental value is found to be very close to fR thus Specific heat at constant pressure : Represented asC, dQ ) > Lad st ie , (£+2)R its experimental value is found to bealmost equal to > _ (F#2)R 2 Adiabatic exponent (1) : aR > > G= > C=18 First law of Thermodynamics Statement: dQ=dU +dW (Forzero heat loss) dQ = heat supplied to the system dU =changein internal energy dW=work done by the system * This law is a form of energy conservation. ‘The first Law of Thermodynamics (derivation) Letus introduce certain amount of heat energy dQ into a gas confined inside a cylinder fit with a piston, ‘The gascaneither (i) store energy as random KE of its molecules (dU), or (i) use the energy to do work (dW) in the environment (such as raising a weight on the piston). Thus, the first law of thermodynamics can be written : dQ=dU +dW Note : In solving thermodynamics problems, always take gasas s stem. Sign convention = (i) Whenever heat is added to the system sign is ~ve Gi) Whenever system rejects the heat sign is-ve Work (dW) (V1) signisve Gi) signis-ve vb) Internal energy (dU) : (i) When temperature increases signis ve ) When temperature de sssign Application of first law of thermodynamics : Isochoric process : A process that takes place at constant volume is called isochoric process or isovolumettic process. (Gas will follow Gaylusac’s Law) @ Conditions —+ V is constant Gi) Ifgas istaken from state A having pressure P, temperaureT, and volume V tostate B having Pressure P, temperaureT, and volume V then A —— B (B.V.T) (PVT) [While PV=nRT will relate variablesin samestate ](i) “ (vi) i) (i) (es) w 19 P-V curve dW = (since dv =0 afR AU=—~(h-T) AQ=nC, (T,-T,) Applying first low of thermodynamics (FL.T) 0+AU=aQ = a Bulk modulus ~ 7-2 (dV/V) sp. heat=C, Isobaric process : @ @ Gi) (v) A process that takes place at constant pressure is called isobarie process. (G: Law) Condition : P is constant will follow Charle’s v ss equation —> Proc If gas is taken fiom state A havin pressure P temperaureT, and volume Y, to state B having Pressure P temperaure T, and volume V, then 4A B VT) BVT)20 (awe [Pov =P(V,-V,) =nR(T,-T,) (i) dU=nC, aT AU=nC, (T,-T,) (wi) dQ=nC,dT AQ= nC, (T,-T,) (ai) Applying FLT nC, (T,-T,) =nC, (T,-T,) + aR (T,-T,) => C-C=R (knownas meyer’s relation) Character’ gas constant Gas constant expressed for particular gasin terms of mass is known as characteristic gas constant of that particular ga. R (universal gas const.) Rossa «> M (mol.wt.of gas) Units J/ gmk or I/ kg-k (ex) Bulkmedulus (x) Sp.heat capacity C, Isothermal process : Approcess that takes place at constant temperature is called isothermal process. (Gas will follow Boyle’s Law) (Condition —> Temp. is constant (i) Process equation —> PV= const. Gii) If gas istaken from state A having pressure P, volume V, andtemperaure Tto state B having Pressure P, volume V, and temperaure T then A VT PV.)RT PY, P.V.=nRT (iy) P-Veurve - slope= yy P dP -P v aw= {ray = [ y 4 V M2 =PViny, ne nt =PV ny =PV, in WV ny = PV, In yy, kj a =nRT Inv =ARTIn (vi) dU=0 (vi) Using FLT dQ= dw AQ=nRTh Q= HRT In @ (wi) B=~ yyy 7? dQ (x) Specific heat=C=| gp |=” \ By adiabatic process : Adiabatic Process (Derivation): For an adiabatic process (AQ = 0) Pav R_| RT av + py (y-DInV + In T= Ine!» TVE!=6'; Also, T= 2422 In this process net heat suppliedto the gas iszero () Condition dQ=0 Gi) Process equation PV'=const. (ii) If gas istaken from state having pressure P, volume V, and temperaure T, tostate B having Pressure P, volume V, and temperaure T, then (iv) hope = #2 =P slope= Sy = @ — Aw= J pev Gince Pv =k) ¥ i y ke" py, Py, ok ive w Srp Fe w nC, (T, -T,) (i) Applying PLT we can sce that 0=AW+ AU = AU=-AW or Gi) B=- Gy =P () — Sp.heat aQ C= nat Results : ( _Forexpansion from same initial vol & pressure to same final volume —> Wietic > Wactema > Watstac P| isobarie iscthermat As the area under the P-V graph is largest for isobaric hence its work done is greaterthan isothermal and in similar manner we can say that work done in isothermal process will be greater than adiabatic process.23 (i) Forcompression from same initial state to same final volume Gi) Atpt. of interaction (slope of isothermal) x y~ slope of adiabatic. Polytropic process : It is a process in which molar heat capacity C = constant c=c,+— PaV+VaP =n RAT _ , _PRAV » Pav VaP R Var > ©-o7!