CHAPTER-I Statistical Mechanic 1.1 Introduction : S tatistical mechanics is the branch of science which estab see between the macroscopic properties (variables) Salistical eae ae of TUNGTSe On properties (variables). The : r 's its name implies is not concerned with actual motion or interactions of individual particle, but study of the most probable behaviour of assembly of particles. The word particles is used in a broad sense meaning a fundamental particles i.e. an electron, an atom, a molecule etc. The particles are well define and a stable unit of @ given physical system. The study of Statistical mechanics can be classified mainly in two categories 1. The classical statistics or Maxwell-Boltzmann's statistics and 2. The quantum statistics (Bose-Einstein and Fermi-Dirac statistics). The classical statistics or MB statistics utilizes the classical tesults of Maxwell's laws of distribution of molecular velocities and Boltzmann theorem relating entropy and probability. This statistics is used in case of identical particles of any spin that are to be distin- guished. The molecules of a gas constitutes the most important class of such particles. The M-B statistics successfully explains the properties like temperature, pressure, energy etc. of a gas but fails to explain experimentally observed facts such as black body radiations, Photo- electric effect, specific heats at low temperature etc. Thus the quan- tum statistics was developed by Bose Einstein‘s, Fermi and Dirac. One form is known as Bose-Einstein statistics and other form is known as Fermi-Dirac statistics. The important distinction between these twotypes — is that MB statistics is used in case of identical and distinguishable particles but the BE statistics is used for the system of identical and9. 1] Compartment No. 2 Number of Microstate abod bad adaDifferentiating equation (6) with respect to W, and keeping W, asa dw, From equation (5) we get as 3, Since L118, of equation () ‘that the left hand side must be equated to is called Boltzmann constant and itis denoted by k thus owt), dw Separating the variables, we get aw df =k$— (W) =k Integrating this equation we have, f(W) =k log W+C. £(W) =k log W+C Using equation (1) . S=klgW+C 10), Wher, Cis constant of integration and itcan be assumed tobe ze 3k later interpreted that W as the maximum. number of to be zero. Thus, substituting C = 0 and W = W,., in ) we get Isolated system : of particles which does not interact with its surround- jon of the particles among the rium is that for which the probability of m consisting of molecules of an ideal gas under particles of the system are identical and distin- another and there is no restriction to the number of s which may occupy in any given state.system of large numbe, particles. The ideaticay > "On, istinguishoble ca par ‘Let us suppose that four particles arc in energy state», ‘are in energy state E,, and so on. It is assumed ‘states are available to each particles. ‘Suppose there are N particles (molecules) i 4, «»mbe the number of particles in the energy le ‘respectively. Let &, BB «...-. be the aumber unit | _ with differentenergy levels as shown in figure 1.1. Eon Fig; 11: Distribution of Particles of system amongst different energy levels These particles (molecules) have defini as well as occupy definite positions and hence Points in phase space. In equilibrium, the system temperat it Term T having constant V and the constant i si cn ces tm ip ; ferent ways. The s, as if ays. The secon | BY Sate E,can be selected in (N-1) different aye In general, if first ene Aistinguishable different ways gs oS! Ways, of arranging 2, partic Eyaregivenby B= Nt e W(N—n,) ‘Second y: thle dierent energy ‘State consists of; mea of z 2, particles, the di fiven by aranging n, particles in ey te that ane