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    ASPIRATION xcavemy dream high. beyond the sky IT VAM M.Se. Entrance | CSIR NET | GATE | NEET | JEE STATISTICAL THERMODYNAMICS So far we have bét SPAM. ayes so scopic properties of the in s system without mong fitionso: IN say aim ‘paltles, (molecules, ions, atoms). In a sens hiveGhseu io Berg pepe eR out considering any model or tHe: disadvantages. ff extended to co Bex tefn§ as biologid may not be kn} 5 dictions can be act mechanism ry éyemigrostoy iG jaro Ta ts Man antages as well as aps iB" Bene Seg hy JCF scala ooy ENN thdt it upiegsses even vey 2. lutsthe rate and onthe Fant infSimation can be had provide Wedlingl Acros Chesser ties and the fnatuge afd details Of the microscopic al microscopic piepezties of oe el properties (likes speed,,tnom ntuim, cnert h pate age-pro' fi by quantum g hy hermedynamic mechanics. Theimacostopic c Proper esofthe systeth pipdeserttng i Sieg The limitation.o: wHealal mechanisrn bé t! Pett principles. Statistical mechafiics delfas 0 bridge betyve ena pmo ics and quantum mechanics. Thus ‘theysibject! of she Rtady=oF te J ese Weds éthetmodynamics and quantum mechanics Seed seetical thermody ne iffafarizing this, we can state that quantum mechanics vides informatio ‘about the énéfey of the molecular system, statistical mechanics tells Us aboutthe possible aria Jogeffient of the energy among various molecules of the system, an di ept of probability and partition functions. Statistical thermodynamics deals with the relationships between the probability, partition functions and the thermodynamic properties. The methods of statistical thermodynamics were first developed by Boltzmann (Germany), and Gibbs (USA). With the development of the methods of quantum theory some modifications in Boltzmann's original ideas were introduced by Bose (Indian physicist) and Einstein (German physicist), and Fermi (Italian physicist) and Dirac (English physicist). South Kolkata: 304, Southern Avenue Kolkata - 26. (Near Kalighat Metro) ‘B +91 98369 24983 North Kolkata: 47, Tarak Pramanick Rd Kolkata - 06. (Near Girish Park Metro) @& 491 85829 79309 Website: www.aspirationacademy.in | Email: info@aspirationacademy.in | ASPIRATION rcavemy dream high, beyond the sky ITJAM | M.Sc, Entrance | CSIR NET | GATE | NEET | JEE The energy expressions suggest that the energy of th depend on quantum numbers, For a lower quantum number, lower than that for a higher quantum number, molecules e molecules present ina Syst the energy of tye mil uestion is that hows other words, we, the energy level, Now the q are distributed among the possible energy levels? In now that how many molecules are Present in the lowest how. ‘Ant to molecules are present in the highest en sysleyel and how many are Present in va io intermediate energy levels, Thatsis; SSayilWelwishito,have information about the he possible arrangements “Gee ity Various. quantum, or energy levels Such description is given by the tern eee Rdinoted BY-WATthe vari a various term, statistical mechanics mst ie unfdckstbod refully Si) ‘ $ Used jn Ws gama Common Terms: ¢ : / feat [f LAN 4 derbies: _anieer of ided ie Gthes is cal assem] are singlgparticle then/the assembfy, called Simply a: a system’ ll fa ‘ ES If the e a ee An ensemble insists of; i Each members th¢vense] and same energ) nber‘of replicas of ‘Mbleshas Same number/Ol {tis called’ Micro canonicaf en: 7; 4 vem carp wre % ES, y - The semble consisting oft large mber of