* pay R-(C-C,) _ vaP _ c-c, > c-C, Pav ~ Jef -o = P vO => ImP+KInV=const PVE = cons. K :Polytropic constant Isochoric K=0 [P'*V =const.] Isocbaric K=0 c-c, 1 Isohermal: | K=1 K=Gce-=1 Adiabatic: K = y [PutC=o in theequation of K] c=024 () Characteristic equation process PV" const. i) AW- J Pdv Mv y x+1 -x+1 -y, = J Kav - 1 uv | =x41 ky _k \, =v) Ix _ »R(-T) I-x aR(T,-T)) i) = AU GD (v) From FLT dQ= dW +dU AQ=nR (T,=T,) 7 (~) Sp. heat AQ Cc Mlustration An ideal gas expands isothermally along AB and does 700 J of work. P (a) How much heat does the gas exchange along AB. Ay (b) The gas then expands adiabatically along BC and does 400.J of work. ei When the gas returns to A along CA, it exhausts 100 J of heat to its surroudings . How much work is done on the gas along this path. v Sol. (a) AB is an isothermal process. Hence, AU 4, and Qy>W (b) BC is an adiabatic process. Hence, Qye=0 Woe = 4001 (given) 400J AU,. =-W, ABC isa cyclic process and internal energy is a state function. Therefore, (Av), =0=AU,, + AU, + AU,and from first law of thermodynamics Qu + Qnc + Qu Substituting the values, Wy + Wye + AW, 700 + 0-100 = 700 + 400 + AW.., AW. =~ 500I Negative sign implies that work is done on the gas. Mlustration temperature. An ideal monoatomic gas at 300 K expands adiabatically to twice its volume, Sol. For an ideal monoatomic gas, Mlustration : 25 What is the final 1 mole of an ideal monoatomie gas is expanded till the temperature of the gas is doubled under Sol Given T, = 400 K and 1, = 27 = 800K AT~1,-T,- 400K AU =n, AT (3) = a “Rr \400) = 600R The given process is VT = constant PV Putting = we get R ws PV’ = constant Comparing this equation with PV constant we have co RRL RR the process V°T = constant. The initial temperature of the gas is 400 K. In terms of R, find total work done in the process 3. and molar heat capacity is26 3, 8 2R-F AQ = nCAT = (1) (R) (400) ~ 400R Now, AW=AQ-AU=~200R 4) Cyclic process : Itiscombination of two or more thantwo processes in which initial and final state ofthe systemis same @ dU=0 7 Total change in LE. is zero because initial & final temp. issame oe Gi) Applying FLT dQ= dw v Gil) Network done in a cyclic process is area bounded by process curve on PV diagram. ie Ve ie ey of eyelic process Total work done (+ve and —veboth) > Total heat supplied (only + veheat) to thesystem v= (iv) Effie x 100 Carnot Heat Engine : @ As according tothe second law of thermedynamies whole of heat can never be converted into work, the question then arises under what conditions the conversion of heat to work is these questions Camot developed an ideal heat engine which is supposed to consist of the following four components (1) Acylinderwith perfectly non-conducting walls and a perfectly conducting base containing a perfect gas. as working substance and fitted witha non-conducting frietionaless piston’ (2) A source of infinite thermal capacity maintained at constant higher temperature T, (3) A sink of infinite thermal capacity maintained at constant lower temperature T, and (4) Aperfectly non-conducting stand forthe cylinder. a Teal Source Gas Ty, Sink Stand 1, Here itis worth mentioning that as all the above mentioned components cannot exist in reality, Camot engine is an ideal (hypothetical) engine which can never be actually constructed27 () @ wi ii) (v) © Carnot Cycle jor Working of the Engine] : ‘The working substance in a Carnot engine istaken through a reversible cycle consisting of the folloing four steps The cylinder containing ideal gas is placed on the source and the gas, is allowed to expand slowly at constant temperature T,, absorbing heat Q, This isothermal change is represented by the curve AB in the indica- tordiagram. ‘The cylinder is then placed on the non-conducting stand and the gas is alloweed to expand adiabatically till the temperature falls from T, to