| i | Introduction te | CHEMICAL ENGINEERING THERMODYNAMICS Sixth Edition J.M. Smith * H.C. Van Ness ¢ M.M. AbbottChapter 1 - Section A - Mathcad Solutions 1.4 The equation that relates deg F to deg C is: t(F ‘equation by setting t(F) = «(C). ‘Guess solution: Given Find(t) 240 5 a F 1.5. By definiti Peo F = massg 3000bar P-A 1.6 By definition: Pp = = F = massg 3000atm 1.7 Pabs = p-g:h + Patm 13,535.28 em? Patm = 101.78kPa 18 p= 13.535-50 om Pam !=29.86in_Hg Pats == p-8-h+ Patm 4 8 (C) + 32. Solve this Ans. Note: Pressures are in gauge pressure. A= 12.566mm" mass = 3844kg = Ans. A= 0.023 in? mass='10007 Ibm Ams. b= $6.38em Pabs = 176.808kPa Ans, f= 25.62in £27179 psia Ans. Pats1.10 Assume the following: p := P := 400bar hes aa 1.11 The force on a spring is described by: F = K x where K is the spring constant, First calculate K based on the earth measurement then gyters based on spring measurement on Mars. On Earth: F= massg=K-x mass := 0.40Kg = 1,08em K = 363.333 D F ss mass.g F = 3924N m On Mars: 0.40em Fears == Kx FMars = 1.453N FMars sie 7 = 46335 Ans. mass 8Mars = ( Poenve ve After integrating: Ip) eee 8 onenver \ Poca ‘Taking the exponential of both sides Me Dene) RT and rearranging: Phenver = Pseae 2982 mol3 cov atm R = 82.06 Tes (10+273.19K ZDenver = Imi mol Me ne zpemver = 0.194 Rr Mey (tome) Ppenver >= Psca'e Ppeniee = 0.823atm Ans. denver = 0:834bar Ams. 1.13. The same proportionality applies as in Pb. 1.11. 2186-5 Almoon ?= 18.76 ¢ learth = Sloot Aleath = 113.498 Smoon M i= Alegrthlbm MS.113,498lbm Ans. Wimoon = M: moon B.767IbE = Ams. O0dolt T 114 cost = =20dollars jg Ltr costeleg = SGollars. 19 ht row 100k day Whe day 4 dollars costhuty = 18.262 Solas costelgg = 25.567 Solar yF yr goo dollars COSttotal *= COStbulb + COSteIee o “Ans. 11S Ds 125k mass == 250lbm gis 2.169% § Patm i= 30.12in_Hg A= 120787(a) F := PatgyA + mass-g FE b) = (b) Paps = 7 (© Als 17 Work = FeAl APE := mass-g-Al 1.16 D:= 047m Pawn 2= 101.57KPa (a) F 2 PatmrA + mass-g F () Paps = Ans. (©) Al:=0.83m = Work := F-Al Work 215.8481 Ans. AEp := mass-g-Al aid Ans. 1.18 us 40 3 Bea <1 Ans. Work := Ex Woik = 1x 10%kI Ans. 119 Wdot = -0.91-0.92 Wdot := 200W g Wdot mdot := ———~_—— g-Ah-0.91-0.92Chapter 2 - Section A - Mathcad Solutions m 24 (a) Myt := 35-kg 9.8: Az -m Work = Myre Az Work = 1:713k) Ans. (b) AU jotat == Work AUjoigh = LTISKI Ans. (©) By Eqs. (2.14) and (2.21): dU + d(PV) = Cp-dT Since P is constant, this can be written: My20-Cp-dT = Myo-dU + Mypo-P-dV ‘Take Cp and V constant and integrate: My20-Cp-(t2-t1) = AU tonal Cp 7 18+ kg-dege Mino := 25-kg 17 = 20,02deRC | Ans. (A) For the restoration process, the change in internal energy is equal but of opposite sign to that of the initial process. Thus 715k) Ans. Qs= AU otal Q © In all cases the total internal energy change of the universe is zero. 2.2, Similar to Pb. 2.1 with mass of water = 30 kg. Answers are: (a) W=3.43 kt (b) Internal energy change of the water = 2.86 kJ (©) Final temp. = 20.027 deg C @ Q=-2.86 kt 52.4 The electric power supplied to the motor must equal the work done by the motor plus the heat generated by the motor. 9.7amp E:= ov Wdotmech = 1-25hp Weotelect = hE Wetecg = 1.067 10° W Qdot := Wdotelect ~ Wdotimoch Qdot £134.875W Ans. 2.5 Eq. (2.3): AU'= Q+W Step 1t02: AUty := -200) Wyo := -60003 Qi2 == AUY—Wi2 Qi $8109 Ans, Step 3 t0 4: Ans. Step 1 to 2 to 3 to 4 to 1: Since AU' isa state function, AU' for a series of steps that leads back to the initial state must be zero. Therefore, the sum of the AU' values for all of the steps must sum to zero. AUtyy = 4700) AUty3 = ~AUty2 - AUEsy- ALLY, AUg; = 40007 Ans. Step2to3: AUtp3=-4% 10°F Qo3 = -38003 Ans. Wo3 = AUQ3- Qos Wha = 5200" For a series of steps, the total work done is the sum of the work done for each step.Wat := W134i - Wi2 — W23 ~ W34. Step 4 tot: AUty == 47001 Qat = AUtg) - War Ans, Note: Qu23a1 = -Wi2341 241 The enthalpy change of the water = work done. M := 20:kg q 4.18 id ‘At := 10-degC ‘ ee eg dest M-Cp-At eS Ans, Wdot 2.12 Qs 75k —12KI W:= AU-Q i J Ans, AU ss -12-40 Q= AU Ans, 2.13. Subscripts: e, casting; w, water; t, tank. Then me AUy + My-AUy + mrAU, = 0 Let C represent specific heat, C= Cpecy Then by Eq. (2.18) meCerAty + My-Cw Aty + meCr At kg my = 40k my = Skg 50: ia Cte 05 te = 500-degC ty = 25-degC ty :=30degC (guess) Given =meCer(t2- te) = (my-Cw + meC)-(t2- tr) to = Find(t) wy SR7TeaeBe Ans. 7215 @) ) © 247 2.18 (a) (by W mass := I. G 4.18—— kg Cy IB T= 1K AUL= massCy-AT AUR 418K) Ans, AEp == AUt AEK = AUt = 50m D:=2m astp A=3.142m" indot = p-rA —mdot = 1.571 x 10°48 8 Wdot := mdot-e-az Wdot = 7.697% 10°kW Ans. Ur = 7620-2 ke Hy =U + PPV) Up = 2784.48 Po := 1500-kPa kg Ha = Uz + P2-V2 AU = U2-Uj AH := H2-Hy Ans. an e277 Ans, : keDz Sem 222 Di m Sem uy 2% $ (a) Foran incompressible fluid, p=constant. By a mass balance, mdot = constant = u,Ayp = uzA,p. (b) 2.23. Energy balance: mdot3-H3 ~ (mdoty-H +mdotz-Hz) = Qdot Mass balance: mdot ~ mdot; ~ mdoty = 0 Therefore: mdoty-(H3 ~ Hy) + mdoty-(H3 — Ha) = Qdot or mdot-Cp-(13 ~ T)) + mdotg-Cp-(T3 — T2) * Qdot T3Cp-(mdoty + mdotz) = Qdot + mdoty-Cp:Ty + mdoty-CpT2 T5degC SdegC —mdoty = O.8—= Ty ka 18 kek Qdot + mdoty-Cp-T, + mdotg-Cp-T2 fmdoty + mdot)-Cp Ty 43.235degC Ans. 2.25 By Eq. (2.32a): By contim incompressibility225m Dz = 3.8m ATA O019deC Ans. Ans. Ans. molwt = 29 KE. 101 By Eq. (2.30): a ae 2.27 By Eq. (2.32b): t-Wsdot Qdot ==9.904kV Ans. V2 _ 72 Pi also sell Vi Ty Po By continunity, constant area See TP AH = Cp.aT = Ria R(T2-T1) 10Ty := 579.67-rankine Alby R= 3.407 tol-rankine Tp == 578-rankine (guess) Given Tz := Find(T) Ty = 578-821 rankine Ans, (119.15-degF) 228 uy 32 up 200-2 Hy 3349-2 3 s kg 2 usu? By Eq. (2.32a): Q:= Hp - Hi + Hy = 31125- kg (quess) By Eq. (2.32a): Given uz = Find(u2) Som Continuity: Ans,ty = 250-degC -mol By Eq. (2.19): Q:= mCy-(t2-t)) Q=13728k] Ans. Take into account the heat capacity of the vessel; then ks 100-k by = 0.5: " 4 = gdege Q 2s (mycy +mCy)(t2 ~ t1) Qs 10140 Ans. () ty := 200-dege ty 40-degC n= Amol Cp = 29,1,— ule _ Pee nokdeg® By Bq. (2.23): Q = m-Cp:(t2-t) Qe=18.62kI Ans. 231 (a) t= 70-degr ty = 350-degF 3-mol BTU © 5 By Eq. (2.19): y inokdegF by Eq. (2.19): QenCy(2-u) Q= 200BTU Ans. Take account of the heat capacity of the vessel: my = 200-lbm, cy = 012+ Pi Tbyydege Qs (my-cy +Cy}-(t2=11) Qi 10920BTU Ans. (b) t) := 400-degF ty = 150-degF nt=4-mol BTU Cpi= 7. By Eq. (2.23): pes" noldege idea QO TU Ans. Qi nCp(ty- 11) o 22.33 Hy = 1322.6—— Ha == 1148, oe up ot Tb Tbs s a 8° Vy = 3.058-—— Vo= 7814 y= Bin Dy 10in ibm Ib En? yor 4 Ib rade a ndot = 3.463 « 10° M u2= n997 see 22 =u Fg, (2.328): Wy := Hp-H) +2 W, = -173.99 BTU 2 Ib Wot :=-Wemdot Wat 2:39.52 hp Ans. BTU BTU ft gm 234 Hp 3075 — Hy = 330 2520-5 — molwe:= 4482 : ae ge eee mmol a 3 f f Vp 9255. Vy = 0.28 Dps4in Dz Tein 1 pe 7 nin Da dot = 679.2632 br We = 5360. BEY ibmol Ws Q = 98.9 BU mohwt Ibm 5g ATU Qdot := mdor-Q —Qdol, = =67128——= Ans. 13taeLeg Eee kg n= 34.602mol 23.9.2 mol arom’ Ty om Vy = 83.14. = vy = 249422 molLK P mol Whence 9 Ws --P-2-V} Ans. T25 Ty = 13 Whence T= 3-Ty Cp = 29- ae AH := Cp(T2-T)) ia ‘Ans. Qi=0AH Ans. aU = St Ans. a SO took 2.37 Work exactly like Ex. 2.10: 2 steps, (a) & (b). A value is required for PV/T, namely R. J Ty i= 293.15-K R= 8.314 molK Py == 1000-kPa (@) Cool at const VItoP2 7p (b) Heat at const P2 to T2 2 Po T2=Trs Ta =29315K 1 ATy:=T2-Tag AT, =303.835K AT, Ta-T) AT, = -263.835K 14AH, = Cp-ATp, AH = 8.841 10° mol : aed AU, = Cy-AT, AU, = 5.484 10° — mol 3m RT) Vi = 2437x109 Vp vp = 0.028 mol Pp ‘mol AUg+Vi-(P2—P1) Hy = -7.677% 10° f 5 oat mol AH ~ P2(V2- Vi) Uy = 6.315% 10° mol Ans. 18Chapter 3 - Section A - Mathcad Solutions -fa \ 1a) aa peat (4p) «= 1{5] e\dT) p ew) At constant T, the 2nd equation can be written: Bea mS lecaP ese 4418107 Sbam! py = 101-p) P Pt ap = ROOD AP = 225.2bar Py $ 226.2-bar Ans. om? 34 b:=2700bar c= 0.125 