assemblies (systems) each having the same‘valu@cofoN~-V,-audeh leda canonical ensemble. At equilibrium each assembly (membe temperature, but not necessar ‘ily the same the ensemble average value, ba Occupation number'| . ‘ et of Itis the number of system present in that particular state. The st » occupation number is called a distrib ielisi8\ call fethie canonical ensemble has the same energy E. The value of E will fluctuate about ution. ASPIRATION xcaveny dream high, beyond the sky UTJAM/ Se, Entrance | CSIR NET | GATE | NEET | JEE Suppose we have to distribute 100 distinguishable balls into five boxes in such a way that each box contains 20 balls. This over all distribution is called a macrostate, The detailed description of the distribution that balls numbered from 1 to 20 can appear in one box, 21 to 40 in the second, 41 to 60 in correspond toa macrostate is referred to as thermodynamic probability. bal Statistical weight factor A degree-of degeneracy-df's igular energy level, and is equal to the energy states ofan, nepefaffor ail energy level ofa particle in the three dimertSeni bos pate (aed ithe statistic it 3 ue etd va i Stquival fi I * \ ofthe system! rétek sider two coins “a-and ‘bt | Forekcnple, con; (H) and 1 I(T) <éh beSicHievedin.two wayssfes (i) Coin ‘a"ghows a Heddaind coi Tae ‘onfiguration showing 1 head Bs ay configuratio’ BA 4s, : ©, c T Siiorrtininy THE CONCEPT OF ona ATA, Wo SOR Statistical mechanics ed UES a system by a suitable sum of the properties 6! system. lican explain a desired property of individual constituent composing the Distribution: 4-particle, 2 energy level Energylevell: 4 3 2 1 0 Energylevel2: 0 1 2 3 4 ee South Kolkata: 30A, Southern Avenue Kolkata - 26. (Near Kalighat Metro) ‘+91 98369 24983 North Kolkata: 47, Tarak Pramanick Rd Kolkata - 06. (Near Girish Park Metro) ‘@ +91 85829 79309 Website: www.aspirationacademy.in | Email: info@aspirationacademy.in | (a4 IE) ~ ASPIRATION scavery dream high. eyond the sky IITJAM| MSc. sak NET | GATE| NEET | JEE Js (420), (32 1), (242), (1:3), (0:4) ~ These are called macro state. Let us consider a, b, ¢, d represents the particle, we can place all a, b, c,d in one way, Macro state: abe abd acd acd (3:4) dcba «+ (3:1) macro state corresponds to foui —+ 4 micro state -ostate. These four microstates are calleq “Thermodynamic probabili by A thermodynamic systepitl emi Phe 5 aygtemu ne various’ sirjbuti (particle) according tothe! ams s eee peter we Q. Define Tera pa eA on, & NePei From Boltzmann distribution law, n, = @ 49198369 24983 B +91.85829 79309 EFTeEU South Kolkata: 30A, Southern Avenue Kolkata - 26. (Near Kalighat Metro) North Kolkata: 47, Tarak Pramanick Rd Kolkata - 06. (Near Girish Park Metro) Website: www.aspirationacademy.in | Email: info@aspirationacademy.in | “Yer Pa = Fe Partition function 2= 3° 2 (2), 2A) a) Fie Q. Show the relation conn or, Show that: S = NKIn S=NKInZ+K PE [p breve that it] =NKinZ+K, + Kr ASPIRATION xcavemy dream high. beyond the sky NTJAM | M.Sc, Entranco | CSIR NET | GATE | NEET | JEE E =NK Ing += S=NKInZ+ > 1 ding =NKInZ+ =. | nip? S84 T ( i) dinz ».S =NKIn Z+ NKT| —= j.S=NKIn z+ wir 82) 5 Ee dA = -PdV - SdT dA (a) ~F @ 49198369 24983 @ +91. 