T,. This adiabatic expansion is represented by the curve BC, The cylinder is next placed on the sink and the gas is compressed at constant temperature T,. This adiabatic expansion is presented by the curve BC. Finally the cylinder is again placed on the non-conducting stand and the compression is continued so that the gasretums toits initial stage along DA. The closed pathABCDA represents the so called Carnot eyele and the four stages taken together represent acyclic process Efficiency of the Engin The efficiency of a engine is defined as the ratio of work done to the heat supplied, ie., Workdone _ W heat input @ But as for cyclic process AW = ie, W=Q,-Q, Soegn. (i) reduces to Qu =Q nest (ii) Qu Now as in an isothermal processintemal energy remains constant, in accordance with firstlaw AQ= AW =nRT log, (V,/V,) [as AU =0] So and iii)28 Butas for adiabatics BC and DA respectively, Ty =T.Vol and TV =TV,"! Dividing these two result, ry el rl { Va Ve ) (Va \Vp a A {iv Substituting the value of Q,, and Q, from, equation (ii) in (i) in the light of (iv), weget qT n wv) Ty This is the required result and from this itis clear that (1) Efficiency of'a heatengine depends only on temperatures of source and sink and is independent ofall other factors. (2) Allreversible heat engines working between same temperatures are equally efficient and noheat engine inbe more efficient than Carnot engine (as itis ideal). (3) AsonKelvin scale temperature can never be negative (as 0 K is defined as lowest possible temperature) andT,, andT,, are finite, efficiency of a heat engine is always lesser than unity, ie., whole of heat can never be converted into work whichis inaccordance with second law ‘Theefficiency of actual engines is much lesserthan that of ideal engine. Actually the practical efficiency of a steam engine is about (8-15)% while that ofa petrol engine 40%, The efficiency ofa diessel engine is ‘maximum and is about (50-55)%, Mlustration : An inventor claims to have developed an engine that during a certain time interval takes in 110 MJ of heat at 415 K, rejecis 50 MJ of heat at 212 while manages to do 16.7kW of work. Do you agree with the inventor's claim ? Sol The claimed efficiency W _16.7kWh Q, 10Ms But as 1kWh = 108 x (J/s) x (60 * 60s) = 3.6 MJ soy lOPB8 95-55% 0 While maximum possible theoretical efficiency, q, 415-212 Mas = Ty Ty 415 =49 = 49% From eqns. (i) and (ii) itis clear that claimed efficiency is greater than maximum possible theo- retical efficiency; so inventor's c claim does not appear to be correct.29 Mlustration : Sol. During an integral number of complete cycies, a reversible engine wr (shown by a circle) absorbs 1200 joule from reservoir at 400 k and performs 200 joule of mechanical work at ed ol (b) Find the change of entropy of each reservoir. (c) What is the change in entropy of the universe ? (a) By conservation of energy W+0,+0, ie, Q,+Q,=0,-W= 1200-200 = 1000 M And as change in entropy in a re nsible-proces _ 2000. 9, 400 300° 200 s is zero ie, 20,+30,= 1800 Solving equation (i) and (ii) for Q, and Q, we get Q,= 1200 J and Q, =~ 200 Le,, the reservoir at temperature T, absorbs 1200J of heat while the reservoir at temperature T, lose 200 J of heat (b) Now as change in entropy at constant temperature is given by AS = (40/1) So change in entropy of reservoir at temperatures T,, T, and T,, will be respectively -1200__, J 1200 Lang 220 2h 40K’ 300K 309 K Practice Exercise ‘The average energy and the rms speed of molecules in a sample of oxygen gas at 300K are 6.21 =10 2! Jand 484 ms"! respectively. The corresponding values of 600 K are nearly (A) 12.42 « 102! J, 968 ms! (B) 8.78 x 107, 684 ms! (©)6.21 x 107F, 968 ms" (D) 12.42 * 10 J, 684 ms" ‘The P-T diagram fora ideal gas is shown in Figure where AC is anadibatic process. The corresponding PV diagram is. (A) NK B) |) ~— © « © |i < Sy v v vAGG- PH-KTG AND THERMO Variation of molar specific heat of a metal with temperature is best depicted by (A) Answers D Q2 B Q3 D34 Solved Example QL 70 calorie of heat is required toraise the temperture of a diatomic gas at