Solutions Manual to Accompany Molecular Thermodynamics of Fluid- Phase Equilibria Third Edition John M. Prausnitz Riidiger N. Lichtenthaler Edmundo Gomes de Azevedo Prentice Hall PTR Upper Saddle River, New Jersey 07458 http://wvow phptr.com‘© 2000 Prentice Hall PTR Prentice Hall, Inc. Upper Saddle River, NJ 07458 Electronic Typesetting: Edmundo Gomes de Azevedo All rights reserved. No part of this book may be reproduced, in any form or by any means, without permission in writing from the publisher, All product names mentioned herein are the trademarks of their respective owners Printed in the United States of America 1098765432 ISBN 0-13-018388-1 Prentice-Hall International (UK) Limited, London Prentice-Hall of Australia Pty. Limited, Sydney Prentice-Hall Canada Ine., Toronto Prentice-Hall Hispanoamericana, S.A., Mexico Prentice-Hall of India Private Limited, New Delhi Prentice-Hall of Japan, Ine., Tokyo Simon & Schuster Asia Pte. Ltd., Singapore Editora Prentice-Hall do Brasil, Ltda., Rio de JaneiroCONTENTS Preface i Solutions to Problems Chapter 2 1 Solutions to Problems Chapter 3 7 Solutions to Problems Chapter 4 29 Solutions to Problems Chapter 5 49 Solutions to Problems Chapter 6 81 Solutions to Problems Chapter 7 107 Solutions to Problems Chapter 8 121 Solutions to Problems Chapter 9 133 Solutions to Problems Chapter 10 153 Solutions to Problems Chapter 11 165 Solutions to Problems Chapter 12 177SOLUTIONS TO PROBLEMS cHAPTER 2 1, From problem statement, we want to find (AP /27),, Using the product-rule, By definition, and Then, Lex 3210 338 bar °C Integrating the above equation and assuming ap and x constant over the temperature range, we obtain ap=22 ar xr °C, we get AP =33.8 bar2 Solutons Manual 2. Given the equation of state, we find For an isothermal change, 12 @P\ as= (2) av nein y, (ar) = ninth, z wt JLo) oy anne) ( AG = AM TAS = nb(Py—F,)—nRT In] ) (ny MM = AU-TAS = -nkTIn| 2) Py}Solutons Manual This entropy calculation corresponds to a s of steps as follows: 5p, re pbe.15K Pattey 5 (eturated ig sa (saturated vapor, Fisk fatsn P= O03t68 ba) P= 0168 ba) $3 As. +At 43 +5) vag _ (243 1 ASi-99 = Ayap = = OO*CB 1S) 147,197 mot 258.15 an saa f hy ar Because v=" (ideal gas), Aszy3 =-Rln| 2) \Aa) = 48.31451)xinj 0 COs, 8.70.1 mot 5 = 8°(11,0, vapor) =147.19-28.70+ 69.96 188.45 JK! mot4 Solutons Manual 4, Because a =22v, > Rr RT Ps ate 2-3/0 40 As 0-23 Lol“, mot, 5. Assume a three-step process:Solutons Manual (1) Isothermal expansion to v = 2 (ideal gas state) (2) Isochorie (@ is constant) cool- ing to Ty (3) Isothermal compression t0 5 For an isentropic process, As=As) +s) +As5 =0 a-(2) an(S) a Because s=s(v, 7), by using the relations (S) - (2) ; (Maxwell relation) then, Thus,To simplify, assume Solutons Manual Then, (82.0578)*(T3)~ 48] _ 5,999) jy 21S 600-45 r 7 -203K 2 Because <1, Thus,7 Solutons Manual Because lz RT the second virial coefficient for van der Waals equation is given by pt RT 7. Starting with du Tas ~ Pd As Then,8 Solutons Manual 8. The equation / \ Pt aT (o—m) ean be rewritten as 0 ‘At the eritical point, there ae three equal roots for 2 =v, or, equivalently, ap) 2p a) (ar) _, Sra, or re rer, (u-v,) =08 30.02 +3020-03 @ ‘Comparing Eqs. (1) and (2) a the critical point, ° ao @ PT ame o From Eqs. (3), (4), and (5) we obtain © n=mep.7)? ‘The equation of state may be rewritten:9. Solutons Manual From critical data, ‘m=0.0428 L mol” ‘n= 63.78 bar (L mol")? Kk! ‘At 100°C and at v = (6.948)x(44)/1000 = 0.3057 L mol, 2= 0815 ‘This value of gives P = 82.7 bar. Tables of Din for earbon dioxide at 100°C and v = 6.948 em’ gl, give P= 81.1 bar or z= 0.799, ‘We want to find the molar internal energy u(T,v) based on a reference state chosen so that To,0 0) =0 Then, MT.) =U) —W{Ty, 2) =u v)— us co) +u(T.-> 20) ull 22) w = tim (2) e+ tim (3) ar ed late aber). Schematically we have: Ideal gs Ret. tate Intermediate state ‘State of interest Neca gas Ideal gs (,v> wy (vm)10 Solutons Manual In Bg, (1) we are taking 1 mol of gas from the reference state 4 10 the state of interest 3 through an intermediate state 2, characterized by temperature T and volume 2 > 2, in a two-step process consisting of an isochorie step and an isothermal step. 11» 2 the gas is infinitely rarified, and hence exhibits ideal gas behavior. Then, the second integral in Eg. (1) gives: o o ar= Je-Pat RMT) @ because for an ideal gas cc? = R and because, by the problem statement, the heat capacity at constant pressure of the gas is temperature independent. We have now to calculate the first integral in Eq. (1). To make this calculation, we first transform the derivative involved in the integral to one expressed in terms of volumetric proper- ties. By the fundamental equation for internal energy (see Table 2-1 of the text), ov) _ fap) 2 -(Z) -P ro) “Making the derivative using the equation of state give we obtain 6) Ou a, (v-b tn [ (22) ao to(2=4) 6 Combining Eqs. (1), (2) and (6) we obtain the desired expression for the molar internal en- ereys u(T,0) = (€8 = RUT =T))+ na1 Solutons Manual 10. Inyy =Al—ay)® such that yy as ty 1 Using Gibbs-Duhem equation, sd ing +xdlny, =0 or, because diy ~—d, (sy +45 —D " 2% = 24(1= 4,1) - 2401, diy (1x, )-D) (1X) Then, diny, - 240-1) de, Painy, =-24 foxes (2) tnye=-24e. 2) Iny, = AG2—1) 11. Henry's law for component 1, at constant temperature, is fizkm — (for 0 i, Therefore xy falls with rising temperature This is true for most cases but not always,SOLUTIONS TO PROBLEMS CHAPTER 3 1 The Gibbs energy of a mixture can be related to the partial molar Gibbs energies by Since, at constant temperature, dg = RTin f, we may integrate to obtain 8 = RT ID frst RTI Fi 87 = AP I fag “RT INP where subscript mixt stands for mixture For a component in a solution, dg; ~ RTdIn f,. Integration gives Be =RT Ing? BB? = RT Ing.) Substituting (2) and (3) into Eg, (1) gives Infuige ~In P= Sy, Inf = Sy, In0,P) Because a 2) 8 @ 7Solutons Manual 18 Souinp=tnA| Zy, [= In? a a) Eg, (4) becomes $y, £) 5 nfo = Sv © 2G) Assuming the Lewis fule, J wei» Ba. (5) becomes, I fice = 2,919 pure fsx = Fees This result is rigorous. It does not assume the Lewis fugacity rule Using fugacity coefficients, f= oP and In fist = 94109 4+ yg 109g +InP frise — 94 OPP = (0465)"5 «(0.90)°75 «(50) Saist =415 barSolutons Manual 19 Pure-component saturation pressures show that water is relatively nonvolatile at 25°C, Under these conditions the mole fraction of ethane in the vapor phase (yp) is close to unity. Henry's law applies: fo =H ‘The equilibrium condition is Se =St yeoeP=H(xe AUL bar, op #1 and H(T)= Pix (T= = 303104 bar 033x107 AL3S bar we must caleulate gy Inop =f = I Using 7.22% 10-5 P? we obtain op =0733 Because Henry"s constant /7 is not a strong function of pressure, ry =e 8? BHO (0.733)x@G5) 303x108 xpo 4. The change in chemical potential can be written, Ay = 0) woSolutons Manual 20 ‘The chemical potential may be defined as! wnt 2 Combining Eqs. (1) and (2): 1 (aaa In fi=FFl RT Em, }p Using total volume, Y= npv, np =m, +m Mp tof Yn to 2] ny tof © BD" Pm) a) RT. Taking the partial derivative and substituting gives fA WRF 2-5 vb var ) 1 ‘The same expression for the fugacity can be obtained with an alternative (but equivalent) ation: and thenSolutons Manual 2 wtearnfS] — GPerm Ai | By dinton yy =[24) resi ee chang canbe wens Om Sri pha A-S na Tne -RT) Then, | -ut-ar (a4 an} wont “RP and dtnpa! RT) Using the equation for Aa, atmo RT) YP yy toh tnfpain{ Mice |_| Arana] 1 my RT my by V—njb V—nyb =In Pu 20h) T= nyb (7=npo} Hence, MT (_b\ Amy lo)Solutons Manual 2 a) Starting with Eg, (3-51): For a pure component (1, =n) wae n} =p) 75) RT a From Eq. (3-52), 2 But, and P Substitution gives Par v Jor arn 80,0 b) Starting with Eg, (3-53): For a pure component, y; =. To use Eq. (3-53), we must calculate [=] Pressure P is a function of T, V, and n andSolutons Manual 23 (ap) (am) (av lan), lar), (el But, Is Then, / 7 (2). -fee-t phan = 2av-ar-2t = [2ar-rre-1 Now Eg, (3-54) follows directly 6. The solubility of water ino is described by Any Henry's constant can be evaluated at | bar where f= bar Then, ny= = 286 bar = 140°C) x 35104 To obtain f; at 410 bar and 140°C, use the Steam Tables (e.g., Keenen and Keyes), Alterna- tively, get fat saturation (3.615 bar) and use the Poynting factor to correct to 410 bat.Solutons Manual 24 RT Inf, = Ag) +410 bar = At s410 ae —T A410 ber RT'n fi =282 Je! (from Steam Tables) (282)x(18) Inf =U) = A= Bsiasyx Then, fy = 4.4 bar at 410 bar and 140°C and. x= fe # J ooise WT) 286 h 0 ‘This may be analyzed on a P-T plot, Assume | mole of gas passing through the valve. three-step process applies: 1, Isothermal expansion to the ideal-gas state. I, Isobarie cooling of the ideal gas. IL Compression to the final pressure. For this process,Solutons Manual 26 Ah= Aly + Alyy + Ah =O Since h (TP), But, Then, and Substitution gives (616.1) P, = G35 5 mol“! Kx (10 bar em? J} x (200-300 K) + (-950) «(1 bar) P,= 58.9 bar 8. From the Gibbs-Helmholtz equation:Solutons Manual 26 or, alternately, a *) TD yao w (7) Because, at constant temperature, as) = ara. @ ‘we may substitute Eq. (2) into Bq, (1) to obtain an(t RAPP ) From the empirical relation given, 307 2 in£=o.067P-222 pooorzp? SAO P T T 30.7P-+0.16P? = 4 R ALP = 30 bar Ad = (8.31451)x{(-30.7)x(30) + (0.416)x(30))] Ah = 4545 J mot 9. Consider mixing as a three-step process: () Expand isothermally to ideal-gas state. (UD) Mix ideal gas. (UID) Compress mixture isothermally, Starting with du=ey arfr(2) 7) a]Solutons Manual 27 Integration of this equation to ‘Therefore, xia), any 59141 mol” Me [1 bar)x(1 em’) = 0.1 Joule] A = (because isthe mixing of ideal gases) Spi _Exfann +2182 Janda x= 0.)+ 32] Vai mPa Au = 50 J mol Anal = Amigt = Aay + Aty + Au, = 364 J molSOLUTIONS TO PROBLEMS cHapTteER 4 1, At25 A we can neglect repulsive forces. The attractive forees are London forces and induced dipolar forces; we neglect (small) quadrupo- lar forces. (There are no dipole-dipole forces since Ny is nonpolar.) Let I stand for N, and 2 stand for NH, London force: Sayay Nh ith Since, ay 17.6% 107% om’ ay = 2261075 cm? 1, =15SeV= 248x107 Nm 115 eV= 184x107! Nim then Fbendon = 62010" N Induced dipole force: 29Solutons Manual 30 D=110-"¥(erg em)! 47 D= 1471078 (erg em?)!? ig! = 38 «1078 (erg em)! Neglecting all forces due to quadrupoles (and higher poles), (pit _ pplondon rind Fr" = 65,8 10-1" N 2. From the Lennard-Jones model: ‘Atracive potential = —4e 2° =r Attractive foree ‘Assume force of form, fe\o* F (constant = & EF Force Using corresponding states: (s) (J (constant xv)? = Buz = (constant) T, al. where a. and Bare universal constantsSolutons Manual 3t (ec forceCHy (constant) (/Bcng Wenig)’ Tore substance (constant) (€/®)y (on) )" Bl eeg) 2x10 ecu) | (1 em TorcesubstaneeB aT.) ” pw,,)? 210°" em) Force substance B = -4x 107!” dyne Force = 4x10" Dag =-8%10- org By the molecular theory of corresponding states: ty Ti f2) ear) le) Foe _( 6 (e-2 isa universal function maya u " Since ¢/k=0.77T, (taking the generalized fumetion f as the Lennard-Jones (12-6) poten- tia), Pas =P (180 K/120 K) Tgp =-120%10-" erg =-12.0%10-8 5Solutons Manual 32 4. For dipole-dipole interaction: Hay Pedy = FE 1009) (rer with, /1B,,8;,6)=2c0s0, cosB, +sin8, sin, cos(6, +6,) For the relative orientation: = 180" goo" Pda) = HEL state) HL Gx.) Gaegr?) For p,= s,=1.08 D= 3.60310" Cm and r= 0,5x10° m, 2) (3.603.107)? (Gn) «(88542 x10) xO5x107 Tid) =-187«107'5 For the relative orientation: 0-90" yoo For the dipole-induced dipole interaction: Fy 2 poy 2 Hie ge (Bos 0, +1) ars Geos", +1) ane 2are,, For the relative orientation:Solutons Manual 33 —— F -gooae10-)P x@.60x10- ay 24 BA03107) 60510), $7.77 x10 J 28,0107 J , ' 8 8-90 (3.603107)? x (2,60%107) QL t1a4xio™) xoxo? 2x (1.1124 107) x (0.5 x10™ y 485x103 J 48x 108 SF 5. The energy required to remove the molecule from the solution is Lf eat Foal a1 e235 a=3.0x10% em u=2D (See, for example, C.J. E, Bottcher, 1952, The Theory of Electric Polarization, Elsevier) E~ 461x102 Jimolecule = 2777 J mot! 1a) The critical temperatures and critical volumes of N and CO are very similar, more similar than those for N, and argon (see Table J-4 of App. J). Therefore, we expect No/CO mixtures to follow Amagat’s law more closely than Nz/Ar mixtures.Solutons Manual 34 b) Using a harmonic oscillator model for CO, F = ~Kx, where F is the force, x is the displace ‘ment (vibration) of nuclei from equilibrium position and K is the force constant. This constant ‘may be measured by relating it to characteristic frequency v through: wel [K(me + mo) 3n\ mcm where mc and mg are, respectively, the masses of carbon and oxygen atoms, Infrared spectrum will show strong absorption at v Argon has only translational degrees of freedom while CO has, in addition, rotational and vibrational degrees of freedom, Therefore, the specific heat of CO is larger than that of argon. 