Lbar Pp = $00-bar gm V2 Since Work = f PdV abit of algebra leads to vi Pa Wor =e] oar Pe Pi Alternatively, formal integration leads to Po+b Work := c-] Pz - Py — b-In Pi+b 35 K=aibP 0.1107 atm? V:= 1+? (assume const.) Combine Eqs. (1.3) and (3.3) for const. T: Pa : Work = vf (e+ bP) PAP Work =16,65atm-° Ans. Spy 16eee kJ 3.6 L210" S.doge™' Cp = 0.84 Mis Sk 2 P eae 8 Yee Pix Lb ty = Odeg ty = 20-degC eolim w= bebar = = 1 1590 kg 1 Bt 2 Bt ‘With beta independent of T and with P=constant, dv p= Bar Vo i= Vi-exp| B-(t2-t1)] Vigil =MAV AV pat = 7.638% 107%? Ans, Work := -P-AVioigi (Const. P) Work = 7.638 joule Ans. QeMCp(p-t) Obit Ans. AHiotal “= Q Ans. AU otal != Q+ Work Ans. 38 pyre sbar Pps debar T= 600K Cpe ZR (a) Constant V: weo and = AUS Q= Cy-AT AT = -525K AU := Cy-AT Qand (b) Constant T: Po) Work := R-Ty In} =| Puy (©) Adiabatic: Q=0 and AUS WS CyATTz = 331.227K AH = Cp-AT Wand a= 73215 Ans. ee mol Vi; = 4.988% 19 3 mol Step 41: Adiabatic J AUgy = 4.597 x 10° AUA ‘mol Aig = OP(T-T) any, = 6.436% 10° mol J J Qa = 0 Qa1 = 0— mol mol Way := AUgy RT Pp == Sbar Vo= P2 Step 12: Isothermal AU, 18J mol AK » AH = Pe 3 J Qi -R-TrInj =| Qi = 6.006% 10° — Pi mol 6.006 10° mol Wiz -Qi2 Wi2= P3-V: X03 15 = 400K P3:=2bar V3 = V2 Ts R Cy(T}-T2) AUg3 = 4.157% 103 Step 23: Isochoric U3 mol Allg = Cp(T3—T2) AHg3 = ~5.82x 10° mol J Qx3 = Cy(T3-T) — Qx3 = 4.157 10° — mol Was = 0 Wo = 0-4 mol mol 3 P4 = 2bar T4 = 378.831K V4 = 0.016 mol ‘Step 34: Isobaric AU3g = Cv(T4- 13) AU34 = 439. on mol J Cp(T4-T3) AH3g = -615.996— mol Qs4 = 615.996 mol W54 = 175.9994, mol 3.10 For all parts of this problem: T2=T, and AUS AH=0 Also Q = -Work and all that remains is to calculate Work, Symbol V is used for total volume in this problem, 19Work = 2982] Ans. (b) Step 1: adiabatic compression to P, L Pt vew(e] (intermediate V) Vj = 2.702m? 2 Wy = 3063kI a Step 2: cool at eonst P, to Vz Ww P2-(V2- Vi) W = 2042k) Work := Wi + Wo Work = $106k] Ans. (©) Step 1: adiabatic compression to V2 (intermediate P) P= 62.898 bar Wi = 7635k) Step 2: No work. Work :=W, Work ='7635K. Ans. (@) Step 1: heat at const V, toP) Wy Step 2: cool at const P, to Vy W2 := -P2-(V2- V1) Work := W2 ‘3200k7 Ans. 20(©) Step 1: cool at const P, to V2 Wy = -P1-(V2- Vi) W, = 1100k3 Step 2: heat at const V; to P; W220 Work := Wy ‘Wor itdoia A" 3.17 (a) No work is done; no heat is transferred. AU'S AT=O T= Ty = 100-degC —_Not reversible (b) The gas is returned to its initial state by isothermal compression. (Vv Work = n-R-Tn 2) but MRT = Po-V> ae Vian? Vo Work := P2:V>_In Work = 878:9K1 Ans. re sis 3.18 (a) Py := 100-kPa Pp = 500-kPa Ty = 303.15-K 5 Cp cy=2 ves bead Adiabatic compression from point 1 to point 2: KE Qin = 0 AU,2 = Wi2 = Cv-aTi2 mol AU,2 = Cy{T2-T1) AH)2 = Cp(T2-Ti) Wig AU)2 ak AHy2 = 5.13 eT Same) 24Cool at P, from point 2 to point 3: = AHD3 AHQ3 Ans. kK Qag = 5.15 Ans. mol Isothermal expansion from point 3 to point 1: AU) = AH) = 0 FORTHE CYCLE: AU = AH = 0 Q= Qin + Q3+Q51 Work := Wy2 + W23 + W3i Qaa oo Work vo04 2 SSS Snel 5 ‘mol (b) [each step that is 80% efficient accomplishes the same change of state, all property values are unchanged, and the delta H and delta U values are the same as in part (a). However, the Q and W values change, 2 Step 12: Wiz = — P 12 08 Qu2 = AU 2 ~ Wir Ww: Step 23: Wo3 52 0.8 2Qg3 == AUp3 ~ Wo3 Step 31: W3) = W31-08 Qs = -W31 FOR THE CYCLE: Q = Qi2+Qz3+Q31 pene 192 — mol 3.19 Here, V represents total volume, vi (a) Isothermal: y= Ppt V2 eT z= 600K P= 200kPa = Ans. v es Work = PV; ma ‘SOR) Ans. Wa vi Po V2 b) Adiabatic: Pep tee Tye? (0) Adiabati: 2 @) eT BY P25 69.65kPa Ans. 994.4k) Ans, 23(c) Restrained adiabatic: Work = AU = —Pexr AV. Pext = 100-kPa Work := —Pexe(V2- Vi) Work'= 400K) Ans. PL AU = nCy-AT Tas, AS: Ans. P2'= 147.57KRa = Ans. 3.20 T3 t= 323.15-K Wi = RT) Ing) 25025 mol Step 23: Qa3 = AU23 Q33 = 2.079 AU; = -2. 79 mol mol Process: Work = Wia + Wa3 Q= Qi2+Q3 24AH == AH}2+AFy3 AU = AU 2 + AUa3 321 By Rq. 2.328), unitemass basis: motwt = 28-2 ane Lau? =o mmol 2 But AH = Cp-AT Whence AT = 322 3 = 403.15-K AU = 20792 Ans, mol Each part consists of two steps, 12 & 23. Work := W23 wok 67608. Ans. = = mob 2Q:= AU — Work Qe e463 Ans. = mol Tre Ts AU)? = Cy(t2-T) cp(t2-N) Qu2 = AH ky 2 = -Q12 W)2 = -0.831— Wi2 = AU}2- Qua 12 sy P3 kJ W 3 := R-To-Inj — W323 = 7.718 — 93 := RT (2) 23 Ral Work := Wi2+ Was Work = 6.986 Ans. EE pene es eA i Q = AU - Work Q=-4808— = Ans. Pinal os © bet P= P3 Ty (2) Pi AHp3 = Cp-(T3-T2) 03 := AH3 AUp3 = Cy-(T3 - Ta) Work := Wi2 + W23 Woks Ans. ‘mol Q = AU - Work Q=-2.894 For the second set of heat-eapacity values, answers are (kJ/mol): AU = 1.247 AU = 2.079 (a) Work = 6.762 Qe 26 51S3.23 3.24 (b) Work = 6.886 = Q= ~5.639 © Work = 4.972 Q= -3.725 Ty = 303.15-K Toi=Th T3 = 393.15-K Py = I-bar P3 := 12-bar Forthe process: AU:= Cy(T3-T)) AH = Cp(T3-T1) av= isnt mol Step 12: P AS a cep 12: Pa i= Pye eect KI Wi2 = 5,608-— mol Step 23: For the process: Q= Qin+ Qs Ans. Work = W3 = -P2(V3~ V2) = -R.(T3 -T2) But T3=T) So. Work = R-(T2-T;) >) Also WERT) “(| ‘Therefore 1 (p\ 12-T In} ae sf 50-K Py = 4-bar PB) OT 27328 3.26 ™2-T aa P Pre == | PS227obe Ans. 1 Va t= 256-em> Define: ae Py Assume ideal gas; let V represent total volume: P)-Vp= P2(Va+Vp) From this one finds: ap__-Va VatteD 4 Vp Vp 37503cm? Ams. Py Vat+VB r T)=300K Pj Cy =Cp-R ‘The process occurring in section B is a reversible, adiabatic compression. Let P(fina) = P2 Ta(final) = T Tp(final) = Ty nA = ng, Since the total volume is constant, 2naRT1 _ nyR(TA+Tp) u = = o (a) Pp := 1.28-atm Q) Pr Ta c= 2-Ty Ae Q=na(AUa + Ug) Define = 2 q=Cy(Ta+Ta-271) A Ta = 43025K Ans,(b) (©) (@) Combine Eqs. (1) & (2) to eliminate the ratio of pressures: Ty 13 425.K (guess) Tp := 300-K pial (Ta+Tn) t Give Tp=Ty| The me tye) ay Ans. Ta+Tp Poss P @ Ans. cy-(Ta+T3-2T1) Ans. Tp = 325-K By Eq. (2), Py =1.823aim Ans. @ Ans. q=Cy{T,+Tp- 2-71) Ans. Eliminate Ta +T_ from Eqs. (1) & @): PRETO Ans. Q) Tg=319.06K Ans. a) 49528K Ans.373.15-K Pry RT Given Bl+ Guess: ; c : Given => V2 := Find(V2) 3 Va’ Eliminate P from Eq, (1.3) by the virial equation: V2, : Bl c\ly eter (sae Work = 12.6. v Sere mol VL (b) Eliminate dV from Eq. (1.3) by the virial equation in P: ») oP (eta Pe AVERT) zc}? Wi-RT ? Pr Pr 30 em’ vy = 30780 mol Ans.Note: The answers to (a) & (b) differ because the relations between the two sets of parameters are exact only for infinite series. 332 Te = 282.3K THDBISK Tye Ty = 1.056 Pe P, = 0.238 Pe (guess) 3 va ®t v= 2066S mol Given PVC RT “agem V := Find(V) v= 1919 Zz Ans. thol (b) By := 0.083 - oe Bo = 0.304 * By = 039-217 By = 2.262% 10> 742 Pr ee Z=1+(Bo +o: Bie £20932 (©) For Redlich/Kwong EOS: 0 Qe 0.08664 Table 3.1 Table 3.1 a(T,) = Eq. 3.51) ET2-P, B(Tr.P,) = a r Eq. (3.50) Calculate Z Guess: Given Eq. 3.49) Z-B(T,.Pr) + Blt e) a0) PP) ESE, Ri (ererBl PD) gery Find(Z) Z = 0.928 v ee 9165 Ans. (@_ For SRK EOS: e=0 2 = 0.08664 ¥ = 0.42748 Table 3.1 r ne | 2 ( 3] ‘Table 3.1 (Tyo) =[1 + (0.480 + 1.5740 - 0.17607) UT) ¥-0(Tr0) : a(t) eal) Eq.