P=N-nc, =—W=n)! e. "8 \(N=n, =n, )t is Process can be continued for all available particles and for all energy states and then by multiplying P., Py, Py ........ete. The total number of ways of meaningful arrangement as P=P,xP.xPx [art an eat a ayl(N=a,—n,)t] ~ ~ 1 ea) the probability of locating a particle in a certain energy then the probability of locating two particle ,in the same energy. IIbe g,xg,=27 probability of locating is gi. Hence the given distribution is given by G f particles in the energy levels Bp» By ones be the number unit associated with different energy levels E, total probability W of asystem, which will be probability of distribution multiplied by the probability, Itcan be expressed as welWis NES af) Where, 11 denote the product sign for various values of i Condition for most probable distribution : ‘The most probable of the particles of system among the energy states in im is that for which the probability of occurrence is maximum. The most probable distribution can besen(B) f both sides of equation (5) BREW banter] FW = logN!4 SI logs —n,! sete 1 number of particies is very large, factorial terms be Spproximated using Stirling formulas x!=xlogx—x equation (6 )be Written as 10SW=NlogN-N +n, bee, ~(0,logn, A] fog W =NlogN-N4 ¥[n, leg, =n, logn, +, As the total number of 2s moleculesis constant, we have following relations m+n, +n, +.........¢n, =N= Yn, =N = constant... Since th and 2B, +2,8, +n,E, +._+0,8, ‘Now equation (8) can be written as log W = NlogN-N +n, logg, ~En, logn, +n, Using equation (9), we can write logW =NlogN-N +n, log, —¥n, ogn, +N log W =NlogN + Eniloggi-Cnilogni Differentiating the above expression, we got 8(logW)-5 (NlogN) +5(n,loga, )-¥5(0, oe n,) ButN and g, are constants =En,E,=U= constant...(10) semssn(11) i SlogW)=0+ Stoge,.n, ~ Bila, 2, Hogn, 5n,] | 8(logW)= Plog g; 0, — Pn, —logn, 6a,). But from equation (9) 5N=3En, =0 8(logW)=[loge, .’n, —logn, 5n,] ‘\ >. (lo W) = 5 (loge, logn,) 5a, = Fquation (9) and (10) can be written as Zin=0N =o... and Lon E,=3u -0. 4) Those two equations can be added to equation (12) by making the use of Lagrange method of undetermined multipliers, Let & and B be these multipliers. Let: ‘we multiply by—a to equation (13) and by-B to-equat ) and adding them to equation (12) we get Z[log(g,)—logn, ~4-BE, ]n,=5(logw) For most probable distribution, 8 (logW)=0 therefore we write Lllog(e,)—logn,--BE, in, =0 Since, 3ni 0 As itis the change in number of particles + Hlog(g,) -logn, -0-fE,]=0 -(a+BE,)=0 B to Boltzmann theorem S =k log W <.85=k5(logW)7 2882kxI 5 . ln Toss Bane) +58= ka En, +kGZE, da, assuming Yn, = 0 *8S=kax0+kBEE, 60, +.8S=kp3U ~6U=ZEi6ni From the first law of thermodynamics 8Q-sUHPSV Again from the second law of thermodynamics . 8Q=T8s vas-£Q “TSS =5U+P5V But V is constant ..P6V-0 TéS=8U 58S = se From equation (2) and (3) we get AS Nis constant, En, =0 and craluate B we have to eliminate a (3) Ke og om th : Now writing nas n(B), g, a g(B) and EB, as. Where, n(E).dE = Number of particles each | : between E and E + dE. ‘(£).dE = Number of unit cells having energy range betwee + dE corresponding to the momentum range P and P + 4. So auton (1) canbe writen a= B= SEN nee n(E)dE =g(E)dEe*.e Lee) a(B)a= 5 ffexaytef fd. dp, dp, ol is the volume of single unit cell in the phase space, JJ fax.dy.dz = v= Volume occupied by the system in entire position spa es Fig. 1.2: Volume of Momentum Spaceoot SY" ean This equation gives value of a . Thus; knowing the values of « and P, Maxwell Boltzmann distribution law can be written as v =pm(d e+e) m(2vdv) = mv.dy the values of E and dE in equation (1), the number Speed range v to (v +dy) is given by BAY as Sag -n(B)ae =2¥ xB? xdexN,(_¥_)",. n(E) 2m)" xed; =z) e SN at Oey xe gr vee) This gives the Maxwell Boltzmann; energy distribution law. This