85829 79309 Perez 30A, Southern Avenue Kolkata - 26. (Near Kalighat Waele a) North Kolkata: 47, Tarak Pramanick Rd Kolkata - 06. (Near Girish Park Me Website: wwwaspirationacademy.in | Email: info@aspirationacademy.in | =~ LGD ASPIRATION coven ASPIRATION acavemy aEsey dream high. beyond ee eat? iran [ M.Sc. Entrance | CSIR NET | GATE | NEET | - dinZ) (dz, + nr( aT hel Nir (a Zz lev), élnZ 2 Pena 20% xa av | This can be also written as c,=K|_@ma “ aes ASPIRATION xcaccuy dream high. beyond the sky ITT JAM | MSc, Entranco | CSIR NET | GATE | NEET | JEE fa The chemical potential'and CTE ‘The chemical potential jt of any component in a mixture is given as oA a on, where, niis the number of moles of it type of species. ‘The molar partition function. Qn related as - Equations (1) and (2) give, Gs =-kTIn} + Hy =—kT (2) }0A, Southern Avenue Kolkata - 26. (Near Kalighat Metro) B +91.98309 24909 North Kolkata: 47, Tarak Pramanick Rd Kolkata - 06. (Near Girish Park Metro) ‘@ +9185829 a Website: www.aspirationacademy.in | Email: info@aspirationacademy.in | 7 iY ASPIRATION $1955; dream high. bey iE iran ase xtance 3 | Gare | NEET| ray Ht with altitude (height) is know ree jon of pressure AGP ae enc The formula which relates the varial Barometric formula. Assumptions: (i) The earth's atmosphere 60! tains, ne tational force. (ii) The force acting on the suidystbe (iii) The temperature of given by the to ovetie grQune 72) ctiigiper unitarea, flu summa tseance above the grou arose sectional area (A), Lette) peland (2) bethe pressure re ae dP) iv ahi )- As the fluid From equation (1), - d Integrating both the sides ASPIRATION caveny dream high. beyond the sky IIT JAM | M.Sc, Entrance | OSIR NET | GATE NEET | JEE "Ma = [inp =—TEn . in’. Meh RT Mah Pag etre ‘di ition formula, ane i 1.0 bar Iculate {He difference in ‘om of thé, iner and the ally <>) aw For wit Inches “ata, (atmospheric pressure is reduced to Halfz-Assume:Ay al igeWalue of temperature 250K and the average molar mass, sera mol}, ed Follow Class. Wiese acer utss yee isel sty WAGE statistical method — AR Si ‘@ +91 98369 24983 ‘@ +91 85829 79309 PECe eS South Kolkata: 304, Southern Avenue Kolkata - 26. (Near Kalighat Metro) North Kolkata: 47, Tarek Pramanick Rd Kolkata - 06. (Near Girish Park Metro) Website: www.aspirationacademy.in | Email: info@aspirationacademy.in | ASPIRATION cave \ dream high. beyond the sky NEET | JEE NTJAM | lranco | CSIR NET| GATE 4 (ERTS RO According to Gibbs Helmholtz equation~ (=) 2 AH+T| SO AG=SH+T| GF), From this equation, it is evident that at absolute zero ie. whi te) However Nernst’s observed that a; perature iS lowered towards absolute j { en T= 0, 4G=4H. / 9 Zero asymptotically. zero, the value one or, zero but the value re, This result is One of the most important col orem is that st imp i i nt conclusions of Nernst's heat theorem i Jimas=0 [(%] __ P South Kolkata: 30A. & tha ASPIRATION rcavemy dream high, beyond tho sky IT JAM | MSc. Entranco | CSIR NET | GATE | NEET | JEE again, imac =0 [om kirchoff's equation (2) -acr} F On the basis of Nernst’s heat theorem, Plank in 1912 proposed the third law of thermodynamics, THIRD LAW OF THERMODYNAMICS ;| On the basis of Nernst’ 1 inal posed the third law of thermodynamics. wry if temperature’ "The entropy of @ gules Zero at the sNornst's Heat theorerlinAS=0 © (LATA, } Plank's Third law Jims =0 But after development of statistical thermodynamics it was clear that entropy of a substance is equal to zero, only if it is perfectly crystalline substance. If the system is not in internal equilibrium, e.g. super cooled liquid on solid solution the entropy may not be equal to zero at absolute zero. On the basis of this, the statement of third law is modified as follows ~ South Kolkata: 30A, Southern