@51) — B(Tr,Ps) Eq. (3.50) Calculate Z Guess: 09 Given Eq. (3.49) Z= 1+B(Te,P,) —a(Tr)-B(tr Ps) ETN aR Zi=Find(Z) Z = 0.928 a Ans. (©) For Peng/Robinson EOS: wi o 1-¥2 Q:=007779 = 045724 Table 3.1 iN a(Tr,o) [ 1+ (037464 + 1.542260 - 0.269020") ( 11,7) Table 3.1 2aT) - tai) Eq. 3.51) B(T,,P,) = e “ Eq. (3.50) Calculate Z, Guess: = 0.9 Given Eq. (3.49) Z~B(T,.P,) Z = 1+B(TrPy) ~ a(Te) B(Tr.Ps) Grealt.F)(e+05R) Zi=Find(Z) 7 = 0.92 333 Ty 3053K 9 T= 323.15K Pos 48.72bar PH 15-bar © = 0.100 cm? om? @ c= 9650. ve 179 a ‘mol Given PV. T V = Find(V) Z ad Z=0807 Ans. 0422 (b) Bo = 0.083 - S22 By = -0.302 By = 3.517x 1077 33Pr : : 1+(Bo+oBi= 250912 V ERT y 2 634 ans. Tr P % H mol (©) For Redlich/Kwong EOS: o Q = 0.08664 WY := 0.42748 Table 3.1 W-a(Ty, a(T) = 7, Table 3.1 a(t) walt) Eq. 651) OT, B(Tr.P:) Eq. 8.50) Calculate Z Guess: Z:=09 Given Eq. (3.49) Z-B(TrsPe) Z=1+B(Tr.Pr) ~ a8) B (Pate bes TP) Ze=Find(Z) Z = 0.906 at (@) For SRK EOS: ol =0 = 008664 Y= 0.42748 Table 3.1 r Pe 2 5 Table 3.1 14 (0.48041.5740 - 0.1760")-(1—1,? v-a(Tr,o) 2 (T,) = Eg. 8.51 TesPy) = Eq. 3.50) a(t aie 851) B(TrePe) = 4. (3.50) Caleulate Z. Guess 20.9 Given Eq. (3.49) Z-B(TrPr) i 1+ (tr.R) alt) B(te PT BUTr.Pr)}(Z + o-Ps) 34Les ind(Z) Z = 0.907 Ve (©) For Peng/Robinson EOS: 142 o 1=$2 Q:=0.07779 = Y= 0.45724 Table 3.1 2 1 a(Tr.a) = [ + (0.37464 + 1.542260 - ol - Jl oa q(t) = ¥a(T.0) Bs) B(T,,P)) = ae Eq. (3.50) OT : Tr Calculate Z Guess: Z=09 Given Eq. (3.49) Z~B(Tr.Pr) Z= 1+B(Tr.P,) —4(T;)-B(Tr.Pal Find(Z) Z = 0.896 334 Te = 318.7K T= 348.15-K T, = 1.092 1S-bar =— Pr = 0,399 Pe (guess) 3 vekT ye i939 mol Given 35Z=0893. Ans. V = Find(V) 0.422 o 083 - Bo = -0.283 Tr 0.172 139 - —— By = 0.02 42 Tr Pr Zi 1+(Bo+oBi} = Z= 0899 (©) For Redlich/Kwong EOS: 2 = 0.08664 W = 0.40748 Table 3.1 w-a(Ty) Table 3.1 1)! By. B50 a(t) a q. 3.51) Eq. 650) Calculate Z Guess: Z:= 0.9 Given Eq. (3.49) Z:=Find(Z) Z = 0.888 @) For SRK E os Q2:= 0.08664 = W = 0.42748 Table 3.1 1 36Table 3.1 of ae W-a(T;,@) OT; a(t Eq. (3.51) B(tr,P,) Eq. (3.50) Calculate Z Guess: Z=09 Given Eq. (3.49) 2 148) a0) C8 ae Z=Find(Z) Z = 0.895 (©) For Peng/Robinson EOS: ozity2¢ -¥2 007779 -W = 0.45724 Table 3.1 a(Tr,@) = [ 1+ (0.37464 + 1.542260 ~ 0 ct ata v-a(Tro T,) » ~~ Eq. (3.51 TrP, eC) Saat 4-51) B(Tr.P, Eq. (3.50) Calculate Z Guess: Zi=09 Given Eq. 3.49) Z= 1+B(Tr.P.) ~a(T,)-B (TPs) Ea Ea Find(Z) ZRT P 0.882 v 37335 T= $23.15K 1800-kPa, Tr = 0.808 Py = 0.082 By = -0.281 Z= 0.939 (©) Table F.2: molwt := 18,0155 mol or 337 Z=0931 Ans. = 124.99-.molwt gm . HS ea Y= 22525 Ans. eS nol cm? D=5000-— — n:= mol mol?Ts 273.15-K Given ae lte tse £(P,V) = [ 4 1 0858 O86 2906 a@86 0858 [oes Pi=[- a0) bar oars] asia aaa 720) o782 0765 0822 140) 0.757) 0718 0.5+0.1781 10 O74 aati 05-0281) 180] O78 624 D503 ~_ 200) 0735 losr7 | 050.4161] O74 388 0540 468i Note that values of Z from Eq, (3.38) are not physically meaningful for pressures above 100 bar. 39BP; Zij= 1+ Eq. (3.37) 23; 0 7 Be Ze 2 = 20 7 7 1 40 0583] 0858 O86 60 0.306] 0.506; 0885 89 D867 0.888) 088 yoo] bar foar9| 0812 0749 120 0764 id oa 140 O7er a 050178 160) ‘O74 O87 05+028i1 120) 0733 0628 O5+O.366i 200 0735) 577 DE+OaT6I ‘o743| oss 0590. 468) Note that values of Z from Eq, (3.38) are not physically meaningful for pressures above 100 bar. Eq. 8.38)oe oO 50 100 150 200 Pi-bar ! 3.38 (a) Propane: Ty = 369.8-K 42.48-bar @ = 0.152, T= 313.15K 13.71-bar T, = 0.847 Pt 0323 Pe Q = 0.08664 WY = 0.42748 Table 3.1 0s WaT, (Tr) = Tr Table 3.1 (Te) = Eq. (3.51) OT; O-P, B(Ty.Pr) = Eq. (3.50) Calculate Z for liquid by Eq, (3.53) Guess: Z:= 0.01 40Given Z= B(T,.P,) +(Z+6-B(T,.P,)}-(Z vo} BE) Z = Find(Z) Z = 0.057 Vv: Ans, Calculate Z for vapor by Eq. (3.49) Guess: Given Z-B(Tr.P,) Z(Z+B(Tr.Px)) Z= 14B(Ty,P,) —a(T,)-B(T,,P2) Z:=Find(Z) — Z = 0.789 Racket equation for saturated liquid: Ans. For saturated vapor, use Pitzer correlation: 0.422 Bo = 0.083 - = Bo = -0.468 By = 0,139 2172 7 RT Te Vv == +R-(Bo +o Bi) 5 Ans, aParts (b) through (t) are worked exactly the same way. All results are summarized as follows. Volume units are cu.cm./mote. RIK, Lig, R/K, Vap. Rackett Pitzer (a) 108.1 1499.2 94.2 1537.8 (b) 45 1174.7 98.1 1228.7 (o) 122.7 920.3 1028 9904 (@) 133.6 717.0 109.0 805.0 (@) 148.9 1516.2 1254 1877.0 (H 158.3 1216.1 130.7 1296.8 (g) 170.4 971.1 1374 1074.0 (i) 187. 768.8 146.4 896.0 (i) 153.2 1330.3. 133.9 1405.7 @ 164.2 1057.9 140.3 1154.3 (k) 179.1 8353 148.6 955.4 @ 214 645.8 160.6 795.8 (m) 61.7 12525 535 1276.9 (n) 64.1 1006.9 55.1 1038.5 (0) 66.9 814.5 57.0 853.4 (p) 703 661.2 59.1 707.8 (q@) 644 13187 54.6 1319.0 (0) 674 1046.6 $6.3 1057.2 (8) 70.8 835.6 58.3 8564 () 748 669.5 60.6 700.5 23.39 (a) Propane Ty = 369.8 Po = 42.48-bar T = 313,15K P, = 0.323 o-l & Q. := 0.08664 WY = 0.42748 ’) a(t.) [| 1-+(0.480 + 1.5740 ~ 0.1760 W-a(Tr.0) i OP, a a(T;) == ¥-a(tro) Eq. (3.51) B(Ty,Pr) = Eq. (3.50) OT; Calculate Z for liquid by Eq. (3.53) Guess: Z=001 Given Z= p(ty,P,) +(2+68(te.P.)}{2 +08 (Tr.P9) aha (Ts) B(Te-Pr) ) Z=Find(Z) = Z= 0.085 -V sS Ans. Calculate Z for vapor by Eq. (3.49) Guess: Z=09 Given Z-B(TrP,) Z= 1+B(T:.Ps) —a(T): 8(1P) eat Zs eT) ind(Z) Z = 0.78 vetParts (b) through (f) are worked exactly the same way. All results are summarized as follows. Volume units are cu.cm./mole. SRK, Lig. SRK, Vap. Rackett Pitzer (a) 104.7 1480.7 94,2 1537.8 (>) 110.6 1157.8 98.1 1228.7 (c) 118.2 904.9 102.8 990.4 (@) 1285 7033 109.0 805.0 (e) 142.1 1487.1. 128.4 1577.0 () 150.7 1189.9 130.7 1296.8 (g) 1618 9478 1374 1074.0 (b) 1771 7478 146.4 896.0 @ 146.7 1305.3 133.9 1405.7 @ 1569 1035.2 140.3 11543 (k) 170.7 815.1 148.6 955.4 (@ 191.3 6285 160.6 795.8 (m) 612 1248.9 535 1276.9 (a) 63.5 1003.2 55.1 1038.5 (0) 663 810.7 57.0 853.4 (p) 69.5 6574 59.1 7078 (@ 614 1296.8 54.6 1319.0 () 63.9 1026.3 56.3 1087.2 () 66.9 817.0 58.3 856.4 (705 652.5 60.6 700.5T= (40+273.15)K Ty = 0.847 Pe P, = 0.323 From Table 3.1 for PR: 1 He r + (0.37464 + 1.542260 - 0.269920") ( - ll a(T,,0) o=lty2 1-J2 Q:=0.07779 Y= 0.45724 a(t) = valtee) £4.51) p(T?) au Eq, (3.50) Calculate Z for liquid by Eq. (3.53) Guess: = 0.01 Given Z= (TP) +(Z+8-B(T.Py))-(Z eatery 1+B(T;,P:)-Z a(t) 8(Tr.P) ) Z=FindZ) = Z= 0.089 Vv at Ans. Calculate 2, for vapor by Eq.@.49) Guess Z = 0.6 Given Zz B(Te.Pe) Z+e-B(Tr,P,)}-(Z+o-B(Tr,P,)) 1+ B(T,,P,) ~4(T;)-B(Te,P,): a Tee Lis Find(Z)— Z = 0,766 call 454.55" Ans, inol. 45Parts (b) through (t) are worked exactly the same way. All results are summarized as follows. Volume units are cu.cm./mole. PR, Lig. PR, Vap. Rackett Pitzer (a) 922 1454.5 94.2 1537.8 (b) 97.6 1131.8 98.1 1228.7 (©) 1044 879.2 102.8 990.4 (@) 113.7 678.1 109.0 805.0 (© 125.2 1453.5 1254 1577.0 (132.9 1156.3 130.7 1296.8 (g) 143.0 915.0 137.4 1074.0 (h) 157.1 715.8 146.4 896.0 @ 1294 1271.9 133.9 1405.7 @ 1386 1002.3 140.3 1154.3 (kK) ISL2 782.8 148.6 955.4 @ 1702 597.3 160.6 795.8 (m) 54.0 1233.0 53.5 1276.9 (n) 56.0 987.3 55.1 1038.5 (0) 584 794.8 57,0 853.4 () 614 641.6 59.1 707.8 (a) 54.1 1280.2 54.6 1319.0 (©) 563 1009.7 56.3 1057.2 () 589 800.5 583 856.4 () 62.2 636.1 60.6 700.5 463.41 (a)Forethylene, — molwt : 28.054 oe To = 282.3-K mo @ 2= 0.087 T = 328.15-K ‘T, = 1.162 From Tables E.l & E.2: Zo = 0.838 Zg+@Z, 2 = 0.841 i8-ke molwt (b) T= 323.15-K 115-bar r P hres Ty = 1.145 Pes Py = 2.282 Te Pe From Tables E.3 & E.d: Zp = 0.482 126 P-Viotal Z=%+oZ Z= 0493 A 2171 mol ZRT mass := nemolwt mass =60,898kg" Ans. 3.42 Assume validity of Eq. 3.37). 3 V, = 23000 7 , ‘mol Prev RT 3 om? Z; = 0.922 B= —(Z)-1 B = -1.942x 10° — =a 2 p 1) = With this B, recalculate at P, a70.422 Bo := 0.083 — —s Bo = -0.146 Tr Bi ore By = 0.104 a Ty Te + (Bo +o-B)) R— Ans. For an ideal gas: 34 T= 320K P v tek Te 1028s? 3 “i mi Vig = Vere | Viig = 96.769 mol 08, Vionk = 035:m? mig i= tg = 49 7'SB4R Ans. ig mmolwt 0422p = 0.449 16 483 em! Veap = 1318x100 mp = 2341kg Ans. tr T, = 0.701 P, = 0.064 T Te P Pris Po molwt := 58.1232 mol V = 9.469 10° mol Ans. 3.46 (a) T 1, = Ty = 1.091 © P Prem e Py = 2.874 motwt := 30,0722. mol 0.100From tables .3 & E.4: Zo == 0.463 Z, = 0.037 Ze Loro% Z=0A459 oer = 90.87 mol Viotal . methane = —o™ mahane = 49.64Kg Ans. ‘molwt Vv () ye total P = 20000-kPa PVE ZRTS ZR TpTe 40-kg o Ts whee onl a= 29.5480! Zz Rte re Whence, at Pee P, Pe y 4.105 Tables E.3 & E.4 are two relations the same variables which must be satisfied at the given reduced pressure. The intersection of these two relations can be found by one means or another to occur at about: Ty = 1.283 and Whence T= Ty-Te T=391.7K or {18,5:degC Ans.Whence P= 4.6752 at Tyee 2 Tr = 1.056 Te This equation giving P, as a function of Z and Eq. (3.54) in conjunction with Tables E.3 & E.4 are two relations in the same variables which must be satisfied at the given reduced temperature. The intersection of these two relations can be found by one means or another to occur at about: Py= 1582 and Z:=0338 Pos PyPy Ans. ae 3.48 mater = 15-ke Veota V = 26.667 gm Interpolate in Table F.2 at 400 degC to find: P= 9930:kPa Ans. 3.49 Ty 2s 298.15-K ‘Tr = 0.977 Py := 2200-KPa Pri = 0.452 Veotat = 0.35:m° From Tables E.1 & F.2: Z=Loto2, Ty = 493.15-K Tr = 1.615 Assume Eq. (3.37) applies at the final state. 