contant pressure from 30 to 35°C. the amount of heat requried (in calorie) to raise the temperature of the same gas through the same range (30 to 35°C) at constant volume is (A)30 (B) 60 ©s0 (D)70 Sol (aQ), _ C,AT _ Cy ah La (40), nCyaT Cy _ (4Q), (AQ), = “Tg =50cal Q.2__ A vessel contains I mole of O, and | mole of He. The value of y of the mixture is (Ala (B)1.50 ©) 1.53 (D) none of these Sol C,,,=4-52— rn 2 Coie =2R+R=3R Q3__ Anidealis taken through a cycleA — B > C+ Aas shown in Figure if thenet heatsupplied inthe cycle is 5J, then work done by the gas in the process C > Ais cm) (Pa) (A-SI (B)- 10 ©-155 (D)-205 Sol. Work done =area under the curve 10 J; 5=W,,+10 or W,,=~5J Qt A glasstube scaled at both ends is I m long. Itlies horizontally with the middle 10 em containing Hg. The ‘two ends of the tube, eqaul in length, containair at 27°C and pressure 76 cm of Hg. The temperature at one end is kept 0°C and at the other end it 127° C. Neglect the change in length of Hg column. Then the changein length ontwosides is (A) 123m (B)10.311 em (B) 9.9m (D) 849m32 Sol, Qs Sol, Initially /=45 em 2/+10=100 em) =P (say) 45cm 45m jem Hej Sy we arc Applying gas lawatendA, ASAP _ (45—x)AP, 300 273 45AP _(45+x)AP, 300 400 AtendB From (i, (i) and (iii) ¢ x) 273400 =8.49em (ii) (iii) Find the amont of work done to increase the temperature ofone mole of an ideal gas by 30°C ifit is expanding under the condition y 4: 1?” (A) 166.25 (B) 136.23 PV=RT for I mole we frav=J8Fav v=cr’ 2er ar av=5 2 or or “37 fer(2 at y= [RT we [Jr R(T, -T,) =166.21 (C) 126.25 (D) None of these33 Sol. Q7 Sol. Qs Sol ‘A mereury thermometer read 80°C when the mereury is at 5.2. em mark and 60°C when the mercury is ‘at 3.9 cm mark. Find the temperature when the mercury level is at 2.6 em mark. Lh _al(T,-,) _1,-7 1, ai(T,—T,) T,-T, 5.2-39 80-60 or 5,2-26 80-T, 1.3 (80- T,) =2.6 (20) or T, ~ 40°C A vertical cylinder pistion system has cross-section S. Itcontains | mole of an ideal monoatomic gas. under apistion of mass M. Ata certain instant a heater is switched on which transmitsa heat q per unit time ot the cylinder. Find the velocity v ofthe pistion under the condition that pressure under the pistionis constant and the systemis thermally insulated. Mg Gas pressure =P, + “g> , Where Mis mass ofthe pistion. AsC,=2R sCy= 5 3 3 AU = SRAT= > PAV 3 Q= PAV + AU = PAV + 5 PAV 2 AV=Sdx 5 or Q=q, t= > PSdx dx 2q OF at Ms \y s) A typer pumped toa pressure 3.3375 atm at27°C suddenly bursts. Whatis the final temperature (y= 1.5)? (a)27°e (B)27C oc (D*) 73" TP) Y= TiPy ~8-@) 4 (Th) AB} A 300 or T, = 37577 = 200K =- 739°C | Copied to clipboard.34 Qs Sol Sol 3 Moles ofa gas mixture having volume V and temperature T compressed to 1/Sth of the initial volume, Find the change in its adiabatic compressibility if the gas obeys PV' =constant [R=8.3 J mol—K] Bulk modulus By (1) 1 Compressititity C=[ B)” yp and AC=C~C 1 or > of XY marl] With » d P= S*P, 11 ith y= 75 am , ac al i+ 13x 0.90: pls 1 19P RT But =PV=nRTorP Vv AC 13.(0905)V —0.0248V © 19x3x8317T oT ‘One mole of an ideal gasis contained under a weightless pistion ofa vertical cylinder ata temperature T. What work has to be performed in order to incteascisothermally the gas volume under the pistion n times ‘The space over the pistion opens into the atmosphere. LetA be the area of cross-section F F+PA=P\A » | F=(P,-P)A Work done by the agent | we JFdx= [(P,—P)Adx | v \ P = Te, Pav dv =P,(n—Dv- fart Vv =RT(q-1)-nlog.y35 QL Calculate the heat absorbed by the system in going through the process shown in figure (Aj3l4s (B)3.145 (C)3.14 1055 (D)none 200 (volume) 490 Sol. Heat absorbed = =nx(P)(V) = 3.14 (100x108) (10010) 14) Q.12_ A mercury manometer consists of two unequal arms of equal cross-section 1 em? and lengths 100m and 50cm. The two open ends are sealed with airin the tube at a pressure of 80 em of mercury. Some amount of mercury is now introduced in the monometer through the stopcock connected to it. [fmercury resis in the shorter tube to length 10 em in steady state, find the length of the mercury column risen in the longer