z n Elementary statistical Scanned with CamScanner thermodynamics Defenttion of slate Thermo dynamic | thermodynamics, or statistical mechanics, is the ° o ° ° ° °o.°8 S ° °° ° 2 Oo Cieen g.2 Ws soy oo oe Arnot ef gai Aocalisod- system macroscopic and microscopic properties of a system. yr _Nact : 4 a Dishing U SABE 1 encical, SS ee of mel particles Ja austig wiable as Uiee sening . di fFeviert a vibration Boraetween or Cxpand 2 Some; amon s i (mele tenginy Creduce 20 | Fh Two kinds of particles sy Z inet ve g the Pracchan bh Cogs Pauses Oe with owt / + for warren ces ceheces| | sldentical particles, ori [f eabaciey i 7 E ideal gas particles (such as gaseous molecules), is also calle -localized particles. : ‘Distinguishable particles (Such as the sr will be introduced in this chapter. atoms in crystal), is also called localized batts Only theScanned with CamScanner E mete (8.2 Energy level and its degeneracy 9... Ne one stebe ) mesmrCclenter( eG } f LH \ “I ‘a y Ned state is the sumof | HA o ti Sears ses toon reapers s —— Nebo , nuclear (n), vibrational t=O) s are said to be egenerate, if the Samajenergy ————a Lyemick es I (r) and translational (t) a oy bevad 447A component, such that: eae ye SECO Tne Point 3 ober = mess contel Yee EXE FETE +E 48, wtle Stechic sgise'y a fd eneray Neda, ua Ding, OF one vu Bees , moleae ( . "OF Particle este os s amov nh ORF colale Los SF enexoy Soe a We Abized edlse pean 4 Seas 5 - * n The degree of freedom of movement : Rotation we ave Calling about af | puke ee sransitonaneS] — "Cenker OF mass © ~—| Sast diaterc (2 aon)! “mbroaseor’e 2 fo matter bow myn Ke aides! gy ele ul lea oF ie Pepe coos 7 Arse Wwe afte Ealing ude (OO OSE Wie 4 Taninin Tonio : ae "a ‘eae Sq ck SMaA adem eA’ ie molecule € containing.n __&< \, atoms hag3ndegr tally i Three.of these degrees of freedomtan be assigned to motion of the center of mass, two orthree to. rotational motion. Vibration i Gyasaxs. 5 = 4 degrees.of freedom of: —eae ae 4 ration; nonlinear molecule of H,. O.has hah 3%3°6=3 degrees.of freedom of <0 fy vibration, lq nonser of {recaone : Tach dng symm ye Srey Fan Js 3 Soares ae e : ae ye = Vil 7 sudea “HF of Carrs 2) 24 Sf win bey 8.2.2 Translational particle Va J all energy levels except Ground energy Ra i < are degenerate. : wu 7 frase of Amdeutes WE 7 Example At 300K, 101.325 kPa, 1 mol Where h=6.626X 1074's, ing are itegrals 2, ra + of H, was added into a cubic box. Calculate s. The number om hon ly Youd /s Lake the energy level ¢,9 4 aground stat, and the...) eneray r energy difference between the first excited, Laue a a ra a +m) 5 state and ground state. Axe t nyt @ A A Snead ss He Cove mer Scanned with CamScannerfe keg wes? Bx66626010°9 gst 0 5 }x3.347 x10" x0.02462"" ) c Seltion Tete atthe cond ae oS 8 san 6=11,622x10“~@) e Bons § e ya RE A —oonscan? wet rd cuttel= 6 =p Beg 8 40 40 one 2 ‘inane tcsmanneneh 5 22- $8110 = S811 | in Sepak 3 es - we Gant 3 Gare Saniculi a GEM tp2O88 10) 6.02210" =3.347x10ke sf ie ergy difference i smal! hat the trilational artic et less E ——s Gun Hs & hat the energy changes of different energy levels can be think 8 a becavig 2-0/Sg_ (fas a continuous change approximately. : Is He + me ne ahove 2-08 xis? kg Zdirecry a So wie ake 8.2. One-dimensiona\\harmonic, scillator ered and rotator Giatomic) : , Nec os 2 PrpEritS Coming Fron vibe ahs, ional energy level offi Seavore BAN ie V=0,1,2,02 = 00 Ler .