0.422 Bo := 0.083 - ——— Bo = -0.113 Ty! 12 B= 0139-22 B= 0.116 42 Tr 61303.15-K Te i= 304.2-K T= oe Veotat = 0.5-m? Pe 73.83:bar a := 0,224 Bo ~ 0.083 - 2422 Bo = -0.341 16 Tr 172 By = 0.139 — om By = —0.036 Ans. T, = 0.613 Po := 34.0:bar Pr = 0.03 i 3a 3 molwit == 28.0145 Vig = 342-62 Bo = -0.842 62T, Z = 0.987 Rapor Aiyapor = 5.718 10” mol ZRTp ee Final conditions: anol 2-Viig iota “= T-mol + Myapor — i Dtotal Tre Ty = 2.363 359.2bar Use Redlich/Kwong at so high a P. Q = 0.08664 W:=042748 a(T) = Th a(T;) = 0.651 Wea(ty)-R-Te QRTe —_—_———._ (3.42) Sess (3.43) Pe © o.o01m> been oe) Peat 26.737 mol mol Ka A (3.44) = dsoli bar Ans. “VIB Vive) For isobutane: Te = 408.1-K, 3.52 Py = 4-bar 6.48-bar Po ‘Tp = 415KFrom Fig. (3.17): Pry = 245 ‘The final T > Tc, and Fig. 3.17 probably shoutd not be used. One can easily show that _ Pe with Z from Rq. @.54) and Pr ORT ‘Tables E.3 and E.4. Thus 0.181 Z=032 Eq. 3.68): Vo = Vp et Ans. Pr 3.53 For n-pentane: Po i= 33.7-bar py = 0.63-22 em? Ty = 291.15K AIB.ISK Pp t= 120-bar P2 Pa = euuiPe Ty = 0.62 Pri = 0.03 Trg = 0.88 Pra = 3.561 From Fig. 3.17): py = 2.69 i P12 By Eq. 3.65), py = pp 2 Prt Ans.3.84 Forethanol: Ty := 513.9-K = 6148-bar P= 200-bar 3 Ve = 167. ‘mol From Fig. 3.17: Pr Pp Ve imolwt 3.55 For ammonia: Te = 405.7-K T= 293.15K Pe r= 112.8-bar 857-kPa em? Ve = 2.5 Ze = 0.242 mol 0.2887) 1-1) Eq. (3.63): Viiquia = Ve all ) | Bo = 0.627 By = 0.534 x Viiguia = 27-11 ed mol Pre Pp = 3.253 ® = 3.25: Ans. Tet Tr= 0.723 Te P, = 0.076 33 om Vyapor = 2616 : mol Ans. Alternatively, use Tables B.1 & E.2 to get thevapor volume: Ze 0.929 Zj = -0.071 ZLot@Z, Z=0911 Vv, _2ZRT fapor = AV i= apor~ Viguid 10 gal. of gasoline is equivalent to 1400 cu ft. of methane at 60 degF and 1 atm, Assume at these conditions that methane is an ideal gas: f-atm Ibmolrankine R = 0.7302 519.67-rankine P= atm Vv Ve= 1400-8? - nso n= 3.6891bmol RT For methane at 3000 psi and 60 deg: Te: 190.6-1.8-rankine T= 519.67-rankine T, = 1515 Pe = 45.99-bar 3000-psi P, = 4.498 0.012 From Tables E.3 & E.4: Zo = 0819 Zy = 0234 ZL ko+o2 Z = 0.822 56Ans. 3.39.T Calculate the effective critical parameters for hydrogen by equations (3.55) and (3.56) 43.6 ee Te = 30.435K 21.8K L+ 2.016T Pos — 5 __sbar P. = 10.922bar 44.2K 1+ 2.016T P, = 0.294 guess of volume: mol Use the generalized Pitzer correlation 0.422 Bo := 0.083 - Tr Bp = 0.495 By := 0.139 Z= 0823 Ans. Experimental: 2 = 0.08664 Y= 0.42748 ‘Table 3.1 W-a(T) Ta Table 3.1 a(t;) = Eq. G51) 87QP, B(Te,Pr) 2= a Bq. 3.50) Calculate Z, Guess: Zi 09 Given Eq. (3.49) Z(2 + B(Tr.Pe)) Ans. Experimental: Z= 1+B(TesPr) ~a(Ts}B(Tr.Pe} 1.7787 0.012 Te = 190.6K Po := 45.99bar Atstandard condition: T= [to = sy + oe T = 288.706K Pitzer correlations: P:= latm ral T= 1515 es P, = 0.022 i Pe a 7 Bo := 0.083 - 2422 2 139-9172 By = 0.109 1 1 Pr Py Zo 1+ Boe %q = 0.998 1 = Bre 24 = 0.00158 ZRT m Z=Zo+o21 Z=09% Vps a Vy = 0.024 P mol an 5 | 5 (a) At actual condition: T =| (50- 325 + ila P := 300psi Pitzer correlations: eee Tel T, = 1486 P, = 0.45 Te Bo = -0.141 580.172 By = 0.139--— By = 0.106 Tr Pr Pr Zo = 1+Bo Tr Zo = 0.957 = Bee Zy = 0,0322 3 Z = 0.958 V2 = 0.00109 7 mol V2 ete a2 915 10°. Ans. 24 Vi an day © D = 22.624in A= 0.259m" wis Ans. ole3.62 0.012 0.087 O41 0.140 0.152 0.181 0.187 0.19 0.191 0.194 0.196 02 0.205 021 021 0.212 0.218 0.23 0.235 0.252 0.262 0.28 0.297 0.301 0.302 0.303 0.31 0.322 0.326 0.286) 0.281 0.279 0.289 0.276. 0.282 0.271 0.267 0.277 0.275 0.273 0.274 0.273 0.273 021 0.272 0.275 0272 0.269 027 0.264 0.265 0.256 0,266 0.266 0.263 0.263 0.26 0.261 Use the first 29 components in Table B.1 sorted so that «o values are in ascending order. This is required for the Mathead slope and intercept functions, tope(w.Zc):= (-0.091) intercept(«,Zc) = (0.291) R i= cor(w,Zc) = (0.878) R*= 0.771Chapter 4 - Section A - Mathcad Solutions 4.1 (a) Ty = 473.15-K T= 1373.15-K n= 10-mol ForS0%: A= 5699 B=0801107 C= icpHi(473.15,1373.15,5.699, 0.801103, ICPH := 5.654-10°.K AH:=RICPH Q:= AH GaN Ans. (b) To := 523.15-K T }473.15-K ‘= 12-mol For propane: A 1213 B= 28785107? C= -8.824-10"° rep (523.15, 1473.15, 1.213, 28.785-107 =8.824-107 °,0.0) = 1.947-10° ICPH := 1.947-10%K AH := R-ICPHL Q:=n-AH QS 194K 107K Ans. 42 (a) To = 473.15-K n= 10-mol — Q:= 800-K 3 6 Forethylens Ass 1424 pe AAROEIOT™ 4.39210" K ev 1 = 2 (guess) Given Bo 2(2 C133 Qe {| A-t06 a1) Bape? | +S (2- | = Find(t) = 2.905 T:=tTo 13745K Ans, (b) Tg := 533.15-K n= 15-mol Qs 2500-KI 31.630-10°* K For I-butene: A := 967 iB c 613 (guess) Given Qen {| a-to6-0 +E ne -]-Snie ee ) Find(x) 7 = 2.652 3.8K Ans. (©) To == 500-degF n= 40-lbmol Q:=10°BTU Values converted to SI units To = 533.15K 1.814x 10'mol Q = 1.055 x 10°ks 14.394:10- 4.392.107 K KR For ethylene: A 424 c= 2 (guess) Given t= Find(t) 1 = 2.256 T:=tTo Convert given values to SI units Vv = 7.079m9 = (T— 32degF) +273.15K To = (To ~ 32degh) +273.15K T = 1187.37K To = 323.15K 66.985 mol A= 3355 B= 057510°° 0.0 =D=-0.016-10° 1ePh{323.15,773.15,3355,0.575-10" 3,0.0,-0.016-108) = 1688.702 @ICPH := 1648.702-K AH:=R-ICPH Q 465% 1 BTU Ans. 4.4 molwt := 1001-22 To =.323.15-K 153.15-K mol 0000: z= 20000-kg n= 9.99 10'mol mohwt For CaCO3: Ais 12572 B=263710° =D = -3.120-10° repHi(323.15, 1153.15, 12.572,2.637-107°,0.0,-3.120-10°) = 113554 ICPH := 11355.4K AH ss -ICPH Qs mal 4314% 10K) Ans. 4.7, Let step 12 represent the initial reversible adiabatic expansion, and step 23 the final constant-volume heating. Ty = 298.15K T3 = 298.15-K Py = 121.3-kPa P. Pp = 101.3-kPa P3 == 104.0-kPa T2 = T3 = 3 cp = 30.bule (ques) T) = 290.41K molK Ans, 33.70 309.2 30.25 341.9 48.98 | 353.2 |K 41.06 es 40.73 353.9.a aedenaceese ey AH isthe valueat — 4Hexp is the given 25 degC. value at thenormal —q,, := C7315+29K yp, _ Te boiling point, Te 366.3 357.2 0.635 0.658, 366.1 336.7 0.587 0.674 AH = | 433.3 Ss AHexp = | 393.9 b> tm=| 053] te =| 0.028 4123 363.2 0.504 0.649 392.5 358.2, 0.539, 0.639 (a) By Eq. (4.13) eee AH, ~ AHexp PCE = | ———*. 100% This is the % error AHexp (b)4.10. The In P vs. 1/T relation over a short range is very nearly linear. Our procedure is therefore to take 5 points, including the point at the temperature of interest and two points on either side, and to do a linear least-squares fit, from which the required deriva Eq, (4.11) can be found, Temperatures are in rankines, pressures in psia, volumes in cu ft/bm, and enthalpies in Btu/lbm. The molar mass M of tetrafluoroethane is 102.04, The factor 5.4039 converts energy units from (psia)(eu ft) to Btu. (a) T := 459.67+5 AV := 1.934~0.012 +e 18.787 7 21.162 0 1 Data: P= | 23.7 = =— y= h(P} ais P= [23767] t=] S| x= oe = h(n) 26617 10 29.726 Is slope = slope(x,y) slope = ~4952 (-P). 3 aPaT =: slopdPdT = 0.545 _ Tay-dPaT “3.4039 AH = 90,078" Ans. ‘The remaining parts of the problem are worked in exaetly the same way. All answers are as follows, with the Table 9.1 value in (): (a) AH = 90.078 (90.111) (b) AH = 85.817 (85.834) (©) AH = 81.034 (81.136) (@) AH = 76.007 (75.902) (©) AH = 69.863 (69,969) 654a 119377 3364 34.72 334.3 32.082 |-SE ty 1=/ 5126 |K Py =| 80.97 bar Ty =| 397.9 | 153.822 356.4 45.60. 