tube, Sol. Letp, and p, and be the pressures in centimetre of mercury in the two armsafter introducing mercury in thetube, Suppose the mercury column risesin the second arm to/, cm, hem Jem h Using pV = constant forthe shorter arm, (80cm) (S0em)= p, (50cm — 10cm) or p,= 100m, (i) 1g pV = constant for the longer arm, (80cm) (10cm) =p, (100-/,)em ii) From the figure, P,=p, + (I~ 10) em.36 Sol 3 4 Thus by (), 100m + (J, 10) em. or 110 cm—/,em Putting in Gi), (110 ~1,) (100 ~ 1,)= 8000 or, 12-2101, + 3000=0 or 1-155 ‘The required lengthis 15.5 em. Anideal gas has pressure p,, volume V,, and temperature T,. It is taken through an isochorie process till its pressure is doubled. It is now isothermally expanded to get the original pressure. Finally, the gas is isobarically compressed to its original volume V,,, (a) Show the process on a pV diagram. (b)What is the ‘temperature in the isothermal part of the process? (c) What is the volume at the end of the isothermal part of the process? (a) The process is shown in ap-V diagram in figure. The process starts from A and goes through ABCA. : oN (b)Applying pV=nRTatAand B, p,V,=mRT, and (2p)Vy-aRT, Thus, T,-2T, ‘This is the temperature in the isothermal part BC (©)As the process BC is isothermal, T, =T,,=2T,, Applying pV =aRTatAand C, p,V,=nRT, and p,V, nRQT,) V.2V Figure shown a vertical cylindrical vessel separated in two parts by a frictionless pistion free to move along the length of the vessel. The length of the cylinder is 90 cm and the pistion divides the cylinder inthe ratio of 5 : 4. Each of the two parts of the vessel contains 0.1 mole ofan ideal gas. The temperature of the gas is 300 K in each part, Calculate the mass of the piton. 90cm37 Sol Qs Sol Let /, and/, be the lengths of the upper part and the lower part of the cylinder respectively. clearly, /,= 50cm and i, area of coss-section of the cylinder be A. The temperature in both parts is T= 300 K. 40 om, Let the perssures in the upper and lower parts be p, and p, respectively. Letthe Consider the equilibrium of the piston. The forces acting on the pistion are (a)its weight mg 4) (b)p, Adownward, by the upper part of the gasand (c) p, A upward, by the lower part of the gas. Thus, p,A=p,A+mg (i) Using pV = nRT for the upper and the lower parts, p,,A=nRT (i) and p,A=nRT. - ii) Puttingp, Aand p, A from (ii) and (iii) into (i), aRT _oRT iE oRT}1 1 ‘Thus, m= £ L (0.1mol\8.33 /mol-K)300K)[ 1 1 ~ 98m/s [0.4m 0.5m} =127Ke Figure shows a cylindrical tube of volume V, divided in two partsby a frictionless separator. The walls of the tube are adiabatic but the separator is conducting. Ideal gasses are filled in the two parts, When theseparator is keptin the middle, the pressures are p, and p, inthe left part and the right part respectively The separator is slowly slide and is released at a position where it can stay in equilibrium, Find the volume of the two parts L- mnduucting, the temperatures in the two parts will be the same. Suppose the common Asthe separator i temperature is T when the separators in the middle. Let n, and n, be the number of moles of the gas in the left partand the right part respectively. Usingideal g equation, and ‘Thus, efi) n, Pp The separator will stay in equilibrium at a position where the pressures on the two sides are equal. Suppose the volume of the left partis V, and of the right partis V, in this situation. Let the common pressure bep’. Also, letthe common temperature inthis situation be Using ideal gas equation38 Sol and or, [using (i) Also, ‘Thus, A gas is heated isobarically and the heat used for external work is W. Find the total amountof heat supplied. AQ= AW + AU nRAT (¥ =(nraT) | =nRT + nC, AT=nRT+ - [. W=aRaT] A vessel contains a mixture consisting ofm, = 7g of nitrogen (M, =28) and m, = 11 gofcarbon dioxide (M, = 44) at temperature T = 300 K and pressure p, = 1 atm, Find the density of the mixture. m, +m, Let V be the volume of the vessel. Then p,,,.— 2 Letp, and p, be the partial pressure ™, then p, V= RT and p, Prix m,M3 +m5M, = (#11) x28%44x107 10° Tx4d¢11x28 8.3300 = 1446kg.m-*= 1.446 per litre