can be written as alt) =e The curve n(E) against E is not symmetrical as shown 1.3. For smaller values E, the ee “xponential term becomes almost onc and n(E) varies as, 2”? which is parabolic. For larger values of E, the exponential curve becomes important and the curves falls off exponentially. The arca enclosed by the curve and E f axis gives, the total number of Particles. The curves also "(5 indicates that a large number of particles have an energy ian a) m as Maxwell-Boltzmann law of speed es ofa gas, In this equation n (vis the corresponding tothe maxima 0 ey of the curve. Fig. 13 : Variation of py, of particles with ber the en a ttyMig: 14 Variation of n (y) potted against v at different temperatures WT . Ata given temperature, the area under the distribution curve is "qual to the total number of molecules in the 848. Thus we have Nefa(r)av Since, the area must be same at all femperatures; the distibution Gurve must flatten as the temperature rises. Abexe figure shows the speed distribution curve for the molecules arbitrary temperatures. In figure n (v) is plotied exist sped Most probable speed : {Te most probable speed ofthe molecules is that peed at Which the number of molecules per unit range of speed is maximum, From the M.B. distribution law for molecular « ee PEM, the ‘number of molecules per unit range of speed is given by a ‘value is called the most. Probable speed (v,) at that temperature, = MOA a(S) tne ‘Taking logarithm of oth the sides ofthis equation nano) ens anne Differentiating this equation w. +10, we get 1 day), ee 2_mv AO) de 042-2 vo eT + SG] za av v kT ‘As the most pmbabie spead v ~ . the number of molecules n{v) is maximum, Mathematically, the condition isgiven byie Atv=v, M9 dv Equation (2) can be written as Most probable speed =¥, = PET yay EE cnt) Vim m Average Speed (¥) ' ‘The number of molecules whose speed lie between v andvtdv“* qyya sapppaed so AnquINU yo WOHELEA + FP (9). tN rolaye afta 2 (A) pop, arembg ueayy 1004, <= 145 a5 a°se8 yooysad v 40} yeu PUL o% Smt] Or hes =e =| (eee = i Da) Ae) Pe F wl ey = ‘ ee by (Gee) (Jr -* z a ue) (xzyz (g mega! joe} Ge) Cf 2e|e (eee ApeT, A a joa as Aq woAid 51 paods oBeioav og op | fil i Geos) Gahi-e co Aq woald st [ex39,u1 sup Jo anyea ayy, “speBoq Uueuzyog-[Joaxeyy ay JO suo St qedouur SuUySp oa wg EE oe pase 9% A cs snc Nu, = ee! “aWeyoau0n MmIS=1 © | mi01A=5 4 sti= mh © ] Agpqeqaud oareufpouuons wan ‘(opepmd prpsqos! j pso WN “L “se puv Adonua usoinjaq worynfos 322x9 St Bum : ae c sone Polleo st umsuoo sureuras £Biou9 [2}0} spt JwUp Os w9}SAS 32 WIM yoer3m 300 wayshs Jo aesooT (2 saneysoxoeus JE Ui SOYMISOIOIN (4 ayersoxoeut o} Suspucdsois09 aye a io qej0y stew oqyso1oou w Jo ANqeqosd oyueuKpouLaK YM sgjorued Jo wiasKs y “9 Hh soreysoxoqu jo zoquinu ayy“ } Trjo20N © *s osoyd peuoysuawp x18 ur 1120 uWun Jo owmjoa ayy, -z ——_sefouredyossqunu kay] aonsed coe cs eds umuatiow puv aoeds uorwsod jo uoneuiquosoyy, | oai® Aue Kénaco wos yoy) s2jpnHed jo 1aquina son 5 nL ae ies0900N © Seo it STSOATTPN PUE aIESOIIWY (Q ee > ASIOWAXa - S{ warsAs © wt sojanied Jo uornqusip astound _ B yo sired quaiayj1p ut quszeypIp st Yor wioIsKs so Apadoud ayy. ON (P) Cn)a=(ua 1) uo, 111M 944 (7) UonEnbe pue | ggg Ut? tos; uaip ‘sed uation yo peods oBexone jo sey o1 jenba- UeBoupay so poods oSvioae aif) “L dua) ye “soddng .Answers to multiple choice questions : (1) a, (2), B)«, (4) 6, (5)b, 6), (7b. #eeee by Vins (8-17) (8-19) (w-13) 8. ‘Show that mos: probable velocity of gas molecuteig v, «,[2KT m S19) WIT) W19) 9. Find most probable velocity when: m =3%10 gm, T=27'C and K=1.38x10-“ergs /K. (6:16 10. Explain the terms, energy states and density o 1. What is unit cell in a phase space? Show that B) unit cell in phase space is h’. 1 Wh 12, Derive Maxwell’s distribution law of molecular speeds, Gin ——