349.8 AlTis the valueat “Hep is the given pony O deg value at the normal Typ = 223:15K boiling point. Te 2109 246.9 0.509 0.623 J AH =| 118952 Atle :=| 10995 |. ty =| 0533 | Ti =| 0.659 gm 2178 1942 0491 0.629 (a) By Eq. (4.13) AHexy — 100% This is the % error ‘AHexp(2,732,016 J (g) -105,140 J (hy -38,292 ( 164,647 (i) -48,969 J (ky -149,728 () -1,036,036 J (m) 207,436 J (s) -492, 640.5 (8) 109,780 J (u) 235, (v) -132, (ow) -1,81 030 J 038 J 07,968 J (x) 42,7205 (y) 117, @ 175, 4403 305 J 4.22 The solution to each of these problems is exactly like that shown in Example 4.6. In each case the value of AH?399 is calculated in Problem 4.21. Results are given in the following table. In the first column the letter in () indicates the part of problem 4.21 appropriate to the AH% 9, value, TK | AA | 1038 IDCPHIS @| sis | 587 | 4187 i @ [773.15 | __ 1.861 | 3.394 [923.15 | 6.018 | 9.779 “3,716,381 @ [973.as [981i | 9.248 189,876 @_{583.15 | -9.523 | 11.355 59,918 | @ [683.15 | -0.481 | 0.004 ~1,038,452 in) | 850.00 4575 |_-2.323 - () | 1350.00| -0.145 | 0.159 (o) [1073.15 | -1.011 (e) | 723.15 | 1.424 (Q_} 733.15 4.016 | 117,204 | fu) | 750.00 7.297 247,202 (@) | 900.00_|__2.418 =128,504 (w) | 673.15_| "2.586 “1,803,784 (x) | 648.15 0.060 22 Coy [1083.13 [4.175 76ition of a combination of Eqs. (4.18) & (4.19) with evaluated parameters. In each case the value of AH(9g is calculated in Pb. 4.21, The values of AA, AB, AC and AD are given for all cases except for Parts (e), (g), (h), (k), and (2) in the preceding table. Those mi follows: [PartNo.[ AA [103.ap [1064c | 10-S.ap | © -7.425| 20.778 | 0.000 3.737 @ 3.629 | 8.816 | 4.904] 0.114 (h) -9.987| 20.061 | -9.296 1.178 ®) 1.704} -3.997 | 1.573] 0.234 @ -3.858| -1.042] 0.180 [ 0.919] 3 150.1082 day 424g atm (60-32) Sk +27, ISK T= 288.71K P ‘The higher heating value is the negative of the heat of combustion with water as liquid product. Calculate methane standard heat of combustion with water as liquid product: CH, +20, > CO, +28,0 Standard Heats of Formation: i Ajo? = 02 = Orel = 285830. mol A co2 + 2-AH p201ig - AH icra — 2-AH p02 HigherHeatingValue := -AH, AH, = -8.906x 10°. mol Assuming methane is an ideal gas at standard conditions: P gol Sq 1.793 x 10°—— nae a a 7425 Calculate methane standard heat of combustion with water as liquid product Standard Heats of Formation: CH, + 20, > CO; +2H,0 AHgco2 AHapo1ig AH.crg *= AHgo02 + 2-AH 201g ~ AH cH ~ 24H 22 890649 3 AHecH: cash Calculate ethane standard heat of combustion with water as liquid product: Standard Heats of Formation: CyHg + 7/203 -> 2CO, +3H;0 1560688 mol AH ec2H6 = Calculate propane standard heat of combustion with water as liquid product Standard Heats of Formation: CyHy + $0, —> 3CO, +4H,0 104680 = mol Abicaus AHeosHe = 34H ¢co2 + 4-AHARotig~ AHte3H8 ~ 5-AHjo2 eS Gas b) has the highest standard heat of combustion, 784.26 4.28 2H2 + 02=2420() C+ 02=CO2%g) N2(g)+2H2(g)+C(s)+1/202(g)=(NH2)2CO() AHy99 == AH, + AH + AH ‘ANog On the basis of 1 mole of C10H18 (molar mass = 162.27) Q = -43960-162.275 Q=-7.133x 10°F This value is for the constant-volume reaction: C1OHI8(1) + 14,502(g) = 10CO2(g) + 9H20() Assuming ideal gases and with symbols representing total properties, Q= AU = AH-A(PV) = AH-R-T-Angas T= 208.15-K Angas ‘= (10 14.5)-tnol -7.145 x 10°F AH = Q4R-T-Atggs AH This value is for the constant-V reaction, whereas the STANDARD reaction is at const. P.However, for ideal gases H = f(T), and for liquids H is a very weak funetion of P. We therefore take the above value as the standard value, and for the specified reaction: CIOHI8(1) + 14.502(g) = 10C02(g) + 9H20) AH 9H20(\) = 9H20(g) AHyap = 9-44012-5 ‘C1OH18(1) + 14,502(g) = 10CO2(g) + 9H20(g) yap, AHbog = 6748436) Ans. 794.29 FURNACE: Basis is 1 mole of methane burned with 30% excess air. CHa + 202 = CO2 + 2H20¢@) Entering: Moles methane =n = 1 Moles oxygen ng = 2-13 ng = 2.6 Moles nitrogen ny 15 26 2 ng = 9.781 1 Total moks of dry gases entering n= my +m. +15 13.381 At 30 degC the vapor pressure of water is 4.241 kPa, Moles of water vapor entering: 4.241 —_ 42H 13.381 = 0.585 4 701.325 - 4241 7 Leaving: C021 mol a) 120 ~ 2.585 mol @) 2.6-2= 0.6 mol @) Nz --9.781 mol @ By an energy balance on the furnace: Q = AH = AHy9g + AHp For evaluation of AHy we number species as above. 1 5.457 1.045 3AT0| | 1490 | A e 7 10" 06 3.639 0.506 9.781 3.280. 0.593 4 Ris 8.314 Swi pe YB A= 48.692 B = 0.010897 80‘The TOTAL value for MCPH of the product stream: Mcpit(303.15, 1773.15, 48.692, 0.897.107, 0.0,-0.5892.105) MCPH AHp := R-MCPH-(1773.15 — 303.15) From Example 4.7: AHgog := ~802625 Q = AHp + AH29g QF 9.895 11 9.89511 “10,61 Ans. HEAT EXCHANGER: Flue gases cool from 1500 degC to 50 degC. The partial pressure of the water in the flue gases leaving the furnace (in kPa) is m2 pp. 101.325 pp = 18.754 ny tn +n3 ng ‘The vapor pressure of water at 50 degC (exit of heat exchanger) is 12.34 kPa, and water must condense to lower its partial pressure to this value. Moles of dry flue gases: n nengtng n= 11.381 Moles of water vapor leaving the heat exchanger: 1234 101.325 — 12.34 ‘Moles water condensing: An mi ng = 1.578 2.585 1.578 Latent heat of water at $0 degC in J/m« AMEgg := 2382.9-18.015 ‘Sensible heat of cooling the flue gases to 50 degC with all the water as vapor (we assumed condensation at 50 degC): MCPH(323.15,1773.15, 48.692, 10.897. 10" >, 0.0, -0.5892-10°) = 60.01086 MCPH := 60.01086 Q = R-MCPH-(323.15 ~ 1773.15) - An-AHs9 Q''=766;677:] Ans. at4.30 4NH13(g) + 802(g) = 4NO(Q) + 6H2O0(@) BASIS: 4 moles ammonia entering reactor Moles 02 entering = (5)(1.3) = 6.3 Moles N2 entering = (6.5)(79/21) = 24.45 ‘Moles NH3 reacting = moles NO formed = (4)(0.8) = 3.2 ‘Moles 02 reacting = (5)(0.8) = 4.0 ‘Moles water formed = (6)(0.8) = 4.8 ENERGY BALANCE: AH = AHg + AHg9g + AHp = 0 REACTANTS: 1=NH3; 2-02; 3-N2 4 3,578 3.020 0,186 65 | A]3.039) B=} 0506|-10? D=| -0.227 j-10 24.45 ) 3.280, 0.593, 0.040 ea: A Svai B yn Bi D Yi 7 i i A= 118.161 B= 0.02987 D = -1.242x10° TOTAL mean heat capacity of reactant stream: McpH(348.15,298.15, 118.161, 0.02987, 0.0,-1.242-10°) = 126.61632 MCPH := 126,61632 AHg := R-MCPH-(298.15 ~ 348.15) The result of Pb. 4.21(b) is used to get AHggg = 0.8-(-905468) PRODUCTSi=NH3; 2: 2; 3-NO; 4-20; 5=N2 os 3.378 3.020 0.186 25 3.639 0.506 0221 32 A= |3.387 0.628 |-1073 0.014 |-10° 48 3.470 1.450 0.121 24.45 3.280. 0.593) 0.040 82A Yiwai A= 119.65 B= 0.027 D= 8.873% 10" Yai D Yer By the energy balance and Eq. (4.7), we can write: To:= 298.15 t= 2 (guess) Given tisFind(t) 9 1328300 Tis Ty K-t Ans, 431 C2H4(g) + H20(@) = C2HSOH() BASIS: 1 mole ethanol produced Energy balance: ayy = Q = AHg + AHgog AHp9g := 277690 — (52510 - 241818) AHy9g = -8.838x 10" Reactant stream consists of 1 mole each of C2H4 and H20. 1.424 14394) 4.392 As B H10-* C= 3.470 1.450 0.0 A ae Yai Yee =-4322x10° D S 00 os > jh’ 0.121 Yd Lixo A=4894 B= 0.01584 McPH(298.15,593.15,4.894,0.01584,~4.392-10"§,0.121-109) = 11.1192 83MCPH := 11.1192 Ag := R-MCPH:(298.15 ~ 593.15) AH = -2.727« 10" Q = (AHR + AHo98}-5 £5115683) Ans. 4.32, One way to proceed is as in Example 4.8 with the alternative pair of reactions: CH4+ H20=CO+3H2 ‘AlLyogq = 205813 CH4 + 28120 = CO2 + 4112 AFLgogp += 164647 BASIS: 1 mole of product gases con! CO; & H20 0.6275 mol H2 g 0.0275 mol CO2; 0.1725 mol Entering gas, by carbon & oxygen balances: 0.0275 + 0.1725 = 0.2000 mol CH4 0.1725 + 0.1725 + 2(0.0275) = 0.4000 mol H20 AHg9g := 0.1725-AHz9gq + 0.0275: AH 9gb AHgog = 4.003 x 10" 02 0A 1.102 9.081 2.164 x ( ) oe jo cs 10° ® b= (.°° Ji’ 3.470 1.450. 