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Partition Function

The document discusses the partition function in the context of an ideal gas and its correlation with thermodynamic quantities such as entropy, Helmholtz free energy, and Gibbs potential. It explains how the partition function, Z, is derived from the distribution of gas molecules across energy levels and its significance in calculating various thermodynamic properties. Additionally, it provides equations for mean energy, pressure, and specific heat related to the partition function.

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8 views5 pages

Partition Function

The document discusses the partition function in the context of an ideal gas and its correlation with thermodynamic quantities such as entropy, Helmholtz free energy, and Gibbs potential. It explains how the partition function, Z, is derived from the distribution of gas molecules across energy levels and its significance in calculating various thermodynamic properties. Additionally, it provides equations for mean energy, pressure, and specific heat related to the partition function.

Uploaded by

samik2005king
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We take content rights seriously. If you suspect this is your content, claim it here.
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3*0-4. PARTITION FUNCTION AND ITS CORRELATION WITH THERMODYNAMIC QUANTITIES : (a) Partition Function : Let us consider an assembly of ideal gas molecules obeying classical statistics e.g., Maxwell Boltzmann distribution law. Following this distribution law, let n, molecules occupy r'* state with energy between E, and E, + dE,, and degeneracy, g, . Then ny = ge te ErAE erdoD OF ENSEMBLES-1 eruop ores te aw where sothat total number of molecules in the assembly N=Dn, = Ax g 098 N e Nay get az 2) where Z is called the Boltzmann partition funetion or simply the partition function. The term Lee represents the sum of all the g,e® terms for every energy state of the given molecule. Consequently the quantity, Z, indicates how the gas molecules of an assembfy are distributed or partitioned akong the various energy levels and is called « partition function faking the weight, {ofan individual level as unity, we can write the equation (2) as Zey ef a @ With entropy, S: Zaropy is related tothe weight, of most probable configuration by $= ROE Gnas: w where for @ classical system having total number ‘of molecules as. v(E6)} t wehave o= win, or Jog w= logN'+ D (n, log 6, ~ 108 n,) Using Stirling approximation ogi!= logan. woget logo NlogN-N+D, (fogs —n, eM, +1) According to MaxwolL-Boltzmann distibation law, fr the most probable configuration, we have “a era serene tae wo that loging = MlogN-N+S° {n,log 8, —n, loge, Ae )+0,) =NlogN-N4E my loge, - nloge,- low a+ n BE +E ny ‘Taking En, =N, total number of particles, and En, of the assembly, we get 108 Opax = Vlog - Nlog A+BE N = Nlog + BE =NlogZ+BE (Using ea. 2) in eq. (6), we find that entropy Stinger clone ib stop? eget ‘ E -wenz+t s2ve Foranideni gee 6-387 woth stig which gives the entropy of the assembly of ideal gas molecules. (ii) With Helmholtz free energy, F : Helmholtz free energy F is given by E-TS E-TUkNlogZ+ E/T) = E-NATIOgZ-E NAT og Z. With total energy, E+ ‘stem of N particles (assembly) is given by Due sera ey : ‘5 using ea 6 (osing oe" (using eq. 2) METHOD OF ENSEMBLES yarn on ENB mnLeewarwsis ey Since 2=¥ ge8 2D chr we have for isothermal isochorie transformation “nets, 4(% a (@) -z sector =ZE (using eq. 8) C E a ae ip _nkT? (az E=NE= (%, 2{ 2 cog2] a {2 os2 (ieoe], ° (iv) Wiehenthatpy, #1: Eutalpy in given mepspretear (or idat gas PV = 7) 12 emer] 200525] +47 sar{ 2 on ao (W) With Gibb's potential, G: Gibb's potential is given by G=H-T 2[ 2, + RT~7( kN log z v= won| toga) onr-r(enmezet (Using eq, 5 and 10) m2 eg] orn | 2.2), -variege (oe2] (sing 6q.(8) = RT-NKT10BZ aa 150 ELEMENTARY STATISTICAL MECHANcg (vi) With pressure P of the gas: Pressrei given by oF (3), 3 =| Zon) va using eq. (7) (vii) With specific heat at constant volume, Cy : o-) = 2) mer? Zio, = 2 mr? 2 oe2n] e 2 og2) 47? -m[arZ-o2 7 ton2) 03) Ex. 1. Show that ifthe partition function is given by Z, then mean energy, E, is given by 1 (logZ), where ® ir Refer to the cas (i of relation ofZ with total energy E. We have shown therein eq. (8 tht EAD sb e% w Further 20D ge Bey pect or B BE y (Using e@. 1) which is desired.

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