Stability Criteria 7 7.1 Solution @PA/AN?), y= OH/AN),y = QV/AN),/ V/A) =-VOWV, 9 AT,P) SaT+VaP V@P/0V), y= VA substituting, 72 Solution we Tag -ne tad lt 0 F\ represents a large total volume (-» =) where the mixture behaves as an ideal-gas mixture, that is V=NRT/P But, dA =-S dT PAV + hydNy + WAN, y/AD yy OPN Also, Bs. Tap) = RO In fg +g) = RT In Py 9g(D = RTIn (yh) + 2D72 Stabity Cetera Chapter? RU NAT) vA) The ubtting into, (), west iW 1.5) Ra Ny RP EL) — yl) 2 (a @ a Differentiate with respect to. keeping V, 7, constant ap = big AN) xn =(RT/N,)~ RT In P20 yy = Jp PPAND yy, AV +OP/AND vy OLN yn ® But (@P/2Np)r v= RI/Y since (QP/ANg) is to be evaluated at Thus, Eg. (3) becomes, Aan=(RT/N) | PPAN D5, AY > and since (@*P/9N8), vx =i an idesl-gas state fro V" too; Eg, (7-32) results baa= RON,” GPP/ANE) gon dV 78 Sokaion A the limit of stability, y= (@P/@V),= 0. With the van have from Example 7.2 is (dW) equation of tae, we 2a a ari 249 Yh 7 where ‘Therefore, Q bar with @ ‘we have a sevond equation for T and V. Solving Bgs. (2) andl (3) together using MAPLE yields ‘multiple volume roots, using the largest forthe pas and the smallest forthe liquid we getStabily Giteria_ Chapter? Bay © oy Vi, =0.1305 x 10° m/mo, Ty 29% 10° m'/m0, Tyyy = 552K liquid 258.5 K “Thus forthe lig spinodal at? Vyqy=0.1305 x 10? m'/ml, Ty 1 bar 85K ‘Alternatively, with the Peng-Robinson equation of state, we have P=RI/V—b)~ (DAV (V +b) + KV~B)) ® 2g 2a V +8 @P/ay),=0=—RIAV- b+ 2a +8) : = ye (VV +6) + 5(V~2)P 2 Solve fo a7) in Bg, (S) and substitute into Bp. (4). After rearrangement, © roe RF Substitute Eg (6) into (4) to obtain an equation in V.Kterating or using MAPLE with P= 1 bar: Vpn = 9.807 x 10° m/e] Tyg = 2806 K mental value of 269 K. e Both estimates are reasonably close to the expe 7.5 Solon From the slton proved o Probl 52, we sata C,~C, cold generally be expressed inte of PV properties ~cyar(22) ( » a *6r\ 6), so sien a PIN Equation of Sate or popery dat ey we en eve the il pore teria, the stat erro that @ ‘We now can easily see that fora stable system that G-¢20 or C>C, QED!iabilty Citra Chapter 7 ae e iven aliquid mixture of B, C, and D at some 7, P, determine the stability limits and any critical points. Assutne that the solution nonidealty is given by a simple, symmetrial Margules form: AG™ = RT CAN Ne+ NNy + NN,)/N a ‘The criteria for stability and criticality for this temary system are: =0 Ordering ® we 6 Bas. (4) and (5) may be writen as B/E, 661, = WAND ry9,—0 © a= FE/Beeg, 6,5, = PUy/ AMG ny, 9,= ) To use Eqs. (6) and (7), given Ba. (1), @ 0 +g ® where AG is the toa free energy of mixing AG and AG? = (Ny In Ny-+ Ne In Ne+ Ny In Ny—N In NRT © on. a more Faia form, kg In yb] Fy, IRE ao) Tus, AG/RT = Ny In Ny+ Ne ln Net Np In Ny NIN + alNpNet NeNp + NCN)/N ay To introduce the chemical potential, BG c= He Ce=(@MG/INO 9,0 <2) ie +n Ne~ In MRT a3) where GEN Ne HN My NN aaStablty itera Chapter? 1s @© _ we itera oe om Ba, 12) tonsa 77M Ag = e/g + Ny + Nei) 2 g(2a/N N+ (OU NDAD, + (Ny + NNO YAN (Nj ale (U/N9ART as Before proceeding tothe next step, consider the derivative @N,/NG,, 4, (T-Pconstan) 6) UTP No No) dG =— Ney Weal Ha so with a Maxwell eatin: and =~ Ou) (ote that in our short-hand notation, & = e* OWANSnen ae 49 1,2 @ N/A Nay, y/ Mey, a Cp Geg 7a Now, returning to Ea (15), divide by dN and hold 7; P, hy. Np constant Ging = Ohtc/AN 0 5, CONN, + ND=N B= HN) + q(2o/N Kl +) +(0/® +N, +N CONV +) + (1/9 ~ (Nt +o) 9) gq. (19) provides us the equation for stability. In texms of mole fractions Gxc= @e/AN Jp y,n,= C/N Alsg +x +30 + D] + ie pty tet NAG +) $a + (y+ x I+) + /%¢ +9) To obtain in terms of mole numbers (or mole fractions), we return to Eq. (17). (@tte/ANgy, , ean be obtained with Eq. (13): (Othc/AN ey, 9, = Frc= (04/9) (ONAN + Net 2NQ) +N 2H)16 Stabtty Grteria_ Chapter? ‘oto ttn e/a ween obi mexrenion ors are iorncintg, (13nd @ dierent sent Pio (Chy/AM yu, = Gan = AN?) ONY + Ny) 4 (UN) (178) 2) ‘Therefore, with Eqs (17), (21, and @23), & may be determined, Its also instructive to obta Gc ftom Eq, (13), Gigo= Oe/ANy, 9, = 20Q/N)~ 2O/N WN, NG) +U/N—C/) 3) “Thus, to summarize to this point: To determine the conditions of solubility o + Geo=0 from