Avenue Kolkata - 26. (Near Kalighat Metro) ‘+91 98369 24983 North Kolkata: 47, Tarak Pramanick Rd Kolkata - 06. (Near Girish Park Metro) ‘@ +81 85829 79309 Website: www.aspirationacademy.in | Email: info@aspirationacademy.in | he absolute zero of temperature tj ce) entropy butatd 4 iture the e ‘ddoes so for perfectly crystalline substance”. nro, nce in vapour plas "Every substance hasa finite may become equal to zero ant The absolute entropy of the substal e can be determined by folloy,, ng steps- (i) Heat the solids (ii) Transformation of the sub; ting point (79. substance from ok to its mel its melting point. asegf aE Here, Entropy change {, qT a), ar=c, toT=Tythuse finite process is obtai ined by i . y integrating equation (1) from T=" For ve V=0, constant volume process, d , , ASPIRATIOflacavemy dream high. beyond the sky ITJAM| M.Sc. Entrance | CSIR NET | GATE | NEET | JEE I j& s[dS=S-S, =[—taT o 7 o T Using Cy =(0E/2T),, in equation penne (224) we get Iv t 10a alnz S-S= f= 2 oe alee (1 function, — 2-4 fu Integrating by parts wehaven-——~ (2) jon (2) we see that — nigga 9 1 HORT EGE With this concept, sour 22) +kin a E But we know, © ont) ~ [s-E+kinz T aT jy T ‘South Kolkata: 308, Southern Avenue Kolkata - 26. (Near Kalighat Metro) ‘B +91 98369 24983 North Kolkata: 47, Tarak Pramanick Rd Kolkata - 06, (Near Girish Park Metro) ‘@ +91 85829 79309 |: info@aspirationacademy.in | AraeED ‘Website: www.aspirationacademy.in | Em ASPIRATION scx2=0 dream high. beyo gate |GET WEE = ITJAM| M.Se. Entrance | CSIR NET 4 DIABATIC DEMAGNETISATION ; f thermal and part} ises partly out O! Partly oy; ae faced ina magnetic fi field, the atomic dipoles. he entropy of the para-magnetic substa tance is pl ar pe a ian nrg etn of he Ry ecrease in entropy. If the substance is noy, rea sense magmic tsb removed adiabatically, the omropy Will not change as the adiabatic changes are } ggepitropic, On demagnet aera Ly mt dipoles, distributed randomly causi sein-magneticentropy an ere would be a fal] in temperature. Such cool Hiobatic demagnevieston is appreciable only when the temperature is extremshpso ow, as only Such ondition ma; netic entropy approaches q range of thermal en! agntic sibsstatice like 2Gadolinium sulphate’, ferricammonium’ are firs 3 eans of evap rating liquid helium, 0£30,001 gaze: ‘applie the tisein-tem eral re |S counter acted by conducting néntth ériginal temperature is reache gas. > Pumped out and the salt is ther ly isu wiped field js thenswitche ff thie e temperature drops. The lowest ted re'reached by thi a 3 ASPIRATION xcaveny dream high, beyond the sky TYAN M.Sc. Entranco | GSIR NET | GATE | NEET | JEE © tery Last 15 Years C.U Questions on Statistical Thermodynamics ecules, distributed among the possible JE eeEtc . Assuming the expression rium conditions number of She), where A and b are [c.U 2001] 2. Answer tht that it igpFelarea ds dren [.fQ Z Yeo ane (i) Show that Ni. i oyAany jus ofb and show Obability that a [c.u 2001] diva eae What is thi jo mic) value of elange tr deiiol 2 A te Galculate (i) the ie two levels. [k = Nanolecule ifs, Two. cniEylevalove-O and, 6,414 partition funetion nd (if) Fatig, oF trent er of RiSleculdsdnn Boltzmann sons spel dultenperaurelANlS Ze [c.u 2004] 5. From the probabilit).cohtent-of entcopy, acgue f at H +H —» He reaction must be exothermic. 