131. PHASE TRANSITION cone aan aad bene hs culating in phase of three types : solid, liquid and gas. The : ‘am (fig. P a ee ig. 1) separating these phases are called phase equilibrium and pressure all three phi where lines meet is called ‘triple point’; at this unique temperature Presi ases can coexist in equilibrium with each other. Point C is the critical point at which liquid gas equilibrium line ends. The volume change AV between liquid and gas has then approached zero; beyond C there is no further phase transition since i L there exists only one ‘fluid phase’. ey In fig. 2 curve of constant Fig. (1) Fig. (2) temperature T, for an equation of state, P = P(V, t) describing the fluid state of a substance is shown. In the shaded region mixture of two phases can coexist along the horizontal line. If at the given temperature 7, the pressure is sufficiently low so that P P,, then there exists again a single phase with a unique value of V. The stability condition @P/2V <0is again satisfied but | P/V |is relatively large so that compressibility of this phase is relatively small tas would be the case for a liquid phase. ‘For intermediate pressure range PR, 0. ‘The partition function is, where e: i i - Hence therevarel2 termstin the | 12:6 .BRAGG-WILLIAM'S APPROXIMATION : The Standard Mean Field Approximation: e Standard Mean Field Approximation: We may write the Ising model equation * Ey(s)=-eD, 9,5)-wHD, 5, s ; ss : +f) for the energy of the system. fo dimensi able 6,(= Lacon NV Braggiand|Williamsvassumed that the distribution-of.spinsisiatrandom. Let, on a given site* and N. be the number of spins for whid Necba.thenumbessofaepine fguewbichmeminnia! -s;is— 1. Then x is the probability of finding a spin +1 up and x is the probability of finding a spin- 1 down. Assuming random arrangement of spins over the whole lattice, welwrite from 6q. (1) that” satin SY) ony & scanned with OKEN Scannerphase Transitions 383 where 7 is the number of nearest neighbours of 7 a site; N= Nj4N_ is the number of spins; and ae i (Et simply implies th: all the spins are up). Therefore, if N,/N Soba i the neighbourhood of a given spin, then in, eee in spin, then the same average value is likely to occur everywhere on jn the entire lattice, a fract : Refer to art 9°4, where we have shown that the total magnetic moment associated with the ; M=,(N,-N_) 8) Using N=N,+N., We write M=,(N,-N+N,) or we) or (6) Similarly, we can show that (6) Also oD ‘Also from eg. (3), we Bet NON or “W Y gops 2 Wa-N- = (8) Putting eqs. (6), (6). (7) and (8) in eg. 2) We 7 for energy of the system as 1 i aa r --h we (5 uem?y Loom! | Hein i Se @) 5 yeNm? —wHmN a ir the NV sites given by the number of ways we ©” sents of SPiBS OVE! ‘The number of arrangem™ & scanned with OKEN ScannerUsing Stirling's approximation Log, N!=Nlog N-N we can write log, W=log, N! -log, N,! - log, N_! =NlogN-N-N, logN, +N, -N_logN_+N_ (as N=N, +N) = Nlog N-N, log N, - N_log N_ =-(N, +N.) log 1 -N, logiV, = log 1 1 =-[ tog 4 +17 1og +N log b+. tog] o-[rog M0 te] N, Ne NL. =-N|—+log—+4—= lop —= [F ey Ney -N (50+ mlog5 +m) +Za-m)tog 4am] 1 -N[5G+m) log (+m) +2—~m)log(.—m)—log 2] on (10) ‘Therefore energy of the system is S=klog,W Cdk bY 1 1 = ON (5 (1+ m)log(l +m) + (1—m)log(l ~m)—log 2] (11) and Helmholtz free energy : F=E-TS yeNm? —pHmN ~NAT(-1og2+0 +m)log(. +m) +ha =m)log(-m)}..02) ‘The equilibrium value of m (or N, —N_) is determined by aF/3m=0 so that from eq. (12) we write ~eNm—NH— 1,1 1 yeNm —.NH mir 5+ phe d+m-2- Log -m]=0 or em + pH =hT log 2 +™ m) a log G22 = ee 2x (say) 1) & scanned with OKEN Scannerphase Transitions or Lim _ oe = l-m 2x or e*-1 m tanh x wee(14), eel which is well known i result of Weiss theory : For H =0, the spontaneous magnetit ‘ic moment is a w=(15) (16) {js a chain of N spins, each spin int mal magnetic field, H, we can writ 1367. ‘The one-dimensional Isi Jing model nearest neighbours, Neglecting exter nfiguration specified by {55 $2--8n} 88 o() n Saath ft eracting only with its two fe for the enerey of the Ey= ts “Th prencihs fermomagnetic state, where all spins Ste exploit their mutual & ly aligned parallel to each other, has low free enere¥- sxchange energy by being & scanned with OKEN ScannerWe impose the periodic boundary condition Si = 8; @) ‘The partition function is x aS ox (eS sa} oh 4 aS >» DX Tl (oshBe+s; 5,4; sinh Be) ++(8) eet ha where we have used Exp (ess) ={@ (68'=1) male ie (ss =-1, which holds because ss” ‘can only be +1 or ~ 1. terms, each of which is a product of the form (cosey®** (sinh Be)* (9,5, =(cosh c+ss’ sinh c) . The expression of products in eq. (3) gives a sum of 5)5)41) = Graphically these terms can be displayed by thick (corresponding to factor ss’ sinh Be) and thin (corresponding to factor cosh Be) links forming the ring. It can be argued that non-zéro terms are the first term {cosh Bey" and the last term (sinh Be)" so that © Z=2"((coshBe)" +(sinhBey”] =2 (cosh Be)", for N >>1. because cosh Be >> sink Be for Be-—S + for T #0. Therefore kT Helmholtz free energy for the system is | FS-kT log, Z Nin y 2° Fig. (8) N Ising spins arranged in a ring. =-NkT log, (2 ‘cosh re giving energy of the system as © scanned with OKEN Scanner