7. Electron affinity is the energy released when an electron is added to a neutral atom (or mole- cule). Tonization potential is the energy required to remove an electron from a neutzal atom (or molecule), Lewis acid = electron acceptor (high electron affinity). Lewis base = electron donor (low ionization potential), Aromaties are better Lewis bases than paraffin, To extract aromatics from paraffins we want 1 good Lewis acid, SO, is a better @ Lewis acid than ammonia, 8. From Debye's equation: indepeadeat of 7 Measurement of molar volume, v, and relative permitivity, ¢,, in a dilute solution as a function of 7, allows pt to be determined (plot total polarization versus 1/7; slope gives 1)Solutons Manual 35 9. We compare the attractive part of the LI potential (r >> 0) with the London formula, The attractive LJ potential is We assume that 42 =1/2(o11 +622). The London formula is Substitution gives seus ih a2 = Cnen)"?| 7 eee" VEouten)| [Ba+4) Only when 6; = 022 and fy =/, do we obtain 82 = (nen)? Notice that both correction factors (in brackets) are equal to or less than unity. Thus, in gen- eral, 2 £12 S(En122) 10, Sce Pimentel and McClellan, The Hydrogen Bond, Freeman (1960), Phenol has a higher boiling point and higher energy of vaporization than other substituted ben- zenes such as toluene or chlorobenzene, Phenol is more soluble in water than other substituted benzenes, Distribution experiments show that phenol is strongly associated when dissolved inSolutons Manual nn 12. a) nonpolar solvents like C 36 “ly. Infrared spectra show absorption at a frequency corresponding to the -OH-H hydrogen bond, Yacetone(cct,) > Yacetone(cuct, ) because acetone can hydrogen-bond with chloroform but not with carbon tetrachloride, Chloroform is the best solvent due to hydrogen bonding which is not present in pure chloroform or in the polyether (PPD). Chlorobenzene is the next best solvent due to its high polarizability and itis a Lewis acid while PPD is a Lewis base Cyclohexane is worst due to its low polarizability. n-butanol is probably a poor solvent for PPD. Although it can hydrogen- bond with PPD, this requires breaking the H-bonding network between n-butanol molecules. butanol is probably better, Steric hindrance prevents it from forming H- bonding networks; therefore, it readily exchanges one H-bond for an- fother when mixed with PPD. The lower boiling point of t-butanol sup- ports the view that it exhibits weaker hydrogen bonding with itself than does n-butanol, b) Cellulose nitrate (nitrocellulose) has «wo polar groups: ONO} and OH. For maximum solu- bility, we want one solvent that can “hook up” with the ONO, group (e.g., an aromatic hydro- carbon) and another one for the OH group (e.g., an alcohol or a ketone). ©) Using the result of Problem 5,Solutons Manual 37 [At 20°C, the dielectric constants are 6 (CCl) =2.258 6, (CgHyg) = 1.988 Thus, s(CCl) 14 (Cats) {It takes more energy to evaporate HCN from CCl, than from octane, AU 170°C and 25 bar: 24 is above 1 Zamine 18 well below 1 zc) is slightly below 1 z a) A mixture of amine and Hy is expected to exhibit positive deviations from Amagat’s law. b) Since amine and HCl can complex, mixtures will exhibit neg law, ive deviations from Amagat’s 9 YarsnSolutons Manual 38 ‘The strong dipole-dipole attractive forces between HCI molecules eause zycj <1, while at gon is nearly ideal. Addition of argon to HCI geeatly reduces the attractive forees experienced by the HCI molecules, and the mixture rapidly approaches ideality with addition of argon, Addition of HCI to Ar causes induced dipole attractive forces to arise in argon, but these forces are much smaller than the dipole-dipole forces lost upon addition of Ar to HCL. Thus the curve is convex upwards, 14, a) Acetylene has acidic hydrogen atoms while ethane does not. Acetylene can therefore com- plex with DMF, explaining its higher solubility, No complexing occurs with octane, b) At the lower pressure (3 bar), the gas-phase is nearly ideal, There are few interactions be~ tween benzene and methane (or hydrogen). Therefore, benzene feels equally “comfortable” in both gases, However, at 40 bar there are many more interactions between benzene and methane (or hy- drogen) in the gas phase. Now benzene does care about the nature of its surroundings. Because methane has 2 larger polarizability than hydrogen, benzene feels more “comfortable” with meth ane than with hydrogen. Therefore, Ki (in methane) > Kj (in hydrogen). ©) Under the same conditions, CO, experiences stronger attractive forces with methane than with hydrogen due to differences in polarizability. This means that CO, is more “comfortable” in methane than in H and therefore has a lower fugacity that explains the condensation in H, but not in CHy 4) _Itis appropriate to look at this from a corresponding-states viewpoint. At 100° Tp ~12, for helium, Ty = 80 At lower values of 7 (near unity) the molecules have an average thermal (kinetic) energy on the order of z (because Tg is on the order of A7'/« ). The colliding molecules (and molecules near one another, of which there will be many at 50 bar) can therefore be significantly affected by the attractive portion of the potential, leading to z < 1. At higher Tg, the molecules have such hhigh thermal energies thet they are not significantly affected by the attractive part, The mole cules look like hard spheres to one another, and only the repulsive part of the potential is impor- tant, This leads to z > 1 for ethane ©) Chlorobenzene would probably be best although cyclohexane might be good too because both are polar and thus can interact favorably with the polar segment of poly(vinyl chloride) Ethanol is not good because it hydrogen bonds with itself and n-heptane will be poor because it is nonpolar, 6) i) Dipole. ii) Octopole. iit) Quadrupole, iv) Octopole.Solutons Manual 39 g) Lowering the temperature lowers the vapor pressure of heptane and that tends to lower sol vent losses due to evaporation. However, at 0°C and at 600 psia, the gas phase is strongly non- ideal, becoming more nonideal as temperature falls. As the temperature falls, the solubility of heptane in high-pressure ethane and propane rises due to increased attraction between heptane and ethane on propane. In this case, the effect of increased gas-phase nonideality is more impor- tant than the effect of decreased vapor pressure. 15. a) They ate listed in Page 106 of the textbook: 1, Qcan be factored so that Qjqc is independent of density 2. Classical (rather than quantum) statistical mechanics is applicable. 3. Tyo = EP pers) (Pairwise additivity. 