0.0 \o.121) A ya AUB = Bi Yc D yn Dj LR8 B= 2396x107? C= -4.328x107 Da 484% 10? ‘The energy balance is written Q= AHR + AHp9g + AHp. REACTANTS: 1=CH4;2=H20 i 1cPHH(773.15, 298.15, 1.728,2.396-10 4.3310 ,4,84-10°) = -1377.435 137.435 AHR := RICPH AH = -1.145x 104 ICPH = PRODUCTS: CO; 3=H20; =H?4 B= 6.397% 10 D = 3.579% 10° rcpi{298.15,1123.15,3.370,6397-10"4,0.0,3.579-108) = 3164.293 ICPH := 3164.293 ‘AHp := RICPH ‘AHp = 2.631 10" Q = (Hp + 4Ha98 + AHp)-J QE 54886) Ans. 4.33 CH4 +202 = CO2 + 2H20(g) C2H6 + 3.502 = 2CO2 + 3H20(@) AFg9gp = — 1428652 BASIS: 1 mole fuel (0.75 mol CH4; 0.25 mol C2H6) burned completely with 80% xs. air. 02 in = 1,8§(0.75)(2) + (0.28)3.5)] = 4.275 mol N2 in = 4.275(79/21) = 16.082 mol Product gases: CO: 1S + 2(0.25) = 1.25 mol H20 = 2(0.75) + 3(0.25) = 2.25 mol. 02 = (0.8/1.8)(4.275) N2= 16.082 mol AH 9g != 0.75-AHl9gq + 0.25-AHpogp Q:=-8:10° 9 mol Energy balance: Q = AH = AHz9g+AHp AH = Q= Ay 3 PRODUCTS: 1=CO2; 2=H20; 3=02; 4=N2 1.25 5.457 1.045 “1.157 2.25 3.470 1450} 3 o121 | 5 = A B K10-* D 10" 19 3.639 0.506 16.082 ) 3.280 0.593, 854.34 As Sima B Yves A=74292 B= 0015 D = 9.62% 10" By the energy balance and Eq. (4.7), we can write: To = 303.15 t= 2 (guess) ) t= Find(t) eee Given Q=AHg9¢ = RY A-To-(t = 1) + To (: = L788 TH542K Ans. BASIS: 1 mole of entering gases containing 0.15 mol SO2; 0.20 mol 02; 0.65 mol N2 S02 +0.502=S03 Conversion = 86% S02 reacted = SO3 formed = (0.15)(0.86) = 02 reacted = (0.5)(0.129) = 0.0645 mol Energy balance: AH773 = AHg + AH29 + AHp Since AHy and AHy cancel for the gas that passes through the converter unreacted, we need consider only those species that react or are formed. Moreover, the reactants and products experience the same temperature change, and can therefore be considered together. We simply take the number of moles of reactants as being negative. The energy balance is then written: AH773 = AHy9g + SH yet AHg9g = ~395720 = (~296830)}-0.129 1: $02; 2: 02; 3: SO3 0.129 5.699 0.801 =1.018 ~0.0645 | A=] 3.639] B:=10506}10-9 D3=| -0.97 |-10° 0.129 8.060. 1.056 ~2.0280.06985 B=258K107 =D McPH(298.15,773.15,0.06985,2.58-10" 7,0.0,-1.16-10°) = 0,019666 MCPH := 0.019666 AH get = R-MCPH-(773.15 ~ 298.15) Alias! 79) Ans. AH373 := (AHg98 + AH pet) 4.35 CO(g) + H20(g) = CO2g) + H2(g) BASIS: 1 mole of feed consisting of 0.5 mol CO and 0,5 mo! H20. Product stream: Energy balance: Q = AH = AH + AHg9g + AHp AHggg := 0.3-[-393509 ~ (-110525 -214818)]_ AH9g = -2.045 x 10" 2 1:CO 2: 120 ; 3.376 0557) 3 0.031 As B= -10 Ds . . 3.470 1.450 0.121 yy Ai B a Bi D “Dee A = 3.423 B=Loodx10 > =D =4,5x 10° Mepti(298.15,398.15,3.423, 1.0035-10" 3,0.0,0.045-108) = 3.8108, MCPH := 3.8103 AHg = R-MCPH.(298.15 ~ 398.15) AH = ~3.168 10° Products: 1:CO 2:H20 3:CO2 4: H2 8702 3.376) 02 3.470 103 5.457 03 3.249, i=sl.4 A= 3.981 MCPH(298.15,698.15,3.981,0.8415-107 MCPH := 4.25405 AHp := R-MCPH-(698.15 ~ 298.15) Q i= (AH + Allg + AHp}-J 0.557 1.450} o3 1.045 (oaae, B ye By D 4 B= 8415x107 D= ,0.0,-0.3042-10°) AHp = 1.415x 10% a 4.36 BASIS: 100 Ibmol DRY flue gases containing 3.00 Ibmol CO2 and 11,80 tbmol CO x Ibmol 02 and 100-(14.8-) 85.2-x Ibmol N2. The oil therefore contains 14.80 tbmot carbon;a carbon balance gives the mass of oil burned: 12.011 0.85 14.8 The oil also contains H20: 209.133-0.01 18.015 Ibm = 209.133 Ibm Ibmol = 0.116Ibmol Also H20 is formed by combustion of H2 in the oil in the amount 209.133-0.12 2.016 Ibmol = 12.448 1bmol Find amount of air entering by N2 & 02 balances. N2 entering in oil: 209.133-0.02 28.013 Ibmo! = 0.1491bmol Ibmol N2 entering in the air=(85,2-x)-0.149 ~85,051-x 88Imo! 02 in flue gas entering with dry ai 3.00 + 11.8/2 + x + 12.448/2 15.124 + x Ibmol (€O2) (CO) (02) (H20 from combustion) 12 in air + 02 im air = 85.081 - x + 15.124 + x = 100.175 Ibmol Total dry air Since air is 21 mol % 02, oar BH2A+X . (0.21-100.175- 15.124)-Tbmol x = 5.913 Ibmol 100.175 [CHECK: Total dry flue gas = 3.00 + 11.80 + 5.913 + 79.287 = 100.00 Ibmo!] Humidity of entering air, sat. at 77 degF in Ibmol H2O/Ibmol dry air, P(sat)=0.4594(psia) 0.4594 14.696 — 0.4594 Ibmol H20 entering in air: = 0.03227 0.03227-100.175-Ibmol = 3.233 Ibmol Ify = Ibmol H20 evaporated in the drier, then Ibmol H120 in flue gas = 0.116+12.448+3.233+y 5.797 + y Entering the process are oil, moist air, and the wet material to be dried, all at 77 degF. The "products" at 400 degF consist of: 3.00 Ibmol CO2 11.80 Ibmol CO 5.913 Ibmol O2 79.287 Ibmol N2 (15.797 + y) Ibmol H20(g) Energy balance: Q = AH = AHy9g + AHp where Q = 30% of net heating value of the oil: 89= -03-19000- 22. 209.13:1bm Ibm 1.192 10°BTU Reaction upon which net heating value is based: OIL + (21.024)02 = (14.8)CO2 + (12.448 + 0.116)H20(g) + (0.149)N2 =19000-209.13-BTU ‘AHg9gq = -3.973 x 10°BTU ‘To get the "reaction" in the drier, we add to this the following: (11.8)CO2 = (11.8)CO + (5.9)02 AH 988 AHgggp = 11,8:(-110525 + 393509)-0.42993-BTU. (yH20(g) Guess: y = 50 Allggge(9) := 44012-0.42993-y-BTU. (y)H2000 (The factor 0.42993 converts from joules on the basis of moles to Btu on the basis of lbmol.] Addition of these three reactions gives the "reaction" in the drier, except for some 02, N2, and H20 that pass through unchanged. Addition of the corresponding delta H values gives the standard heat of reaction at 298 K: AHp9g(y) #= AHo9gq + AH29gp + AH29ge(¥) For the product stream we need MCPH: 1:CO2 2: CO 3:02 4:N2 5: H20 To = 298.15 R= 1,986 T wee T = 477594 3 5.457 1.045 1.157 18 3376 0.587 0.031 ny) =| 5.913 A=] 3.639 0.506 |- 0.227. |-10" 79.218 3.280 0.593 0.040 15.797 +y. 3.470, 1.450 0.121 LS AQ)= Vawra; BO) =YawrB: Do = Yor; 1 = t= 1602 Cply) = R [aoe Pao +420 2 Ty 90Te = 562.2K 8.98bar — Z_ 25 0.271 353.2K That Ty = 0.628 Pe 0.02 Generalized Correlations to estimate volumes Vapor Volume 0.422 PO OURS eet Eq. (3.61) Ty By = 0.139 - By = -1.073 Eq. (3-62) Py Pr Ze lsBox obra Z= 0967 ZRTy 3 Ves V = 2.838% 19° - mol Liquid Volume 257 3 Vogt = Vere) Eq. 3.63) Vat = 96.807" mol ‘Combining the Clapyeron equation (4.11) AH = T-AV-4 Pye a eae with Antoine's Equation Pay =e ™C gives AH ® T-AV- (toy 673 AV V~Veue AV = 2.829 19° mol 13.8594 2773.78 C= 53.00 Answers for parts (b)-(e) J (b) AH = 36.262 mol (© aH=32.278 & mol (@ an=28948 mol (© an=33.838 mol 4.13 Let P represent the vapor pressure, 5622.7. tof 2.) = agsrsis - 227K kPa) r 2.71 ind(P) dpa = p-( 5022-7K _ 4.70504 ia P = 87.396kPa ant = 31600 /2ule mol 68 P= 100-kPa (guess) ) 4.70504: o( | K) apa = 0.0292 KClapeyron equatio V= vapor molar volume. V = Viq+ SY T-apaT F439: Bn v{2¥ 4) Ans. 38): et } 4.14 (a) Methanol: Ty = 512.6K 0.97bar Ty = 337.9K AL: 13.431 -81.28-10~ = 131.1310" © fee q CpL(T) =| AL+ 14 = js eRe Ay =2211 By := 12216-1077 Cpy(T) = (megeres re yee Trsat = ki AHg = 38.301 — mol eikd Ally = 35.645 mol 6912 Text 7 encnet vany+ | cey(naT alt= 49.38" 1 Tost a nes oo mel Q=n-AH ‘Ans. ir (b) Benzene: aH, = 28.273. 55.296 2. moi mol J Ky (© Toluene AH, = 30.625— AH = 65.586 — mol mol 4.15 Benzene T.:= 5622K Pg Tisat 2 451.7K — Tosat = 358.7K Cp Estimate AHy using Riedel equation (4,12) and Watson correction (4.13) Tosat Ten = 0.628 Trasat Trasat = 0.638 30.5882 mol aly = 30.285. mol is adiabatic and isenthalpic. Assume the throttling proces: Guess vapor fraction (x): x := 0.5 Given Cp-(Tisat— Tasat) = XAHy x= Find(x) KE 04982 Ans. 189.4-K 308.3-K 4.16 (a) For acetylene: T, 61.39-bar Ty, T= 298.15-K 70Th T rut Tv ned erat T= 0087AH, = 1691 mol any = 6638-2. mol (b) For 13-butadiene: Agog = 88.5 mol ig (©) For ethylbenzene: AHy5g = —12.3—— mol Ws (@) For n-hexane: AH5g = -198.6— mol KI (©) For styrene: AFg9g = 103.9-— mol 4.17 Ist law: dQ = dU -dW = CydT+P-dV A) Ideal gas: PV=SRT and PdV+V-dP = RdT Whenee V-dP = R-dT- P-dV @) Since p-V? = const then P.8-VO"Lav. from which V-dP —Pb-dV ‘Combines with (B) to yield: Pav = So 14.18 R Combines with (A) to give: AQ = Cyat + a or dQ= Cpar-Rars RH which reduces to Since Cp is linear in T, the mean heat capacity is the value of Cp at the arithmetic mean temperature. Thus Tam ‘= 675 Cem 85+ 0.57:10"?-Tam) Integrate (C): 50K Ans, For the combustion of methanol: CH3OH(g) + (3/2)02(g) = CO2g) + 2H20(g) AHQ98 393509 + 2-(-241818) — (-200660) AH 9g = ~676485 For 6 MeOH: Ans, For the combustion of 1-hexene: (COH12(g) + 902(g) = 6CO2(g) + 6H20(g) 724.19 AHg9¢ := 6-(~393509) + 6(-241818) - (-41950) 27 Ams. AHg9g = ~3770012 AHao@ ='=3,770,01 ‘Comparison is on the basis of equal numbers of C atoms. C2H4 + 302 = 2CO2 + 2H20(g) Bog = [2-(-241818) + 2-(-393809) ~ $2510]. — mol mple 4.7. However, with simpler to proceed differently. Parts (a) - (d) can be worked exactly as Mathead capable of doing the iteration, Index the product species with the numbers: 1= oxygen 2= carbon dioxide 3 = water (g) 4= nitrogen (a) For the product species, no exeess air: 0 3.639 0.506) ~0.227 2 5.487 1.045 | 10-3 “137 2 3.470 1.450 | K oat 11.286, 3.280, 0.593, 0.040. 