ole als 4 Wt W fz 3 a a b b ve we 21 “ < ee i No us Insezrdce wih is the saturation volumes by the intersection ofa elope, ested $0 that aly, this condition may “ a2 at ftlows from the fat ofthe two phases are a3 ‘ent the specific volumes comesponding pressure ser, the prediction of der Waals equation is sures 1.17 and 1.19 and the stuation condition + similar inform tothe te other cubic equations uration more accurately ‘ons BC and FE of the tbe conditions that have Table 1.3, ‘The van der Waals Equation of Sate ‘Standard forms ofthe equation are: (P+ a/ V9 V 6) RT, w eta (2 . a ‘The valve of R given by Eq. 9s not the same as the true gas ‘constant, 8.314 joules/gmo-K: the tre value should be used for evalation ofthe parameters @ and from Eqs. 7 & 8 been realized experimentally, but portion EDC isnot physi cally possible fora pure substance since it comesponds 0 changes of pressure and volume inthe same direction at fixed temperature, ‘Much thought has been devoted to interpreting the meaning of the S-shaped isotherm at negative pressures. A survey of recent work is inthe book of Temperley & Trevens (1978). “The conclusion appears to be that quids are definitly under teasion under thete conditions; for instance, a tensile strength ‘of water of 277 atm at 10 C bas been messired, Since the van der Waals equation is ofthe third degree in volume, any subcritical isotherm has vee ral positive rool, ‘whereas supercritical isotherms have only one eal root, When ‘here are thee real roots, the smallest i interpeeted as the specific volume of liquid phase, the largest as that of the ‘vapor phase, and the intermediate one as physically meaning- less. Cardan's solution ofa cubic equation is especially imple {for real roots, but several other general root-finding methods ae readily implemented on calculators. Although they are no longer of practical value, several char methods of soliton of ‘cule equations have been published, one by Lipka (1918) and another by Collatr (1955). A. large numerical cable prepared by Salzer et al (1958) sometimes may be of Derivation ofthe formulas for a and bs Method 1: At the critical condition, the fist and second derivatives with respect to V at constant T are 2er0. Per Forming these cifeentiaions, ap Ri ae ar) ae aE on op 287. bo 7 ov) a VE “2 Abo, Sunn : Care. wn es polynomial, Eq. 3, are equal. (HV =~ IVVE ABV VEO, (14) Comparison of coefficients of lke powers of Eqs. 3 and 14 Wil lead to the Same results for the parameters a8 by method i FFor mixtures, the parameters are expressed in terms of the ire component parameters by the combining rls: 0 (Eye)? = BE yyy Vay EE rays (18) b= Ey a8) Fugacity equations are in bles 3.3 and 3.4, Residual property equations are in Table 11.3. The Reduced Form of the Equation From the several plots of ertical isotherms that have been shown in thi chapter, ii clear that a point of ifletion appears to exist usta the etal point Mathematically the point of inflection may. be found om equating the first and ‘second derivatives to reo atthe ential volume, thus: Gi) Gere a When these rules are applied to the van der Waals equation, the parameters a and b may be found in terms ofthe critical properties. The results are shown in Table 1.3. The same results also canbe deduced from the observation that the thee I at the entical point, by comparing the ‘with those of ‘A conclusion of great significance, the Prnsple of Core- sponding States, is suggested when parameters @ and D are limited from the van der Waals equation ia