4. P/e=F(r/a) (universal functionality) b)_ In general, assumption 4 is violated. But if we fix the core size to be a fixed fraction of the collision diameter, then Kihara potential is a 2-parameter (a, €) potential that satisfies corre- sponding states. ©) Hydrogen (at least at low temperatures) has a de Broglie wavelength large enough so that quantum effects must be considered and therefore assumption 2 is violated. Assumption 1 is probably pretty good for Hp; assumption 4 is violated slightly. All substances violate assumption 3, but H, isn’t very polarizable so it might be closer than the average substance to pairwise addi- tivity 4) Corresponding states (and thermodynamics in general) can only give us functions such as Values of <8 (for isolated molecules) cannot be computed by these methods, because eye the contributions to ¢® (rotation, vibration, translational kinetic energy) appear in Qj, and the kinetic energy factor, not in the configuration integra 16. Let at represent the phase inside the droplet and i the surrounding phase. ‘Schematically we have for the initial state and for the final (equilibrium) state:Solutons Manual 40 ws wo : % we wi ye iS 5 5 1 oe Tatra Examen Because the molar mass of lysozyme is above the membrane's cut-off point, lysozyme can- not diffuse across the membrane. Let: 8 represent the change in K* concentration in a: 4 represent the change in Na® concentration in B. ‘The final concentrations (f) of all the species in a and fare: Ina: <0 te cle 608 aa g Noy “Noy Bae cB ac gM ae pa inp: e® 7 . 7 = fs nat “Ne! ‘Noy ” “NF ‘The equilibrium equations for the two nitrates are Bee Hog “Hae * HRs ® wy oe Ne Nor Similar tothe derivation in the text (pages 102-103), Eq, (1) yields Sb act en «wos ~ SK Sos Q) SNe ‘NOT “sar “N05 where, for clarity, superscript fhas been removed from all the concentrations Substituting the definitions of 8 and @ gives: (oes -0 ee Se A Nos (3) 08 00. ) + 8-9|=(fet_ 3 (et, °] @leXo3 89) whereSolutons Manual a 97010 mol 17 K* Nos Tg water (using the mass density of water at 25°C: 0.997 g em’) and ee 5001 mol 7 nat” “x03 Solving for 8 and 9 gives 8=4.985x107 mol L“! “ @ = 5.00010" mol I~ Because both solutions are dilute, we can replace the activities of the solvent by the corre sponding mole fractions, The osmotic pressure is thus given by [ef. Eg, (4-50) of the text] o no AP 6 where x is the mole fraction of the solvent (water) given by AEX I-Gho, HA + © Parbeody. th ek ab Because solutions are dilute, we expand the logarithmic terms in Eq. (5), making the ap- proximation In(1- A) =—4 ATE hak ab cab yet, sat ox ma [thoy tha tH Ho, tf. 48K] ‘Again, because solutions are very date, with, Using the relationships with the original concentrations, we haveSolutons Manual 2 TUCO -8-+9)+(c2% -8)+(0)-(C%®_ +8 -9)-(C™*_ - 9) CR) Nos K NoF Na 8 Because “S05 met er) os “wat we obtain ce 708 _ OB rack ~2e%P ch, 46-449) o The lysozyme concentration is BIN 000) mel 4995104 mol Lt TL. Substitution of values in Bq, (7) gives the osmotic pressure 8314.51 Pa L mol"! K"!) x (298 K) x [(2«9.97 x 1073)— (2 « 0.01) - (1.429104) ~(4 «4.985 x 107) + (4 5.000107) (mol 7} 354 Pa 17. Because only water ean diffuse across the membrane, we apply direetly Eq, (4-41) derived in the text ~Inay =—InGsyyy) = EE o where subscript w indicates water. Since the aqueous solution in part ois dilute in the sense of Raoult’s law, y, =1. This ro- duces Eq, (1) to Ryu RT =Inxy = In(l=4 =a) * (a +449) = or equivalently, @)Solutons Manual 43 BTN ng) pare w ALT= 300K, », 018069 mot 17? pre Mole fractions x, and xq, can be calculated from the dimerization constant and the mass balance on protein A: @ vig — Me = 8018 — 15.069 em? mol 0.997 S15 000) mal A 18151075 = xy +2, © (1000 18.069) mol water Solving Eqs. (4) and (5) simultaneously gives xy = 734% 10% 38x10 Substituting these mole fractions in Eq. (3), we obtain (0.0831451) x (300) (538% 10% 4734x105) (0.018069) = 0.01756 bar = 1756 Pa From By. 445) ERE erptey« ai Proting 1/cy th min pascal and yin gL) a fction ofc, we obtain the protein's anotecolr eight Go the ftrept an th second wl exotic eos om the opeSolutons Manual 44 478: 45. 425: ars] slop, Pal gt 38, 0 2 a0 oo BSA Concentration, gt! From a least-square fitting we obtain: Intercept = RTM, = 35.25 Pa L g" 5.25 Pa m’ kg"! from which we obtain RT__ (29815)x (8314) 3525 3525 M, = = 70321 kg mol"! = 70321 g mol"! Slope = 0.196 = RTBY. Therefore, B* = 7.92x10° L mol g?. The protein's specific volume is given by the ratio molecular volume/molecular mass. ‘The mass per particle is 70,321 Na 6.022%10% =1.17«107 g molecule Because protein molecule is considered spherical, the actual volume of the particle is 1/4 of the excluded volume. Therefore the actual volume of the spherical particle is HSx10""* = 295310725 m' motecule™ which corresponds to a molecular radius of 4.1310 m or 4.13 nm. For the specific volume: 295x107 17x 10-9 252x106 m* go! =252 em’ g b) Comparison of this value with the nonsolvated value of 0.75 em? gr, indicates that the par- ticle is hydrated.Solutons Manual 45 ©) Plotting x/ep (with in pascal and cin g L!) asa function of ey forthe data at pH = 7.00, wwe obtain 60 575 . 55: 525. lez, Palo" 478: 45 < 425: 40. 18 Po 3 45 5 BSA Concentration, g t! 0.3317, which is steeper that at pH = 5.34, originating a larger second virial os- cocfficient: Y= 1.338x107 L mol g2= 13.3810 L mol g2 At pil = 7.00, the protein is charged. The charged protcin particles require counterions so clectroncutrality is obtained. The counterions form an ion atmosphere around a central protein particle and therefore this particles and its surrounding ion atmosphere have a larger excluded volume than the uncharged particle Itis the difference between the value of Bat pH = 7.00 and that at plt = $.37 for the un- charged molecule gives the contribution of the charge to B 10002? (13.38 - 7.92) x10 L mol = 1000 4MZovmax In this equation, we take the solution mass density p; ~ pyr =18em™. Moreover, My 70,321 g mot, and myx = 0.15 mol kg"! 4 (5:46 1078) (70,321)? (1.0) (0.15108) _ 1000 162 or 2=+13, Because pH is higher than the protein's isoelectric point, the BSA must be nega tively charged. Hence, 2=-13 19, a) From (4-45) and according to the data: AL RB" (e—ey)+ MySolutons Manual 46 Ploting x/(ee9) (with x in pascal and cp in g 1") as a funotion of © ~ cg, we obtain the solute’s molecular weight from the intercept and the second virial osmotic coefficient from the slope. rao g « (6-60), 9" From a least-square fitting we obtain: Intercept = RT/M, = 14.658 Pa L g'!