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