terms of thet cic equivalents, with the result44 Equations of State Parameters: (soe Example 1.12): o a= MRT? S/P, = 0.42148 RTES/P., @ benyer ie, = ootseaRT,/P, & A= aP/R1T? 5 = 0.42748, /T?5, “ B= bP/RT = 0.08664P, /T,. “) Peyomi fms Bad (Famer oe ease ® . BaP 4 (AB - BY: ABO, a 0.42748 - PR [PSS couse oso Je-oamer ts 0 20, IN, TH SHAY, + 304) aa 3 bP OOMSART, _OOBGEF, 0 RT VR, aT, ao Pa bare (i) Ta 7s Gh). an area ae a O= EEy 9/05) ~ Pat yon +--+ OI + Ie + A= EA. a3) ay ~ Vag, (Redlich & Kwong's original rule), ay = (1 cy )aiay (Zudkevich & Joffe 1970), i) (AP VEG 0.291 ~ 0.04, + w) kyv Teel? —(Prausnitz & Chueh 1968). (19) Fugacity relations are in Tables 3.3 and 3.4, Residual function equations are in Table m3. may need o be developed. A review ofthe literature on the RK equation by Howath (1974) cites 112 references, and ‘many moce have appeared since that publication date. A umber of adjustments ofthe parameters ofthe R-K equation {hat have been tepored is summarized in Table [10 ‘With all the changes that have been proposed over the years, there may be a question whether a given equation it propery called a modified R-K or a modified van dee Waals oF Something new, but the term modified R-K Seems to be poled to an equation with an atacton term of the form Figure 1.16 Three es BO 5 a funtion of 7 1. Pitzer & Cur (195 0 = 0.1445 ~ 0.337 Y= 0.0734 0.46/ 2, Abbott, cited ia Sim B= 0.083 ~ 0.422,efficients and My 1g. 9 of Table 1.9, are drawn, temperatures 6f0.9 and 11. rity that of methine oo ths fflerences between the 0 + 1.S517tw— 0.156130), (1122) ext (1979) wrote °). (1.123) «on the shape of reduced the Redlich-Kwong equation se 1.19 is another compar- rules are the same as for the (1.24) veh as wate, alcohols, and ‘posed by Soave (19796), (1.125) 1.5, Cubic Equations Le ‘able ILL. The Soave Equation (Graboski & Daubert ceficests) Sundard form: BoP+ UA B= BY: AB =O. o aT ae 1 Paty rede frm (te Example 1.16): v8 H+ ‘ an, 384734 te OREO (20) rameters: ¥, = 02599 VV, + 02599) 2=042787RTHP,, 2) Mintures b= 0.08664R7/P., 0) aa=EEv yeas, on 1 + (0.48508 + 1.551710 ~ 0.156130? (1 — 799)P, Eyibj aa O ge zEyydy “a a 1.202 exp-0.302887,) 4 for hydrogen (Graboski& Dauben 1979) wy BRB A= aaP/R*T? = 0.424708, 7}, (6) Cromnarameters: (B= DP/RT = 0.086642, (70 byw GaNeal, as) fees ‘ay in Table 1.12: (16) art aab ky ~ 0 for hydrocarbon pars i tydogen “ VP VE AG (aa~ bRT~ Pot“ —O, (8) Fugacity coelMcents are in Tables 3.3 and 3.4, Residual eopeties are in Table 11.3, 100 50 300 F| 230 as 20 | 2 0 s 100 F. Saturation 2 1 - 001 (ega02 Osea gat terse Figure 1.19 Plots of 250 F isotherms of sulfor ioxie with , oY the Hamens-Knapp, Soave, and van der Waals equations, Gl app, Soave, ations, nd comparison withthe ue saturation curve, “True ves 411 0053, 0516 vander Wale $46 0016S 0258 Note:The solution of Problem 3.26 ptes these renuks for Soave 41.96 09756 05187 saturation pressures and volumes: Hamens-Knapp 41.98 0.0597 0.482658 Equations of sate Table 1.13. The Peng Robinson Equation of State (Pong & Robison 1976) Standard form ar a a Sees eT o Pararcters: a= 0457248737 @ »=oo77=0RT./., o a [1 +(037464 + 1542260 0.269201 —T99)P, 4) A> aaP/R?T? = 0.45124aP,/T?, (s) 2 = WRT = 007180, /1 © obo on 9 —(1— B22 + (4 — 3B? — 2B) 2 ~ (AB ~ BP B)-0. o Mises: aa=2Eyyf00)), o b= Ey, o (omy = (1~ ky Veaaay, (10) A= EEA, ay B= Sy a2) Ay = (1 byXAsdy PS, (3) i as nitrogen + HC Co; + HE ethane + HC propane + HC thane propane mca mcs C6 nCT methane + ¢ neg nc C10 C20 benzene cyelohexane Inolder books these equations for heat capacities and entropy ‘changes with pressure derived from the Berthelot equation sometimes appear and are applicable at moderate pressures near room temperature (Partington, 1950): Cp Cy RU + DP, N67?) 