= 14.658 Pam? kg"! from which we obtain RE __ 298.15) (8.314) My -E. 214.659 14.659 69.109 kg mol"! = 169,109 g molt Slope = 0.053495 = R7B". Therefore, BY = 2.16x10 L mol g? b) The number of molecules in the aggregate is obtained by comparison of the molecular ‘weight of the original ether (= 390 g mol) with that obtained in a) 169,109 ‘Number of molecules in the aggregate Ere 550 Assuming that the colloidal particles are spherical, we obtain the molar volume of the ag- sgregates from the value of the second virial osmotic coefficient B*. It can be shown (see, ¢.8., Principles of Colloid and Surface Chemistry, 19917, P.C. Hiemenz, R. Rajagopalan, 3°. Ed,, Mare cel Dekker) that B* is related to the excluded volume V® through Nv Bae 2MSolutons Manual 47 From a), BY = 2.1610 L mol g? = 2.1610 m* mol kg? and M; = 169,109 g mol 169.109 kg mol'!. The above equation gives /* that is 4 times the actual volume of the particles, (we assume that the aggregates are spherical). Calculation gives for the aggregate’s volume, 5.13%10-5 m’ (or 30.90 dm? mot) with a radius of 4.97%10 m or § nm.SOLUTIONS TO PROBLEMS CHAPTER 5 1 Initial pressure Py + for m moles of gas 1 at constant T and V: fy Su RT wy @ rT, PTH Re : re Final pressure Py ~ after addition of ny moles of gas 2 at same T'and V: where (ny +,)? B= nf By +2nymBhy *BBap Pressure change AP mT AP =P —R = omnis + Solving for By 49Solutons Manual 50 fon > Keon , 0 infin roar TaD THAT hive (Sj, = 0156 bar (at 6 bar, 173K) Next, find the vapor mole fraction of CO, that is in equilibrium with the solid at the speci- fied P and 7: Ye02 = 2 econ? Using the virial equation for the vapor, y Ineo, 2 gltco2 Bo, +211, Biig—coz)~Inz Because yco, <1, we may make the approximations zat, and v= From data for H, (see App. C) at -100°C, By, =88 em® mot which indicates that zy) =1 From correlations: Bcoy = 460 em? mot! 32:1 em? mol Beoy-y = At equilibrium Kooy = Feo, and thenSolutons Manual St feo, 2p exp =f 00,80, +(1=H00, B00, ]} P fF [04 Boo, +(1~3e0, co | Yo; Yeo, = 0.00344 Because yoo, < 0.01 at equilibrium, CO, precipitates To find out how much, assume solid is pure CO. Let n be the number of moles of CO, left in the gas phase, From the mass balance and, as basis, 1 mole of mixture, 0.00344 = ne 099 003417 ‘The number of moles precipitating is 0.01 -0.003417 = 0.0066 moles CO, Condensation will occur in the outlet if 25, > FZ, First it is necessary to find the outlet temperature, assuming no condensation, Joule Thomson throttling is an isenthalpic process that may be analyzed for 1 mole of gas through a 3+ step process: 1, I: Isothermal pres Pp sure changes. I: Isobarie temperature change.Solutons Manual 52 Then a @ @) anu =f [+-»(2 |e a P Assuming that the volumetric properties of the gaseous mixture are given by the virial equa- tion of state truncated after the second term, RT AT, P then, (@), (5) Tip P\ dT Jp where Bais is the second virial coefficient of the mixture Because Briss = 24 Bui + 2vvaBin + ¥3Bo2 3) (=cHy 2=co,) 5 yyy, dia, 2 Aaa PBA ayy, Bi, o pr a 8 ae “ it then o Assume ° 0 Sym, e2 paint = Yow" pcHtg C02 p.COp ® then,Solutons Manual 53 ( ‘i " ( 0 (fon Sa fare Ppa + [| B= { Sas) am h, Jes L a Jp) acl) 3¢ ad) 42) } je, 28s. 20, 2 Bala ° (es Te mt Te A) o From dat As 1-07. 92-03, epi =3622 1K"! mol according to Ea, (8). From Eqs. (5), (6) and (7), <2), = 3412108 Substitution in Bq. (9) gives Ty =2784 K. Second, the fugacities of liquid and vapor phases may be calculated, p vf, ss ‘co, =x PS, Ob. ext dP 'c0, Yeo; Fo, 900, &%P i. RT ‘This equation may be simplified assuming that xco, Yc03 » @fo Saul to uy, AU2ISK, P,, =398bar and vy, = 490 mmol” 1 (49.0) « (1-398) = (898) x exp] 20-398) Seon G98) xexp) (83.1451) x (278), |- asst ogi of vapor icles om fo, = 9conse0nP with, Ingco, =[20%c0, Boo, +i Boos-c,)—Brint be neo, [2x(0.3. (2139) 260.7 +6]Solutons Manual co, 0995 #1 Then Fog #03 bar Foon “Son no condensation occurs. 4. The S rockmayer potential is where jis the dipole moment, ‘We can write the potential in dimensionles } where / isa universal function. J ‘Therefore, we can write the compressibility factor z in terms of the reduced quantities: z= fF, Bi) with,Solutons Manual 5 a) For acetylene: T, =3083K, @ = 0184, ALO°C, Tp = 0.886 = 090 , Using Lee-Kesler charts (see, e.g., AICHE J., 21; 510 [1975] as! /R=3993 0-078 {9-010 As /R=3856 (831451) «13.993 + 0.184) x 3856) Avap' Asaph =T Aap = (273)(39.1) = 10.67 kJ mol a Scag = Drag RT Gp 21) = 10.67 ~ (831451) x 273) x (0.16 ~0,092) x 10° yap! = 915 KI mol! b) CaHyo: TM. =4252K Nz: T. =1262K P,=380 bar P= 337 bar @ =0193 @=004 0, =255 em? mol" 1, =895 em? mol AUA61K Ta = 1084 Te = 365 Using the Pitzer-Tsonopoulos equation (see Sec. 5.7) Be yi =-267 em? mot! By, =155 em} mot! For Byy on (0 +0) = 0116556 Solutons Manual 990) (Try ‘Then, By =—216 em? mol! Brust = 97 By1 + 293¥2Big +33Bp9 =—177.2 em? mol 9 CHAM): ]=1906K ——NZQ!T=162K HG): 1. =332K 7, = 460 bar P.=337 bar P,=130 bar © = 0.008 © =0040 022 = 65.0 em? mol” ve = 99.0 em? mol~ ve = 89.5 em? mol 105 At 200 K: Tp At100 bar: Pe Using the mixing rules suggested by Lee and Kesler: ISS yo! evlys mare Lys V3y9 Fe LO LN Te Ta)? Temi me 7 Pesning = (0.291—0.080 ping )RTe mis! Peis Vem = 84.1 m° mol” Toypigt = 1138 K (Ty =180) Prop = 31AT bar (Py = 318) 1 (hh + hy +h). Enthalpy of mixing = h¥ = hgixsre —5' Using the Lee-Kesler charts,Solutons Manual oT 1383+ 0)= 1334 J mot 6 LiG=5 x 0 bar r=25°C ¥ 40% Ne < Sor He A0% CHa From the mass balance for C3Hy Ya = You +ou(L+Din~YoutI) You = 005396 010 =0.005 + 005%c, icy = 0.01898 = mole fraction of CyHy in effluent ol ‘To find the driving force, note that P= Pes = veqP'% = (0.10) (40)=4 bar PE = P= Key 8 where Sey = xegll ~ (0001898) (533) = L012 bar and - 2p . Ines = pr DeyBey *NaBeyna +p Beyey I-In= ‘Obtain virial coefficients from one of the generalized correlations:Solutons Manual 58 Bic, = 400.8 em? mot! BoseNy =~735 cm moll 35 cm? m Besatty We may estimate 2* =0.95 (feed value) To find yy. 9%y> and figs We know thet (of, /yhg) = 4/5. As fist guess, assume 10. Then we calculate, . 1012 0.0292 (40) (0855) This gives Ny +h = 09708 or With these y*'s, calculate @¢:, again: 2, =0924 and yb, =0.027 That is close enough. Thus, + _ L012 , 1095 bar 3924 Now we must check the assumption z* = 0.95 was correct, sumption is close enough, Jsing the virial equation, the as- Diving force = (Poy — PE) = (400-1095) =2.91 bar 7. Since ff = f°, ae. OP = gay PL As Py, = Using the virial equation,Solutons Manual 59 2 Ing, = 5018s + y2Bi2)— nz 2 Inga = 202822 + ¥1B12)~ Ize Because Po RT >t P Buixg ~-323 em mot! = 524 em? moll, pig = 10067 Thus, 9) =08316 92 = 0.9845 (60) (50) (vo and 2Rer31 * Yn ayy - 2f2)-1m (ov 8. For methane (1) and methanol (2), we may write A= Neglecting the Poynting corrections [Note: the Poynting Correction is 1.035, Including this, we get y2= 0.00268], MOP =x HipSolutons Manual 60 Y202P = x21 2P70} Because xp Use virial equation to get fugacity coefficients: assume yz =1 : 2 sep (4058) (0.0401) SP 314) x OTD Assuming yy =1, yz =0 as first estimate, 91 = 0954 v2 183 Thus, 02 =0.770 and = 0.01867 ‘y= 0000255 ‘This caleulation is important to determine solvent losses in natural gas absorbers using methanol as solvent. 