2“ [c.u 2001] 6. Define thermodynamic probability. Consider a system of six distinguishable particles. One of the macro states has the following distribution of particles. Energy [Oe [le [2e [3 [4e No. of 0 0 2 2 2 Particles South Kolkata: 304, Southern Avenue Kolkata - 26. (Near Kalighat Metro)‘ +91 98369 24983 North Kolkata: 47, Tarak Pramanick Rd Kolkata - 06, (Near Girish Park Metro)‘ +91 85829 79309 Website: www.aspirationacademy.in | Email: info@aspirationacademy,in | sini = "ACADEMY nd the SkY | gare | NEET YEE AsPIRATIO dream high. beyo UITUAM] M.S Entrance | CSIR NET [cu 2 modynamic probability. 1+2 a Calculate its thern . to its maximum value and how? 2 related 7. Which state function of the system Is Icu 2003 , degenerate ener, istributed among non By ley, dis rite down the expression for the partite’ ofn molecules, ergy (U) of the system can be expressed 8. Consider a system o represented by €0, €4, E24 fanction of the system. Show that in as ture and volume of Where, kis th 5 ‘ eer 7" Noe [CU 2003; 9. State Baro {-U 2002) 10. Show th: [cu 2002) 11. Entropyisjaifupctic mi i 2 lude that th functio ic =< Seeks | PE? (cu 20031 : he 12. Derive theBi tzmann' istril olecules Where the energy levels enfer ingen are i isizingethe coyditions involved, Assume BRS [C.U 2003] 13. § io} bbe © be that the relation.¢onné ie FOp ae the partition function Qisgiven by $= MQ ag y Where, E = Internal Ei the Jane , nergy of t - ka Boltzmann constant umber of molecules ij is inth . T=Temperature of the system, “= 14. Calculate the ni levels such that [c.u 2003] umber of wa; ys of arranpi) . on ging 5 dif : energy evel has 1 particle two ee paride: among 3 ene cc. 2003] uth Kolkata: 308, Souther t ‘Ave, / an ASPIRATION xcavemy dream high. beyond the sky TVARt| M.Sc, Entranco | CSIR NET | GATE | NEET | VEE 15. The molecules ofa gas have two energy states zero and eand degeneracies gi and gz respectively, Write down the expression for the molecular partition function. 2 [CU 2003] 16. Three identical but distinguishable particles are distributed among three energy levels 0, E, 2E. Write down the different possible distributions of the particles for total energy (i) E and (ii) 2E. Also obtain the thermodynamic probability for each distribution and hence the change in-entropy for increasing the total energy from (i) to (ii). 1+2+2 [C.u 2004] 7. For what increaseh GBI yee sai Cr i lué ol ture el ssure reduced to half? eis f re OK And the, 2% olar mass 0.029 kg NS is ee [cu 2004] el =10and find Q {C.U 2004] 4% es of interfialienergy((U) and he partition teh. 2 Cy ae [C.U 2004] Oh-degenerate 6 [C.U 2005] 21. Suppose thata particle ts chrad sraclorized by twa.enefGy levels c1=Oand e2= ec with sgnectivelyaWAtean expression for the partition function and hence find the average energy 0} article. 4 [c.u 2005} degeneracies gi and gz respecti 22, Entropy ofa system cannot be negative. Justify. 2 [c.u 2005] 23. The number of molecules in three successive non-degenerate levels of equal gap are 1000, 100 and 10 respectively. Show that the arrangement corresponds to Boltzmann like distribution. 2 {C.u 2005] sw South Kolkata: 304, Southern Avenue Kolkata - 26. (Near Kalighat Metro) ‘@&_+91. 