144) av) rf. Jo (ar jn ft em fe ote of Katz & Firooeabadi (1978) kgm 042 ous. 001 0.01 02 002 0.025 0.025 0.035 0.035 0.035 0056 0.06 003 ‘Two equations were developed by Dieterici (1899) 00 a semitheortcal babi, as decribed by Partington (1950). The fire (e+ aivI v= by ‘The expanded form, VES ~ (bP + RTIPIVS3 + (a/P)V ~ ab/P = 0, (47) rT. a.146) can be shown to have only thre real roots in V3. Consideration of the sells of containers led ar = eet ast Pe pet ‘Actow pressures ors becomes aT e Becerra In terms of eauced ve », wy, 0 Derivatives useful for (%)-75 () 7b ‘The Berthelot and 1 ata and with he van ¢ presses to 1,000 Bertelot equation is aim, except for ethy Dicierii is beter. At} Dieterici usualy pve temperatures above 3 ‘equivalent, Reduced f to be compared in Pre behavior in the vii paricularly that of the ‘Aecent example of fsthat of Harmens & & Table 1.18, Thee eg RT. poe va Py reduces to several ¢ panicular values of p= i. RP benb +o%e- + ravi tay te and AP pene arte144” Furey and Fugacity Coeticient ‘Table 3.3. Fugacity Cooficients of Pure Substances from Some Equations of Stat van der Waals (Table 1.3): a ® o o “9 © tanh) (> a, o Redick Kwong (Table 9) as Poe Th) “ . 2 8 wone-t-m[: (1-2) ]- Ste (i44 o a (8 - =r men) $u(144) ao) Soane Table 1.1) aT aa PW au « . nen rnimafe (1 fem (12) uy ) ' i) ee omen 1 te 8-755 (oats as BWR, BWRS, and Lee-Kesler equations are in Tables 1.16, 7, and 1.18{able 24. Partial Fugacity Coefficients feom Some Equations of State Tan der Waals (Table 1.3) me Pry ve o on VF 2 b= Eydh o bi noir Gop ou al (Tbe 1 aoc ded © 2 us v8) F Erbe HE Eytan tee ek o , at fons ” wank fanvos [E Erma B= Sy by ® 3-2, By Bu a0) Ja= 2p yP an For two components, ' 2 toda pls 9HQBi2~ Bs ~ BN ay nd 7 3 a= pila + 2B 12 Bi ~ Ba) a Redlch Kwong ae 19 ara Poyoe Even) aa nd 8 fhe ints by Ea. 2a A= yay as) aor, as) ng, bi penne] (1 3, 4 (i de-N te 45 -2vaa}n(195) an 4 n(s+2) as) ‘When the combining rule isa = E5240 instead of Ea. 2, replace ¥aa;in Ea. 17 by Sear Tale 1.1) (ea) = (1 ky) Var ReaTy (20) (Continued nest pose)/Pui=2&ik=9ad430b0a0&view=ptés. (08/02/2013 12:50 p.m. Table 34 (continued) Ayo an = Epon boy, A> (aa)PRTY a= bein y= apt ng = 7 2 *) r Peng-Robinson (see Table 1.13) ‘The symbols have the same meanings as for the Soave equation, although the numerical coolants in 0 Fugacity coeticiens based om the BWR, BWRS, and Loe-Kesler BOS are in Tables 1.16, 1.18, and 1.19. Example 3. Fasc of Ammonia rom Experimental Dra end Compaions wit Priftion rom Sex Correlations Data: 7; = 408.6 K, Pe = 111.$ atm, «= 0.28. ‘which 2 CCompressibilles at 100 C and 200 C over & range of pressures ‘Chemie, 4 (1935):426). Use th equation wee ff! «She Ro en spon en “The america vats were found by somputer © Calelaions fon the expecimenal zs, Piz Kesler, and Rede ivong ate summarized as ‘The Pitzer & Cur equation in terms of T,, Pp, and wis LeeKeslr and Redich-Kwong methods are rour sven with Figure 1.10(0). eee "The Lee Kesler dats are given in Tables 56 and 7 from peor, particularly above 8.8 100.Cjrom ‘0560 200 02896 0.458 03126 0.6676 300 02124 02818 02106 02392.0.5466 00 01756 o.tea7 (02087 04081 600 01426 «00794 o.1s0e OTA 0.3888 800 0.1299 00341, 1000 011254 0147 0,144), Eine oi mc nn ty ‘These dua ao excerpted for the preceding table. i