Ea. (19) «+ obsain from Eqs. (17), (21), and (22) + convert expressions to mole fractions and note x94 +p or alteratively, @ # Gee= Geo~ Gc! Gyy=0 from Eq. (19) + obtain Gnas Gam Gua from Eqs. (23), (21), and (22) + convert to mole fractions and note ,= | ee ee we ifereatts oun wih rpc tnd, P ip Np The pie © op topes $n ore, Ee (1721), and 2) ed slighty different technique is illustrated here Gece= Fe/ANr. 9,4, = 9=9 (Gee (Gye Gear. rg ,/ANc atthe erial point where T and P se fixed and the moe frations assume critical vals satelite) | Ore | ne (8) ale! eo en ee7) isn dein oS Gu nd Git ven in Gayot toca (2c (@Nc (21), and ] = QU/N Ny + 01% + NgI— 6 a0/N1 +) 0 1) + (y+ N, AOU N+ ®) (UND ++) 0s) (@Gnc) n Ay ee) aan, +ONe4 Ng lag +0) (NHL +0)+ Oy +Ne+ 2AM +) = (= nv +6) 26) 20s es (% | “ NEN + Wo Np) N16 a/ VL +) (CaN) ~ (Nee N-4a/NV1 +0) (07m) 41001 +0) & With Eqs. (24) through (2 to locate eritcal points expressed in mole fractions, composition values may be searched Some numerical results: For any we can caleulate xe for specified xy subject tothe condition Ge =0.For example, lst = 25 o. 0.286, 0614 02 04 03 2 solution oa 02, 04 os =0175, =0325 06 0085, ~02878. 77 akin e @ Using normal variable ordering in the Fundamental Equation: y and dy = TS — Pav + wd Va Tn general with and the most stable phase will have the lowest value of G ata given T and P. Consider the thre cases: WD T OG/PP gs = Vane T)> GAP), t= Vega T) rote that all slopes are positive as all V's > 0. nT Goh RAT vapor solid Tiguid740 Stablty Crteria Chapter? Segment NQ isthe metastable extension of vapor into the solid region. Segement PQ is the metastable extension of liquid into the solid region and point Q defines the metastable ‘extension of the L-V coexistence curve into the solid region which can be tested to sce if it satisfies the spinodal criteria. ‘Similar reasoning can now be used the other two cases Ao, c Toes vapor solid 9 Z— — liquid es vapor solid 7.8 Solution ara) 7 ‘Along the spinodal, Ay =0 oF (@P/2V),. gas =0, 80 G Zi ar, Ite and at the eitical point V= Vso the slope of the equilibrium vapor pressure curve and the spinodal curve are identical there too. So Rocky is corect!Stabilty Grtona_Chapter7 zat Ineffect the P-T projection of the spinodal is defined by an envelope of isochores (constant ¥) terminating atthe critical point. For further discussion see DeBenedeti, P., Metastable Liquids Concepts and Principles, - 69-11, Princeton (1990) 7.9 Solution Prom Table 7.11 on p. 210 use YY =Hys=@T/2S),, y>0 o Taking the eciprocal (28/01),, y=N@S/AN,>0 @ but from the definition of enthalpy for a single component system and the Fundamental Equation \wetten in intensive Form: AU + PV) =dHl = TAS + VAP ® bbut using the definition of C, ® ‘Thus, using Eq. (4) in Eq, 7.11 Soltion (@) tthe critical point with m: n+? for n yn, ify =U=A5,¥), thea y= A ‘or with reordering, f= U= fV, 5), then y= U4 PV =H “Thus the ertical point criteria can be equivalently expressed as Ayw=0 or ~@P/AV),=0 =0 of @T/AS),=0‘Stabity Crteria_Chaptor7 Gin e en iQ) = as o1(f) om go Given a PVIN EOS and an ideal-gas state C, critical point should be exhibited AT) the singularities for and G, atthe ob) at Ne eo shaw AS LAS os ie e Using the state function property of G and the Gibbs-Helmholtz relationship for a pure ‘component, we ean express the derivative of AG/T as: (aac) _-aH _-c— HY rhe oO where AG'= G°— Gin this case, ‘We can assume that this relationship will apply o ether phase as long as we have a stable or ‘metastable system under isobaric (constant P) conditions, Thus along the P= 1 bar isobar, Eq. (1) ‘canbe integrated from an equilibrium coexistence point to another metastable point: aao/n=-| Sar J If favre, bn +f eal — ar‘Stabity Crtria_ Chapter 7 748 data provided we can estima subcooled state G° and AG“ =0, Assuming that T™! = O°C at I bar, then using the \GIT= 10°C, 1 bar] on a | kg basis for this superheated rather than serlasa eines AG = G — Gt = 283(24.13 + 19.32) - feet esner (at zs]] 283(43.45) = 12,295 J/kg oF 221.3 J/mol (Note: using the corrected value of 7=—10°C, a more realistic subcooled liquid state is reached, Inthis ease AG = GCC, | bar) GH-10°C, | bat) =-12,098 Ig or-217.8 Hino