# ot pal Te MC ENEY jag er tne 3 on z a mnt. weet on |= BaF) BEd 9) % is the reduced mass, The degree of degeneracy i G5 =2I+1 J a dae lileita, Wapunt f E= Slectron and atomic nucleus omic nucies Tho dierene 2 iterene efiveen enere motion otion and nucl nucleus motion electrons and nuclei stay at their (Ground sate} Both degree of degeneracy, 2. for electron motion at ground state and degree of degeneracy, g,05 for ‘nucleus motion at ground state are different for different substances, but they are constant for a given et substance. ™“™ - 8a Distribution and microst ss amon} Foroample,e distribution of 6 identical agi (Ghits of energymust satisfy with the con: 1g 9 ‘The total number of ways of distribution is 26, | is called the number of distribution of states. —_—_—_—_—_—_——_———_ One distri microstates Wp, the sum of all Wg is the total number of microstates £2of a system. That is. 2= Te o ion D of energy levels has a certain number of te Scanned with CamScanner“There are 16 ways of distribution of four distinguishable particles in two identical boxes. a aan) fel @ arb | [Toe 8.3.3 Distinguishable particles + Consider Ndstinguishable riondegenerate energy level localized particles distribute into W, = NN-I)(N-2)--(2)0) = NI Now consider another kind of distribution thatthe numbers of particles occupied in different energy levels are denoted as n,, 2g, ~, 1, All the energy levels are still nondegenerate. 22D M5, sthree different distributions of six particles, The exchanges of particles in the same energy level do not create new microstate because every energy level has only one quantum state. The numbers of microstates for three distributions are We now censider that the degree of degeneracy of energy levels is g,, 9., Suppose number of quantum states is unconstrained. Consider particles ocupy energy level everypartclcan chose ‘one froma quantum states inthe energy evel Rence the ways of Selection form particles are = a gi For all energy levels, the number of microstates enused by the degeneracy of levels Scanned with CamScanner+ the number of microstates for a certain distribution D canbe written as Th Tle =e Td ial 8.3.4 Identical particles + assume that there no rest ‘occupy a given energy level and t + there is only one way form part Therefore, the number of icrost on on the number of particles which can energy levels isnondegenerate. 1 energy bution D fora system is Wo ergy level is degene ibuting a particles in two quantum states which can be: (2+! 2 W= =3 00 ‘energy level. This of 8 persons and (4-1) di dividing walls are indistinguish is equivalent to the permutation of the sum both persons and -)! we @+4=D! “ao + the number of microstates for, particles distributing in. giquantum statesin an energy levels (a,+ g)-1) g,—)! one kind of distribution isthe products of the number of imicrostates for every level m Scanned with CamScanner*Hfaxceg, this equation can be simplified into WT] eaWins gn 2) ta nYei~Wa,-2)-- AB, Waj-2)-~ Scanned with CamScannerRotation eFor linear molecules, F=2 «For non-linear molecules, F=3 0 tk Scanned with CamScanner8. The most probable distribution, equilibrium distribution, and Boltzmann, ibution + 8.4.2 The principle of equala prior probabilities Statistical thermodynamics fundamental assumption that all possible configurations of a given system, which satisfy the given boundary conditions such as temperature, volume and number of particles, are equally likely to occur. 