2monomer) == dimer ‘The equilibrium constant is as as _ fal fa__ Sa) fon (mF Umi fa fa BE ] where ag is the activity of the dimer, and aj, isthe activity of the monomer. The quantity /2° /f2 isa constant that depends on 7, but not on P or y. Then,Solutons Manual 6 fa=hia vere iw eons 10, ay a, \ CH—O—CH S \ at ay, a,ay—o—ayayaya, Disisopropy ether thy buy ether HCI can associate with the ether's non-bonded electron pairs. However, the di-isopropyl ether will offer some steric hindrance. The cross-cocfficient, jz, is a measure of association, Both virial coefficients will be negative; By for ethyl butyl ether/HCI will be more negative, 11. Let a be the fraction of molecules that are dimerized at equilibrium, A = A I-a a/2 ya T-ai2 By assuming the vapor to be an ideal gas, we may write Pr MP (al (AP OaPP oP AL the saturation pressure, P = 2.026 bar and ya = 0493 06726Solutons Manual 82 Then IA ~ Ix ~yaP = (0.493)x (2.026) = 0.999 bar The pressure effect on fugacity is given by Assuming the liquid to be incompressible in the range P* to 50 bar, tn fa(50.bar)__ Una? Fa2026 ba) RT (30 bat)=1 bar 12. a) The Redlich-Kwong equation is RE o-b RTS uly a (1) . +b) If z is expanded in powers of Iv This gives B=p-—4 Rr 2, ab on8 But, Substitution givesSolutons Manual 63 b) Using an equation that gives fugacities from volumetric data, we obtain PT gg Mea 2 + Fan 293 (a)? | Ine RT Evaluate a and 6 using critical dats: Ethylene (I); T,=2824K P= 50.4 bar Nitrogen (2): T, = 1262K P= 33.7 bar 14, = 7.86107 bar em K1!? mot? ay 157107 b, = 40.4 em? mot Substitution gives @; = 0.845, Ai=)19)P = 844 bar 13. Using the virial equation, Brint a ep) RT EBigt ) 0) tte) <9 7 (2), -SCE), Substituting Eg. (1) into Eg, (2) gives (2 ( Bois —s = 2yBj1 ~2y2B12 +2 By ~2By2 = 0 At maximum,Solutons Manual 64 Br 3) Ba By 12 ° Using the corelations, Byy =—1267 em? mot"! (ethylene) 1 (argon) By = ~459 om? mor ‘Substitution in Eq. (3) gives yy sos 14, Consider a 3.step process: Pe idea gases odie gases T Pre gases an The overall enthalpy change is zero: Aify+ Atty eH = AM, = AM + myAFl (1 = hydrogen; 2 ethylene) ant, = 84% -7)+ EE err) a on ant, =0,;-1)+ 2" er) is evaluated using Lee-Kesler Tables.Solutons Manual 65 For heat capacities, we ean estimate o 60) =286 TK! mor! by = 187 5K mot! Atty =0 (Because we are mixing idol gas) (1-0) Ag =] Neti evaluated at Ty= Ty! Tepigy Pe = 2070, = a Poa it Tene P= 20.TPa (Riis | Find 7; by tial and error: p= 07K 18, At equilibrium, In=tR Po a@aP = (1=xc0, PO OX Aap rroatoo-nonarien |’ Assuming coy But Because y4 <308))/(0.446%30) yy 2axt0S 17. Water will condense if f2.4 > £25 Thus, the maximum moisture content, 944.0 8 given by vps Aizo = hizo poy . tho sn0Pho? =xH0Rioe%),, —pAear tio Assuming that the condensate is pure (solid) water, *Ho-1 and fs, ‘Then68 Solutons Manual essay 341,09%)%(G0 bar) = 95 019) _pyp] —_\_150,06 Cin0,0%C0 9 = 50.06 tora) (S145) x 263.15) 890%10"5 210 = 7 H20 Let 1 Ny,2» Oz, and 3 H,0. To get ok se the vial equation of sate Im9f 0 = bs = [2018s +9285 +25Brs)— Bain with Bont = DDL By ro Assume yy << where y, = 0.80 and y) = 0.2. Then, Bryne = 3B) +93Bp9 +20592Bjg =—218 em? mol" Substitution in the equation for Ings gives @; = 0871 As 8901078 7 Sh20 then Jago = 1.0% 104 18. The Joule-Thompson coefficient is defined as kn ($), o ¢ rule with T, P and H, we have Applying the triple-produSolutons Manual oH Ee) AQP J g GH) OF, Because and combining Eqs. (I) and (2) gives From the fundamental equation dif = Td + VaP , we have Therefore, 69 2 @) a 6) o oO Because in this specific problem we want u of the bydrogen-ethane mixture to be zero, Eq, (7) yields ®)Solutons Manual 70 From the truncated-virial equation of state Pu_,,B ak ° ary ° we have ye ote. (= “2 \e- )- P\ue+26) a0) @)p RAV+BA” 0+B) UR) wry Substituting the equation of state Eq. (9) and Eq, (10) into Eg, (8) yields Rr(, BY _ LR +B) | .4) Rweny ay Pv) | [Puwr2e) or equivalently, B=0 02) where B is the second virial coefficient of the hydrogen-ethane mixture at 300 K. Using the McGlashan and Potter equation (Eg. (5-52)], B (7 4 oss0 08642 ca 7) » we obtain By) =114 em? mol~! for hydrogen, and By =-1733 em? 000 I"! for ethane, and By = By, =114 em’ mol"! for the cross term, respectively. Applying Brsixt LL and the material balance yy +33 =1,, we have Bag (em* mol ) 114y? +228y,(1-y)-17330-94) «sy Equations (12) and (14) yield y, = 0.73, Consequently, if we start out with 1 mol of H, the amount of ethane that must be added to have a zero jy is 0.37 mol 19, Because methane does not significantly dissolve in liquid water at moderate pressures, the equation of equilibrium is psc? oSolutons Manual 71 or equivalently, papa? = Phos ex| ® where subscript 2 denotes water ‘The fugacity coefficient from the volumecexplicit virial equation of state is given by Eq. (5+ 33): 8) Ing2 = [201Bi2 + ¥2B22)—B, mnie Le with, Brus = Bi +2028 10 + Y3Ba2 a Similarly, we also have 8) (2) Atthe inlet (60°C, 20 bar Substitute Egs, (3), (4), and (5) into Eg. 2). Solving Eq (2) using vf =18 em’ mol and PS = 149 mmHg, we obtain yh = 0011 (superscript i denotes inlet) Gi) Atthe outlet (25°C, 40 ban Similarly, with of =18 om? mol! and Pf =24 mmiig, we obtain yf = 0.000951 (superscript o denotes outlet). Because the gas phase is primarily methane, the amount of water that must be removed per ‘mol methane is ‘mol water removed yiny$ = 001 ‘mol methane ” 20. Assuming negligible changes in potential and kinetic energies, the first law of thermody- namics for a steady-state flow process is,Solutons Manual 72 AH=0+W, a where A/T is the change in enthalpy, and Q and W, are, respectively, the heat and the shaft ‘work done on the system (by the surroundings) Because we are given the initial and final state and enthalpy isa state function, A/T is fixed inthis problem. Consequently, minimum M7, corresponds to maximum @. Maximum Q occurs when the process is reversible, or equivalently Q= 7AS Henee, Eg, (1) can be rewritten as WW, =aH-TAs ® where Mf, is now the minimum amount of work required for the process To calculate AM and AS from the volume-cxplicit virial equation of state Py my RT 1+BP we take an isothermal reversible