Boltzmann’s Law of Distribution of Ene This law is concerned with the most probable way in which given amount of energy is distributed among the molecules. Let us consider an isolated system in which number of molecules and energy are constant. r Since molecules move randomly in space. Therefore they will have different velocities and different energies but after sometimesthere will be complete distribution of energy. ny, Ey ny E, ng E; ny Ej We have to find that how many molecules out of total are in particular energy state.Boltzmann’s Law of Distribution of Energy Lets consider an assembly of three molecules which shared three quanta of energy. There are 10 possible arrangements for the distribution of three quanta of energy. General formula of permutation. N! ~ my! X ng! X ng! xX ny! -@) wy! Several possible ways in which No. of things can be ordered. 3! 3xK2x1 First possibility W, = wo 3KaxI> 4. Second possibility Wp», = 3! = SKE = 21x! 2xK1x1 3! 3x2x1 Third possibility W, = Tee Tea So W=W,+WetWe =1+3+6 =10 So, there are 10 possible arrangements for 3 quanta of energy. So, eq. 1 can be written as. N! - (2) Ww=— LIN,Boltzmann’s Law of Distribution of Energy An assembly containing “N” No. of molecules having total energy “E”. As our system is isolated. So, total No. of molecules and total energy are constant. Ny + Mg $3 eM = LI My EN eee ee er see eee (3) Ey = LimyE; E, +E, +E. By taking “In” of eq. 2, we get. InW= InN! - In¥jnj! . According to sterling approximation. InN! = NInN—N nV jn! = Lj (ajlnn; — nj) InW = (NINN — N) —¥)j (jlnn; — On differentiating eq. 06, we get. din W = d(NMN — N)—-Yj d(njlnn; — nj) dinW = -Yjd(njlnn, — ny) din W = —¥j (dnjlnn; — dnj) din W = —¥j (Innjdn; + njdinn; — dnj) —Yj (Unnjdn; + nj— dn, —dnj) i Xj (nnjdny) .. we (FZ) . (6)Boltzmann’s Law of Distribution of Energy On differentiating eq. 3 and eq. 4, we get. Lj nj =dN =0 oe (8) Dj dnjE; =dE=0..........(9) By multiplying eq. 8 with “a” and eq. 9 “B”, we get. ayjdn; = ww (10) BL sdnjE;= 11) By adding eq. 10, 11 and 07, we get ad jdnj + PYjdnjE; — Lj (Innjdny) = 0 XJ (a + BE; — Inn,)dn,; = 0 By putting dnj=1 Lila + BE; —Innj) =0 For “n,” molecule above eq. can be written as. a+ BE, —- Inn, =0 a+ BE, — Inn, =0 a+ BE3 — Inn; = 0 a + BE; — Inn; =0 Similarly,Boltzmann’s Law of Distribution of Energy On rearranging this eq. a + BE, = Inny q4) oot Bey = ny e%, eBE = Pf ove eo we (15) By multiplying eq. 15 by}: 085 j BE = Ff my eon (16) By dividing eq. 15 by eq. 16, we get. 2%, eBEy 1"; KT So,