98369 24983 North Kolkata: 47, Tarak Pramanick Rd Kolkata - 06. (Near Girish Park Metro) ‘@ +91 85829 79309 Website: www.aspirationacademy.in | Email: info@aspirationacademy.in | A. GADEMY ASPIRATION caver dream high, boyend the Sh TE | NET IITAAM | MSc. Entrance SIR NET GA IW 2 CLIVE show, rhird law of thermodynamics ai nnd fe Comma son aselid (0 tee you determine the “absolute eng variation of entropy eae int), How would ¥6 eee ren (qaverature r TF pe amour phase at temp! of the substan: 06) istributed among the, stem containing N molecules distribu -€tC, Assuming ste 25, Cotsen an eee Tevel represented by non-degenerate ¢1 alsi the ; under equilibrium eon, it rh odynamic prokabllipy show that ition, jon for therm: ey expression for van theleveleliss : number of molecules (ing Save consuants le 24. State and explain the sau Sa ahoge Tava therey 1.6 [cu 2009 Relvin) is SONS () ShowAthiat re Mf xm of tefoperatu i) Shows Ai 4 herd schema ip : aT on idee ecplbt. estas, Fa] el 26, AGfora [Cu 2007 ‘d eanitpandef thie energy levels. 28. Consider six distineut Gira eules é pian Modynatg, dt sbabilny (WISWhat willdSe'the value of W if one molecule is Temovet Cg 141 [C.U 2007] i Sats 25. Consider a system of nonsiti crac RaS << hich are iste) Fi Particles“at Constant tem, erature whic jistibuted in three non-degenerateasiee ier 1023, 2 isin such a way that €1, e2andes ¥ 1025, 2 x 1923 23 energy levels are equ; and 1x 10: articles tively. Show that the Qui-spaced, 2 P $5 respe y: [cu 20071 systems Ai and Aa, ? Also, tance of this Tesult? 4 ee for configurations aval . What is S Sz, S2 and S. cu 2008] ute the entropie. = RATION xcavemy high. beyond the se intranco | CSIR NET [GATE | NEET | Jee (Wr) of a system of ‘N' distinguishable particles, SA Wt = 2%. Using Stirling approximation find the distribution. Compare Wr and Wia and " [c.U 2008] 32. Consider a system for which the equation of stae( 2) = [cu 2008} ow that the entropy ofa $' edt Capacity equation,to.be apphi Pecan Mca wt Er Hi Lad here Cp is the heat. [cu 2008] Ic.U 2009} of in W to be [cu 2009] peratures by [c.U 2009} the partition em. 4 [c.u 2009} ce sap wage Hal siti e ey te {Partition function. What will be the expressiqnéfor the populatidn'of tite tworfevélg? What will bolita of the populations for anid fo? 24297 Ie 39. Derive an expression for the barometric distribution formula, mentioning the : ions i i 0 bar and 25°C is 100 cm hig! assumptions involved. A container of O2 at 1. sea level. Caleulate the difference in pressure between the gas at the prey a container and the gas at the top. 4+2 i of 40. Derive the expressions for Helmholtz free energy (A) and enthalpy eon partition function. 4 B® +91 98369 24983 South Kolkata: 30A, Southern Avenue Kolkata - 26. (Near ean Boe Ta08 North Kolkata: 47, Tarak Pramanick Rd Kolkata - 06. (Near Giris by en ae Website: www.aspirationacademy.in | Email: info@aspirationacademy. dream high. Entrar 41, Relate Helmholtz enerBy magnitude of the partition level? Comment. 2+2 i maj 42. Give an account ofadiabatic det low temperature, 442 43. For a collection 0 ; function and from it getan 45, State Ner a ff 6. Ob wf oipetric formula 4 can i altitud ie biatiines pressurdte decrease Byia ca W iv = 6 a 47. Calculate 49. Explain, with $-7 did Paramagnetic substances 50. Show that $= ky U-u(9) aN Ing + Y=U(0) T 51. Consider a syst Probables tg mA consist a. Y capeMm ATION, oe neg CORNET GATED # ASPIR a tributed among the pose; “contamina npolegules, TISRES Possible tei a Ladd e id iaienel ved. Show, grap cally thedecrease, er | GATE EET IY dynamic probability, the tae degeneracy of the - the a meast ours - [cu 2014 it can be used __ zon and show how it can to ob gnetization an Icu zen } generate levels, evaluate the Partit} ofthesystem. 4.2 [CU 2012 ac ilityss! hat, aN by | tioning the Le of Haponietri

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