2=ANU,V)=TW, 5 ns of three Example Consider the orient unconstrained and distinguish particles. What is the probability that two are spin up and one spin down at any instant? “Solution Of the eight possi configurations for the system, oftt MTL Tt dit tHe Utd Lut Wy «The second, third, and fourth comprise the subset “two up and one down". Therefore, the probability for this particular configuration is +P=3/8 8.4.2 The most probable distribution = The probability for bution Dis pat Q ‘the microstates of three harmonic oscillators which are distinguishable particles with total vibrational energy of U = $hv| GESEBRSEE Which distribution is the most probable distribution? Scanned with CamScanner8.4.3 Equilibrium distribution + Ina system with large numberof Ny, the most probable distribution ‘may represent all distributions. + Stiting’s approximation ‘amore accurate form InN!= NInN-N NI li =1 xu» aN (N/e™ Consider a system consisting of N localized particles which distribute over two degenerate quantum states, A and B. M denotes for the number of particles in state A and (N-M) in state B. the number of microstates for this distribution can be expressed as re © (v72)QN72)! + Every particle has two possibilities to popt states, state A or state 8, The total numberof microstates for the system would be 24 223 Sam? fs” fesMUN-M)! «The probability for the most probable distribution is ube of pares a is about 20% the then P(S)= oe ~8x10P + We consider another distribution that hasa distribution number ‘deviating m from Nia, its probability would be Scanned with CamScannerWw(E+m) P($tm)= ‘o al “The probably forall distrbution ranging from N N Mako wo Maen «isthe summation oftheir probabiltes. By sing ror futon DP ieee Lies erf(x) == fe dt == feat vey Va ‘swe obtain “F o(¢-myin “fete 0.9999 ae aw w rium is most certainly going tobe the most nor atthe very least, with these kind of numbers, losetoit. 8.4.4 Boltzmann distribution Fora large number of noninteracting particles me) AT n, =2e i. The population can also be expressed in the form of energy level distribution 6 /KT m= Age The total number is N=yn=yae™ N=Dn=yages J # i i Scanned with CamScannerToone) VI e Be hbo as Abe felative pation = PE Jz . ra 2 Jags) er (-Bsaw) N N aw Ikt then any TS AT for any two levels: foratin i 7 = irtiion function - TT ZA a= Dige" The ratio to total nut ‘ 7 n get gee q ‘The distribution that obeys these eq) S tzmann Boltzmann distribution is the most probable distribution. The distribution. The equations are also known as Boltzmann maximum value can be derived by using Lagrange’s method of distribution law. fs © undetermined multipliers Scanned with CamScanner — —— _ 8.5 Computations of the partition, ~daaa_ mosyrensss | = Vid, Wy VeIn - dimentivn less 3 To calcofibe + +8.5.1 Some features of partition functions propery és «(a afTea)the partition function i neddegenerstppfthe cof alin arnan ncn at Ne Fei FE ns a img = a= Lee ety (poet By 2 ee se Oe Pau gal ab = 8,8 rs8vSes8ni + (2) When soBERtt for each terme/kTr0, OF very koe eve a functions for 5, mode motions are expressed as 1 a 3 lim q ==9 On g (ond [st ey t= qW =Dee a +*(3) factorization property Ifthe energy is a sum of those from 7 independent modes of motion, then ery Paltihy : : aS Berg Paltih, prachin have 2" buhdyier ~ ° st hgke 7% wowi OH eet) oad =(isues exo 22) su exp(—F2) ah Lew exp oh Seu exp). Seven FOU Fw We In y ae nebinwmne 382 Zero-point energy I the energy at ground state or the energy as. lowered to absolute zero, Suppose some energy level ‘energy at evel is, thee statels