path from the initial to the final state Expressions for enthalpy and entropy are given by Eqs, (3-9) and (3-10) in the text: H= {lr (Z) renatonat XE ny @) s=f foot InyyP+my InypP)+ms? +mso Substituting BP) from the virial equation of state gives H= mh? + mi a S= mpRBP= Rn lnyyP +1 InyzP)+m80-+mys8 Applying Eq. (4) to this specific problem, we have Au-0 co) AS = RP (ny Boys — B33 —Bp2)— Remy IH, +72 nya) A298 K, second virial coefficients areSolutons Manual 73 By = -419 em? mol" Bip = -1222 em? mol! © Baz =~660 em mol"! Hence, at 298 K, Bane = ETI) By =—740 om mot! Taking a basis of my =1 mol of the mixture initially, then m =n, =0.5 mol, Eq. (5) yields at 298K Ar=0 o TAS =—2485 ki Substituting Eq. (7) into Eq. (2), the minimum amount of work required fo 248.5 kJ mol"! of initial mixture, 21, ‘The second virial coefficient for a square-well potential is given by Eq. (5-39) in the text, a with, @ Substituting €/k=469K, ¢=0.429nm and R=0.3376 gives ‘B(423 K) = 302 em? mol! Because, for a pure component, ing=in£ 22 ° PRT fugacity is given by (BP S= PestSolutons Manual 74 Hence, at 150°C and 30 atm, f= G0atm) xex Te {82.06 aim em? mol = 3894 atm = 39 atm To obtain the standard enthalpy and entropy of dimerization of methyl chloride we assume a small degree of dimerization. In this case, the relation between the second virial coctticient and the dimerization constant is given by Eq, (5-113): Bao Applying P° = R7e° (where e =1 mol “' = 10" mol em is the standard state) gives 10%(em? mot" )K = B-6 Because we only have a weak dimerization, Qe? 5 b= hy == aN yo 3) b= 5 6) and the second virial coefficient is essentially that of pure methyl chloride [Eq. (1)] ‘Combining Eqs, (1) and (3) gives “a 14m? marx (2 ote [ { The following table shows K(T) calculated from Eq. (4) Ti) K 100 10.74 200 0.939 300 0376 400 0.222 500) 0.155 Because the standard enthalpy and entropy of dimeriza jon obey (Eq. (5-114)] 0 =Rink = 2" _ aso plotting ~RInK as a function of 1/7 gives Ah? as the slope, and —As® as the intercept Results are An? = -4.34 kd mot As? = 23.25 K7 molSolutons Manual 75 2. a) Substitution of given T(r) in Eq, (5-19) gives aaa) [0--"yha [0net Aa 2a) [eee [cee AD 2p | o At high temperatures, A/AT?" is small Because e ef sleet tte. when xis small, wwe expand the exponencial 4/47" OAT ay. ir” Substitution of this approximation into Eq. (1) gives: [one iear ff 2) ‘Constant is large (ie. n> 3)Solutons Manual 76 3 AT (n—3)0" 34 LATen=3o" | 1b) From Eq, (3) we sce that itis the attractive part of the potential that causes negative B and is responsible for the temperature dependence of B [the first term on the right hand side of Eq, (3) is independent of temperature] 23, Substitution of the square-well potential [Eg. (S-39)] into Eq, (5-17) gives Ba2nNg Foret AT Par od nV go? +2 aN eT (R903) In the equation above, R’= Ro = 1.55c. For argon, 6 = 0.2989 nm = 0.2989%10 m, ek 41.06 K, and R’= 1,550 = 4.633101 m, ‘The above equation gives for T= 273.15 K, B= 33681075 + (6.202% 1075) 2834 «10° m'mol"! = 28 em? mot ‘The calculated value compares relatively well with the experimental B for argon at the same temperature: Bygy = -22.08 em? mothSolutons Manual 7 24, Substitution of Sutherland potential [Eq, (5-37)] in Ea. (5-19) with N= N gives Bery=20N4) [de years [a yer) a 2) 6 fI8 2acaryt 2aryr? ary aD J ie We now have to replace the approximate result (Eq. (2)] in Eq. (1) and perform the neces- sary integrations, The result is: 2 BT) =2 nN yo" AT) = SN 3ETo* 18(KTPo? 90(KTYF o> S04(kT) a?! This equation is best solved using an appropriate computer software such as Mathematica, TkSolver, MathCad, etc. Making the necessary programming we obtain at 373 K, ‘B(methane) =-20 em mot B(n-pentane) = -634 em mot! In both cases, the agreement with experiment is very good, 25, The equation of equilibrium for helium is fi = fF wo where superscripts L and & stand for left and right compartments, respectively. Equivalently,Solutons Manual 78 sfoitPt =sfoytP® @ n (5-33) of the text gives the fugacity coefficients in both compartments from the volume-enpict virial equation of state In) = [20481 + ¥2B)2)— Boy 8) with ie = Bis +20192B12 +93Ba2 o Further, we also have material balances ae © fot Applying Eqs. (3), (4), and (5)1o both compartments yields pe tnof = [04840-3682 |-[ ob Bu +2n'0-9f Bia +091) Be} © pe wot = 2) onan +d-m" is [4 ox Pay +2080 Bis +B [PE Total mole balance on helium gives nf +nff =002 mol 0 Combining with mass balances on ethane and nitrogen gives ® 002—nb 101=nk Substituting Eqs. (6) and (8) into Eq. (2) yields nb = 0.013 mol Combining this result and Eq. (8) gives of -0013 of = 0.007Solutons Manual 79 26, Because the equilibrium constant is independent of pressure, the more probable reaction is the one that satisfies this condition (1) Assuming reaction (a) is more probable: With this scheme, concentration of (HF), is negligible compared to those of (HF) and (HIP) ‘The equilibrium constant Ka) is Yay Yon io) = = © vu? [Ivy] P? “otal mass halance for (HF) gives vanrygnr 8% Mie) [=r rine = Pu @ where V is the total volume; pyp and Myp are the mass density and the molar mass of hydro- gen fluoride, respectively; np is the total number of moles that can be calculated by assuming that the gas phase is ideal: Py np FE 3) Tae 8) Substituting Egs. (2) and (3) into Bq, (1) yields a Applying Eq. (4) atthe two pressures, 1.42 and 2.84 bar, we obtain for Ky) P (bar) PHF) — Kay 1a? 140 0.0595 284 5.45 0.453 Because Ka) depends on pressure, reaction (a) cannot be the more probable one. [Next we need to check for the pressure independence of Kiyy (2) Assuming reaction (b) is more probable:Solutons Manual 80 In this case, concentration of (HF), is negligible compared to those of (HF) and (HF) The equilibrium constant Kj is Ky © win”? fi-voay PS Mass balance for HF in this ease is Yearygtr(6% Mue)+[1 vans bir Mie =P Pur o where all terms are defined in Bq. (2) Substitution of Eqs. (3) and (6) into Eq. (5) gives ) a af oye Px Myp Ky = o 1-4/5] Pu? _1)) ps LPs | Corresponding values of Ky) at 1.42 and 2.84 bar are Pibay par (GIL) Ki 1a2 140 0.017 2.84 5.45 0.017 Because Ky) is independent of pressure, reaction (b) is the more probable.SOLUTIONS TO PROBLEMS cHaPpTER 6 1, The three equations of equilibrium (in addition to T! = 7" and P! =P”) are nie P= xenuf 220pP = 21h ps0 P asin \with (assuming the liquid incompressible) We write similar expressions for fb and fyi For o” we may write RT Ing = PB +2y2Bi2 +2938t3 ~Boint) and similar expressions for oY and @Y. In these equations, Brisa = 27 Bi ¥¥3B22 +¥5Bs3 + 2yiyaBi2 * 2vyvsBis + 2v2vsBas atSolutons Manual 82 2. Given g” = Axyxpwith Ff / PS (649, and assuming ideal vapor, nP aft DP. “PP At azeotrope, xy ~ yy P Inyp =n acing From the g# expression, ny Ae and Then Because 0x7 <1, ‘Thus, if [41 LRP, an azeotrope exists.Solutons Manual 83 3. From the plot P-r-y we can see the unusual behavior of this system: 1. There is a double azeotrope 2. Liquid and vapor curves are very close to each other. T T T £ § : 1 = A= Lido) 72 Vapor (0) L L L 1 ° 02 oa a6. os: 10 xr 4, Neglecting vapor phase non-idealities, ayy Ph + apy Py wo At the maximum, fa (en) ( 2) conn ean) -ons[ Jp Le Jp en} From the Gibbs-Duhem equation (at constant T and low pressure), QSolutons Manual 84 Substituting Eq. (3) into Eq. (2) and simplifying, (aR -2F)] There are two possibilities QnA -2PE Then ni ne a =1 corresponds to an azeatrope ae ne 2 ‘The solution to this differential equation is xj7 = constant To find the constant, use the boundary condition y; =1when x) =1. Hence yx be! Hence, the curve Pex goes through a maximum at xj =1. This is also an azeotrope (but a trivial one), As yP=ay7yP if yxy = then y, mus 5. Given Aaxyny + Antsy + Avaatg + Ansay + Angtatg + Agate where * rie may nt be immediatly obvious, But 3 i the activity, and the activi of component 1 cant rash unity for any x ess ‘than one bese the sluton wil spit int wo phases of lower aetviy, Se Fig, 625 inthe exSolutons Manual 85 xpeminp with np =m +ng 4n5 4ng the total number of moles. Because arnny= (=*) we find RT In, = Aish + Ash + Avexd tx EGLAi + Ay Aaa) “tran + dug dag) +25%4(Ana + Aig) 6. Calculate T-y giving pressure and for x= 0.1, 0.2, ..., 0.9 ~ bubble-point calculation ‘We have to solve the equilibrium equations: oa = YeKiPE a Because total pressure is low (below atmospheric) we assume vapor phase as ideal: 9, = 1 The activity coefficients are obtained from the equation for GF given in the data. Using Eg. (6-47) of the text we obtain 2 |As the pressure is fixed, temperature varies along with x, (and y,) and is bounded by the saturation temperatures of the two components. These can be casily obtained from the vapor pressure equations. They are given in the form, InP =4 @) Tre from which we obtain the saturation temperature Oy A=InP*Solutons Manual 86 For P! = 30 kPa, we obtain Jf =387.26K for cyclohexanone (1) and Tf =41559K for phenol (2) To obtain the T-xy-y, diagram we assign values for the liquid mole fraction x). Total pres- Pernkl sikh ya-—? _ © i Fe x tye natn To stat the calculation we make an initial estimate of the temperature: aff +xp0 © For example, let us fix x, = 0.5: T= 05%38726 + 05% 41559 = 40142K With this temperature we obtain Rf and PS from Eq, (3), the pure-component vapor pres- sure equations: PY = 47243 kPa and PJ =17918kPa Because we fixed xy, Eqs. (2) give yy = exp-21 x05?) = 0592 and 72 = 0.592 Next we recalculate Af = 73.482 kPa. from Eq. (5), which in turn gives a new temperature, Tr 16.34 K, from the pure cyclohexanone vapor pressure equation, The sequence of calculations is now repeated for this new temperature (we assume here that activity coefficients are independent of temperature), yielding: PS = 30.786 kPa; PY = 71.426 kPa {fiom Eq.(5)] Tf =41534K [fom Eq(6)] 1.S52KPa; Ty 415.40K; Pf= 29.798 kPa ‘After these values, the change in temperature is small and therefore additional iterations leads to no significant further change in the remaining values. ‘We can now calculate the vapor phase mole fraction from xaiPE _ (0.5) (0.592) x (71552) P 30 = 0.706 ‘The whole process is repeated for a new liquid mole fraction. ‘The following figure shows the computed T-x,-»; diagram for this system at 30 kPa,Solutons Manual 87 Cyclohexanone Mole Fraction Similarly, with the data calculated we ean easily draw the corresponding yy-x; diagy shown in the figure below, Vapor Mole Fraction Cyclohexanone Liquid Mole Fracton Cyclohexanone As both figures show, this system has an azeotrope at T™ = 421K and for the composition x03,Solutons Manual 88 7. Assume g! Aisa function of temperature. Then, RT In? = RTI But Because (T-273° At x; =x) =05 and T= 333K, BP = Apigh= 641 J mol" 1) From the equation for Hy we can obtain the infinite dilution partial molar enthalpy of water in sulfuric acid solutions at 293 K and 1 bar as: Tig = lim Thy = lim Thy 41.44 kJ mot b)_ The mixing process is schematically shown below,Solutons Manual 89 ‘Taking the liquid in the vessel as the system, a first law balance gives for this flow process AU =dQ+dW+Hyding + Hiding where work Wis di =-PdV’, done on environment by the rising liquid level, under constant pressure, Then, aU + PV) = dH = dQ+ Hing + Hydny Integrating between initial state (empty vessel) and final state (full vessel), because Hy =HAT.P) ofthe pure acid and Hy = Hy(T,P) ofthe pure water are constant, we obsain H=QsngHytnglly of Q=H-ngllg~MHy But 1 =ngiig-+ngiTy, and the equation above becomes Q= ng(Fly = H4)+ng(Fhy =H) ~ngATTg +m,ATly = AH 0 where ny = I mol and y= 2 mol inthe final state In Eq. (1), the quantity (77, ~11,) is given by the equation given in the data, because the reference state in that equation has been chosen to be pure water at system T and P: 7 134x4 Fig, =-—"*4 gt mot! @ (079835, We need now to calculate the quantity (74—H,), knowing (Hy ~Hl,). This ean be done by using the Gibbs-Duhem equation. ‘At constant and P: Lexy a git, XA xa xydHy+xydHy-0 > diy ai, o Differentiating Eq. (2), at constant T™and P, we obtain: 2x 4(1+0.7983x4)? 3x3, 3x, AOI NTA O7PEIEA) A134 1d mot) (4079835 9) o = 2884 tek mol) C= 079884" Therefore, from Eqs. (3) and (4), df, - 7X4 (KS mol") 3 (14 0:7983% 4)" Integrating Eq, (5) between composition x, and composition x, = 1 (pure acid) givesSolutons Manual 90 oe _ M4 268% H-Titsa~-Ta-Ha~f RB a , 07988.) o (5 mot)! eases" HT4 51-24)? (1079884)? |,” C+07985x 4? We can now calculate the heat load Q in Eg. (1). Setting » = ng +m, = 3 mol, and using Eqs. (2) and (6) in (1), oen|tiSteatmea?_tatega-ap (140.7983x4)7? — (1+0.7983x4) TA Sbeg(l—x4Ml—x4 (1+ 0.7983.) T9834 o [SED] eer Substitution of n = 3 mol and x, ~ 1/3 gives the desired heat load: = 29.23 ks is negative because heat is removed from the system. a) Yes, it's possible, Slight positive deviations merely mean that the physical interaction be~ tween SO, and CyHy makes a larger contribution to the excess Gibbs energy than does the chemical interaction, » So, ~inobuene > 80,1 2 because the tendency to complex (which tends to make g# negative) is stronger with n-butene-2. Steric hindrance in isobutene is larger than in n-butene-2