4 A Yai B: Sg A = 54.872 B= 00125 D = ~1.621«10°K oT cp For the produets, Ape R | FedT Tos 298.15K Jig The integral is given by Eq. (4.7). Moreover, by an energy balance, Algo + AHp = 0 3t= 2 (guess) B Given -AHg9g = R- [at (r- Ye> Ty t= Find(z) + = 8497 T= Tot $225335K Ans. Parts (b), (©), and (d) are worked the same way, the only change being in the numbers of moles of products. () 75 mq, = 14.107 T= 21986K Ans. © no, = 1.5 Ng, = 16.929 T= 1950.9K Ams. (@® no, = 3.0 ng, = 22.571 1609.2K Ans. (©) 50% xs air preheated to 500 degC. For this process, AH ie + AH9g + AHp = Agi = MCPHL(298.15 — 773.15) For one mole of air: McPH(773.15,298.15,3.355,0.575-10°°,0.0,-0.016-10°) 65606 For 4,5/0.21 = 21.429 moles of air: AHgie = 0 R-MCPH-AT AH jp != 21.429-8.314-3,65606-(298.15 — 773.15) s mol ‘The energy balance here gives: AHyog + AHai, + AHp = 7%1s 3.639 0.227 2 5.457 1157 ns = -10°-K? 2 3.470 0.121 16.929. 3.280, 0.040 A =e Ai OB Ss Bi Swi i 542 8.84 B= 0016; D = -1.735« 10°K’ 1:52 (guess) Given tis Find(s) t= 7.656 4.20 n-CSH12 +802 = 5CO2 + 6H20(1) By Eq, (4.15) with data from Table C.4: '= 5-(~393509) + 6-(~285830) ~ (-146760) 3,535,765-3 Ans. 421 answers are found by application of Eq. (4.15) with data from Table C.4. (a) -92,220 J (n) 180,500 J (b) -905,468 J (0) 178,321 3 (©) -71,660 5 (p) -132,439 (a) -61,980.5 (q) 44,370 5 (©) 367,582 5 (r) 68,910 5 75437 4.38 Given Cp(y)-(400 - 77)-BTU = Q ~ AHz98(y) y= Find(y) y= 49.782 (bmol H20 evaporated) Whence (lb 120 evap. per Ib oil burned) Ans, BASIS: One mole of product gas containing 0.242 mol HCN, and (1-0.242)/2 = 0.379 mol each of N2 and C2H2. The energy balance is Q= AH = AHg9g + AHp 0.242 Allgog = (2135100 ~227480)-25 3 Ablggg = 5.169% 10° Products: 0.242) 4.736 1.359 0.725 0379 3280] B:=/0593 [10° D:=| 0.040 |-10° a 6.132, 1.952 1.299, 3 A Drei B Yi D Swi i i i 3 R:= 8314 A 34x10 > D = ~6.526x 10" 71330 B=. MePH(298.15,873.15, 4.7133, 1.293410" ?,0.0,-6.526-10°) = 5.22010 MCPH := 5.22010 AHp := R-MCPH-(873.15 ~ 298.15)-J AHp = 2.495 10° Q := AHgo + AHp Ans. BASIS: 1 mole gas entering reactor, containing 0.6 mol HCI, 0.36 mol 02, and 0.04 mol N2. HCI reacted = (0.6)(0.75) 4HCKg) + 02(g) = 2H20(@) + 2C12(g) For this reaction, 1.45 mol st4.39 5 AHgog ‘= 2-(-241818) ~ 4(-92307) AHg9g = —1.144 x 10 Evaluate AHgp3_ by Eq. (4.21) with To 2= 298.15 T= 823.15 Rix 8314 1:H20 2:CR 3: HCI 02 2 3.470 145 0.121 4442 0.089 | 5 0344} 5 A= B 10 10 3.156 0.623 0.151 =I 3.639 0,506, 0.227 1.4 AA Vwi AB Ys AD Swi 8 35 104 AA = ~0.439 AB = 8x 10 AD = -8.23 x 10 8.23-108) = -0.72949 MDcPH (298.15, 823.15, 0.439,8.0-10~ MDCPH := -0.72949 AHiz9g + MDCPH-R-(T - To) AHgp3 = ~117592 AHg23 © Heat transferred per mol of entering gas mixture: AHg9- An: Qa s c02+C=200 AHg9gq := 172459 (@) 2C+02=2C0 AHyogp. = -221050 (b) Eq. (4.21) applies to each reaction: For (a): 2 3.376 (0.557 0.031 As L771 orm |ao"3 +10 5.457, 1.045 =1:157, As Sarai 4B Yi AD = Smid; 92AA=-0476 — AB=-7.02x10* AD = 1.962 10° Mpcpri(298.15,1148.15,-0.476,-7.02-10" *,0.0,1.962-10% MDCPHa AH, 48a := AH298a + R-MDCPHg:(1 148.15 — 298.15) AH 14a = 1.696% 10° 0.410505 0.410505 For (b): ( 3.376 0.557 0.031 -1 3.639} B:=] 0506-107 — D:=| -0.227 |.10° 2 1771 07 0.867 a3 AA Dwi AB = Y arBi AD =) Di AA =-0429 AB =-9.34x 107% AD = 1.899% 10° MpcPH(298.15, 1148.15,-0.429,-0.934-10",0.0, 1.899:10°) = -0.549680 MDCPHg := ~0.549680 AH) y4gh = AH2ogh + R-MDCPH (1148.15 ~ 298.15) AH agp = -2.249 10° The combined heats of reaction must be zero: coy’ AHy 1489 + 90,°AHi 48h = 0 NCO. ~All fee ae r= 1327 AH 1488 Define: rs ny For 100 mol flue gas and x mol air, moles are: Flue gas Air Feed mix co2 128 0 12.8 co 37 0 37 93,02 «54 o21x 54+ 0.21x N28 0.79% 78.1 + 0.79x Whence in the feed mix: y= —12-8__ 54+021x BS 54 x= + ___.mol 19.155 mol 21 Flue gas to air ratio= Ans, Product composition: 3.7+2-(12.8+5.440.21-19.155) ng = 48.145 93.232 Mole % CO= Mole % N2= 4.40 CH4 +202 = CO2 +2H20(¢) AH9gq ‘= ~802625 CHG + (3/2)02 = CO + 2H20(8) Allgogy = 519641 BASIS: 1 mole of fuel gas consisting of 0.94 mol CH4 and 0.06 mol N2 Air entering contains: 1,35-2:0.94 = 2.538 mol 02 2.538 2 = 9.548 mol N2 Moles CO2 formed by reaction = 0,94-0.7 Moles CO formed by reaetion = 0,94-0.3 = 0.282 J AHa99 *= (0.658-AHa9g4 +0.282-AHy5g4)——AHLo9g — -6.747 10° mol mol 1.658 4‘Moles H20 formed by reactio 0.94-2.0 = 1.88 Moles 02 consumed by reaction= — 2.0.658 + ; 0.282 = 1.739 Product gases contain the following numbers of moles: (1) CO2: 0.658 Q) CO: 0.282 (3) H20: 1.880 (4) 2: 2.538 - 1.739 = 0.799 5) N2: 9.548 + 0.060 = 9.608 0.658 ‘5.457 ‘1.045 1.157 0.282 3.376 0.557 0.031 1.880 3.470 1.450 |-10-> 0.121 |-10° 0.799 3.639 0.506 0227 9.608 3.280) 0.598 0.040 Ss A = Si neai B Yves D Yi R= 831b— A= 454881 B= 9.6725x 10? D = 3.396% 10° molK MC pul298. 483.15 ,45.4881 ,9.6725-10 -0.0,-3.396-104) 49.03091 MCPH := 49.03091 AHp := R-MCPH-(483.15 ~ 298.15)-K AHp = 7.541 x. wi mol i Energy balance: Allpg = BHa9g + AHp AH yg = ~$99.252—— mol AH o:mdoty29 + AH pe ndotfuel = 0 mdow20 = 34.0-8 see From Table C.1: kr A220 = (398.0~ 104.8) kg —AHy20-mdotz20 mol ee ndotfuet = 16.635 see nidotfet 95Volumetric flow rate of fuel, assun ideal gas: ndotfye"R:298.15-K 101325-Pa Gms 441 C4H8(g) = C4H6(g) + H2(Q) Allggg := 109780: = mol BASIS: I mole C4H8 entering, of which 33% reacts. ‘The unreacted C4H8 and the diluent H2O pass throught the reactor unchanged, and need not be included in the energy balance. Thus 1 Tg = 298.15-K 798.15-K ase Evaluate AHy9g_—_ by Eq. (4.21): ot 1:C4H6 2:12 3: C4H8 2.734 26.786 8.882 00 3249} B=) 0422 |107? C=} 0.0. |-10°% D =} 0.083 |-10° 1.967, 31.630. 9.873, 0.0 3 Dw AaB y Sms Swe AD = SY medi AB = -4.422% 10> aC = 991x107 AD = 8.3.x 10° MDCPH(298.15,798.15,4.016,-4.422-1073,9.91-107” 0.083-105) = 1.94537 MDCPH := 1.94537 | AH793 := AHy9g + MDCPH-R-(T~ To) AH 79g = 1.179 x tet Q:=0.33-molAH79g “Qs 4g8967 Ans.Chapter 5 - Section A - Mathcad Solutions 5.2 Let the symbols Q and Work represent rates in kJ/s. Then by Eq. (5.8) Ty = 750K By Ea. (5.8): Buty (b) = 0.35 Qu Qc [Ou] ~ [Work] QG=1.7645e107kW Ans. 54 (a) Tos 303.15-K Ty = 623.15-K 11 = 0.55" Carnot y= 0.282 Ans. 7@) n= 035 By Eq. 6.8), Ans, = NCamot 5.7 _ Let the symbols represent rates where appropriate, Caleulate mass rate of LNG evaporation: V 35-9000. 1.0133-bar ‘T= 298,15-K g Vv ks molwt := 1722 mg = molt png = 625442 mol RT 8 ‘Maximum power is generated by a Carnot engine, for which [Work] | Qs] = |@cl _ [Qu | | Ta [Qc] ]@¢] [ed Te Ty = 303.15-K Te = 3.2K Qc 512-2 -muxo Qe = 3.202 x 10°KW Z (T; Work = Qe| = - ‘ Ans. (Te Qu = Qo+ Work Ans. 5.8 Take the heat capacity of water to be constant at the value Cp = 4.184... kg-K BASK T2=37BISK Q=Cp(T2-T)) Q= asa $ (T A8q20 = Cpl A8jn0 = 1305 kgK Ans. 98AStotal = S20 + ASres (b) The entropy change of the water is the same as in (a), and the total heat transfer is the same, but AS yes = —-| ——— 2 \323.15-K AStotal = ASres + ASH 20 (©) The reversible heating of the wafer requires an infinite number of heat reservoirs covering the range of temperatures from 273.15 to 373.15 K, cach one exchanging an infinitesimal quantity of heat with the water and raising its temperature by a differential increment, 589 0.06-m> Qs 15000-5 AU = Q+W=Q2 n-Cy-(T2-T) 42 3 + Tz = 1x 10K roy 7 By Eq. (5.18), w( 22) nu( 2) y Eq. 6.18), AS = | Cpa | ~ Ren] (= Pu) eos a But Ans. Pi Al T: % 5 Whence aS nev?) ‘AS = 20.794 1 ee (b) The entropy change of the gas is the same as in (a). The entropy change of the surroundings is zero. Whence ASioai = 10.7942 Ans. The stirring process is irreversible. 