os 6 = 6 —& + Taking the energy value at ground state as zero, we can denote the partition function as q°. e, & o = aT - q = 2 8e o — ok, x q =e 9 gue; gaeNg; gaeeg, gnc g: ginc™™g, Since €,¢=0, ¢,00, at ordinary temperatures. De® I 2 =4, +The vibrational energy at ground: S is =th + therefore 0 _ giviakr W W tion in any levels does not depend on the tenergy. «the numberof dist selection of ze N pee ge VT Ni, rat na—get = q Scanned with CamScanner= Deven) 4= LE Sew} >> exp| cot (sae *) Take q,,as an example » eae LOC gar a For a gas at ordinary temperature(@2< = CamT balbee Scanned with CamScannerftheHe molecule is6.006{(6.022 20%)=6,6466Xi0"%kg. Substituting _~-these numbers ad the prope natural constants, we ha a> 4xs'& ») keel ees janpost ayer — Za o-(28eee8 38x10 pala e x01 7820519" t a We Yegummmed te Jv ee —fo2— "bis I garde # of Parhidg = (%) Hoe 8.5.4 Rotational partition function The rotational energy of a linear molecule is given by ¢,=J(F+1)/?/8n21 and each J level is 2/+1 degenerate. iS Ves+ Dexp(- ZU +8) oo T @< n€; 7 a /KT N Mae ote q vay gets, (8.48) “4 Scanned with CamScanneri 8.6 Thermodynamic energy and partition function (3) lela} o(Q) Bae Substitute this equation into equation (8.48), we have Substitute the factorization of partition function for q Only g, is the function of volume, therefore E=kT'C ang) ot nv 9 -t Few eer val vey =U,+U,+U,+U,+U, | Ifthe ground energy is specified to be zero, then -mr( 222") or v Substitute q°=ge"""into this equation, it follows that Sz Kk WQ@t kT Cee) = U° =U-Né, Ittells us that the thermodynamic energy depends on the zero point energy. Ne, is the total energy of system when all particles are localized in ground state, It (denoted as U;) can also be thought of as the energy of system at 0K. Then, U® =U-U, NIV S=nk nf Ye WK 7 Scanned with CamScanner+ UPcan be expressed asthe sum of different energies U® =U) +U2+U8 +U8 +U9 US=U, U%=U, U? -u,- U’=0 U%=0 The calculation of *(a) The calculation of The calculation of U? =U, = NKI? (4+) ar ), din 0.0 = NkT? are =NkT The degree of freedom of rotation for diatomic or linear molecules is 2, the contribution to the energy of every degree is also % RT for a mole substance. The calculation of 1 CL a dinar aT aT 1 yoy U9 = NET’ = NkO, Usually, , is far greater than 7, the quantum effect of vibration is very obvious. When @/7>>1, U°=0 Showing that the vibration does not have contribution to thermodynamic energy relative to ground state. Scanned with CamScanner«Ifthe temperature is very high or the@v is very small, hen@v/T< 3 Scanned with CamScannerIla ee" =] ve =k, 3 ae Aa = Do via 7 + forareaction aA +68 =I +7aM oe Uo Ke NING WO paar 654 int ghee Gaga nab + 1ény + ME «The number of molecules per unit volume is defined as the ‘molecular concentration C, = «The equilibrium constant expressed inthe molecular “Tc f ae =[T (et) Jeno ! oa =e a = Tease eee Cae sp 95 /V ‘scated patton onetin of per nit volume ate condition and denoted by g Le” fl fmter =" stm K.= I dip etl Ws Ta “Relation between concentration cy and molecular concentration Cys ¢y IL is Ke= GILG ID” ayaier WEE Do g-aeitt qi! 1)" (a5! LY 45 + Fora general reaction of ideal gases Scanned with CamScanner\ aN Gora G au ) r (+ FS Va y | » vey (Aiea 0 Ny . Ms In@ =n wa, by be Ie) - Ninny ne ie eo, =n\ S$ + Ov Te e Tye em. oe \ Cot | ey ding <\N. 8 Aimsst zero ot Pies Can be aegliciedt eS mus = SKN Uekt v S SKNT Urpy= H Uduiey)= 4 Ss yiet awk = H 2 C1: A H = wg Scanned with CamScanner