995.10 (a) The temperature drop of the second stream (B) in either case is the same as the temperature rise of the first stream Cp (A), ie, 120 degC. The exit temperature of the second stream is therefore 200 degC. In both cases we therefore have: (463.15) 463.15 473.15 Sq = Cptn| SO Sp = Cprln Ane Sas 15) a ie 8) Ans. (b) For both eases: AStotal ‘= AS + ASB Ans. (¢) In this case the final temperature of steam B is 80 degC, ie., there is a 10-degC driving force for heat transfer throughout the exchanger. Now co 463.15) in( 353 3) Pe 343.15 ) \ 473.15 Ans. AStotal “= ASq + ASB Ans. ag 5.16 By Eq. (5.8), AW = dQ= To Since dQ/T = dS, AW = dQ - To-dS Integration gives the required result. T= 400K To = 300K 582x100 mol 10048 := Cpen| 22 = Crh Ans. Work = Q-Tg-AS Ans, Ans. Process is reversible, 57 Ty = 600K = Top := 300K = Typ = 300K Tc := 250-K For the Carnot engine, use Eq. (5.8): Jw} _ Ty -Tei lant Tn The Carnot refrigerator is a reverse Carnot engine. Combine Eqs. (5.8) & (5.7) to get: ww]. TH Tez [Qc2] Te Equate the two work quantities and solve for the required ratio of the heat avanti 2 (TH i Jaf PEWS Ans Tin (Ta S.18(a) Ty := 300K Py = 1.2bar AH i= Cp(T2-T1) AS = Coral = Cpl 0) anes AS = 1.484. mol 104( aH= 3.8108 mol @ ane mol @ als 6651-1080 mal 5.19 The cycle is the same a identificaitons C=1; D= page 298: For the given data: 5 ( 973.15 - 473.15 7 (1973.15 — 773.15, J mokK J molK J mobK AS = 4.953, AS = 2.618 AS = -3.607 shown by Fig. 8.10 on page 298. With the ; A=3; and B=4, the efficiency is given by Eq. (A) on Work = 3.6x 10° mol Whenee Tp = T) + YOK ov AN 374K Ans. 102525 Pcs T= 800 Step 1-2: Volume decreases at constant P. Heat flows out of the system, Work is done on the system, Wio= {P-(V2-vi)]= {R(T2-71)] ‘Step 2-3: Isothermal compression. Work is done on the system. Heat flows out of the system. ( P: P: Wo3 = RT? of?) = nnon(2) 2 7) Step 3-1: Expansion process that produces work. Heat flows into the system. Since the PT product is constant, Pdt+T-dP = 0 ro ena @ PVERT PedV + Vd? = RT PdV = RdT- V-dP = RT “ee In combination with (A) this becomes PAV = RT + RT = RAT Ty Ty Moreover, P3 = Pye v1 W315 -| PdV = -2:R-(T) - T3) = -2-R-(T} - T2) V3 Qs1 = AU3; ~ Wai = Cv(T- Ts) +2-8.(T1- Ts) Q31 = (Cv+2:R).(T1 - Ts) = (Cp +R)-(T1 ~ Ta) [Wi2 + Wo3 + Wsi] Qa1 350-K 403T, at z Wip = 291x109 mol J Wo3 = 2.017% 10° mol 582% 10°. mol Ws Q31 = 1.309% 101 mol E0068 Ans. 403.15K Py c= 2.5-bar Pp = 6.5-bar Tres “= 298.15-K (Po By Eq. (5.18), AS = Rel With the reversible work given by Eq. (3.26), we get for the actual W: (Po 3 Work = 13-R-T-in| =| (Isothermal compresion) Work = 4.163 10° \Pr mol Q=-Work Q here is with respect to the system. So for the heat reservoir, we have AStotal = AS + ASros 5.27 (a) 1cPS(473.15,1373.15,5.699,0.640.1073,0.0,~1.015-10°) = 6.448223 ICPS 6.448223 104By Eq. (5.14) with P = const. and Eq. (5.15), we get for the entropy change of 10 moles 10-mol AS = n-R-ICPS Ans. n () 100 (523.15,1473.15, 1.213, 28,785.10 = 20.234265 ICPS := 20,234265 By Eq. (8.14) with P= const, and Eq. (8.15), we get for the entropy change of 12 moles R-ICPS as n= 12-mol AS : 5.28 (a) The final temperature for this process was found in Pb. 4.2a to be 1374.5 K. ‘The entropy change for 10 moles is then found as follows ices (473. 15, 1374.5, 1.424, 14.394:10" > 4.39210 0.0) = 10835459 ICPS := 10.835459 n= 10-mol AS := n-R-ICPS AS = 900 aes Ans, (b) The final temperature for this process was found in Pb. 4.2b to be 1413.8 K. ‘The entropy change for 15 moles is then found as follows: 10ps (533.15, 1413.8, 1.967,31.630. 10" >,-9.873-10" °,0.0) = 21.309212 ICPS == 21.309212 AS := nR-ICPS (©) The final temperature for this process was found in Pb. 4.2c to be 1202.9 K, The entropy change for 18.14 kg moles is then found as follows icps(s33.15, 1202.9, 1.424,14.394-10" $,~4,392-10 60.0) = 8.245741 Icps 245741 n= 18140-mol AS = n-R-ICPS AS = 124361 fs Ans. 1055.29 The relative amounts of the two streams are determined by an energy balance. Since Q= W = 0, the enthalpy changes of the two streams must cancel. Take a basis of 1 mole of air entering, and let x = moles of chilled air. Then 1 - x= the moles of warm air. To = 298.15-K ‘Temperature of entering air Tr Tz x€p(Ty = To) + (1 =»)Cp-(T2-To) = 0 248.15-K ‘Temperature of chilled air 48.15-K ‘Temperature of warm air Given Thus x = 0.5, and the process produces equal amounts of chilled and warmed air. The only remaining question is whether the process violates the second law. On the basis of 1 mole of entering air, the total entropy change is as follows. Pp -bar 1; Ty AStotal = * con(Z) +(1=x)-Cp (2 \- nu) \To, 0) Po Ans. Since this is positive, there is no violation of the second law. 5.30 Ty := 523.15-K Cyi=Cp-R Q = AU - Work 1082 Q=-1733x 10 ASreg = 5.718 molK mol J molK AS = -2.301 3:42 PROCESS IS POSSIBLE. 5.33 For the process of cooling the brine: Cp = 3.5 at-=-40K — mdot = 20-82 ny := 027 kgK sec Ty: (Q73.1S425)K Ty = 298.15K T2:= Q73.15-15)K 12 = 258.15K To = (273.15 +30)K Ty = 303.15K AH := Cp-AT SH = 140% kg Te AS = con 2) as = -0.504—_ en ke-K Eq. (8.26): Wdotiqegi := mdot (AH ~ Tg-AS) Wdotigeal = 256.938kW Bi fi Wdotides By Bq. B28): gop — Sees Wade 951.6KW Ans. "t 5.34 E:= 110-volt i= 9.7-amp Tg = 300-K ‘Wdotmech = —1.25-hp Weoteteet = FE Weotetec: = 1.067 10° W At steady state: Qdot + Wdoteiect + Wd0tmech = fut =0 it dot 20" sdotg = Ls! a at 107Qdot := -Wdotetecr~ Wdotmech __ Qdot = -134.875W Ans, Sdowg O-amp = Ty = 300K Waotetect = 2.5% 10° W At steady state: Qdot + Wdoteleat = LU dt Qdot S +sdotg 5.38 mdot = 10——— Ty = (25+273.15)K Py 2= 10bar Ans. (©) Sdotg := mdot-AS (@) Ty = 20+273.15)K — Whost = To AS 1085.39(a) Ty := 500K Py = Obar «TQ 37IK P= Cp To :=300K gag mol mol AH = nCp(T2- Ti) Wes AH WES 9753.8) ‘Ans. as~o(cpu(2) as = 40082 Ti K Eq. (5.27) Wideal = (AH - To-AS) Wideat = “51631 Ans. Eq. (5.30) ‘Whost = 1409:35 Ans. Eq. 6.39) Ans. wy, (a) 3753.8) -5163) 1409.3) 98 (b) -2460.9) 29539) 493] Lois (©) 3063.71 4193.7) 11308 3.7672 (@) -3853.5) 4952.4) 1098.81 36632 (© -3055.4) “4119.23 1063.87 3. 540% SAL Py = 2500KPa Py 150KPa eas ante! 109S42 Qu IK) Wie 045K) Ty (2504273.1)K Ty = $23.15K Tos (25+273.15)K Te = 298.15K [wl Qh] actual = Mactual = 0.45 543 Qy = 150K Qy= 50k) Qp = 100-KT THis 990K = Ty1= 390K = Ty 250K Ty = 300-K sow hy H& a eee (b) Wrst = Te Sq Ans. 544 Ty = GIS +273.15)}-K Tes 204273.15)-K Ty = 588.15K Te = 293.15K Te @) max = 1 <= Ans, (a) n, Tu Gis [Wat] Tmax 0) = 0.6- Max Qdote := Qdoty — |Weor} (actual value) River temperature rise: Vdot Ans.67 6.8 Chapter 6 - Section A - Mathcad Solutions At constant temperature Eqs. (6.25) and (6.26) can be written: dS = -B-V-dP and dH = (1 ~B-T)-v-dP For an estimate, assume properties independent of pressure. 1200-kPa 2095-10 2." ! Te = 408.1-K 28 emK gm om? mobwt + 58,1232 262.7. mol ‘mol Eq. (8.63) for volume of a saturated liquid may be used for the volume of a compressed liquid if the effect of pressure on fiquid volume is neglected. 359 088 | T T =| 360 /-K Tr Tr = | 0.882 | 361) fe (The elements are denoted by subscripts 1, 2, & 3 oF 131.601 2857 3 v =| vere 1] [ee Fiscal | mol (132.68 Assume that changes in T and V are negligible during throtling. Then Eq. (6.8) is integrated to yield: 1AH = T-AS4+V-AP but -vr(P2-Pi) Tr AH= 0 Then at 360K, AS el a We use the additional values of T and V to estimate the volume expansi 3 AV = V3-V, AV = 1.079. AT = 13-7, AT=2K mol -1.Av B = 4.098755 103K"! Vi AT Assuming properties independent of pressure, Eq, (6.29) may be integrated to give AS = cet BV-AP AP :=Po-Py AP = -2x 10°kPa Ty (a8 +8-VraP) Whence t= 10S +B-¥r AP) TORK Ans. Cp molwt : 69 T= 208.15-K Pj = Lbar Pp = 1500bar 3 250-107 87! bar”? Vip = 1003 kg em? By Eq. (3.5), Vo := Vyexp[-1-(P2~Pi)] Va = 937. 54 : 8 Vi tV. 7 Vave "= = Vave = 970.2875 By Eqs. (6.28) & (6.29), AH = Vave-(1- B-T)-(P2- Pi) AU := AH ~(P2-V2~ PV) B AU 8 ns. ke Qs TAS Work := AU-Q 112