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Tue, ofie HR: apm. wef Thers 8532-920 tre ChE gon Elemas fC chap apes Wheat Chime cal 8 ction s f a chennool oo. mer bes thken ng hemted Resetn bynundg Chemicad endtmnt / nears a chemicgd enter > nea cts impale Cominer ro ot Poets of a portcabon rate 6 Mts iclenbity. he 6 chime end vr 3 men ways De cu mponeivn- i“ fo iN el Wh calc, (4 GHe Co [Semavizatinn. — irrangentint, Cae trams, - © Combe nace ) 4 GH, — —)- CHC CH)s Chew hee uns oa Teter oS Part cwlir Neutin pre ceesey van be expressed the rate of oapperanee of a Me bet, 4 np pent ce of a Proce of WN. wp DT chorat & chlor benrenk in poms te Chlorat 4 Merabenzne DIT HO 2A 4 2B "tas c4D chove A rege af react TA ones A disey perons = numder vf moles yA HAAN (oF ee) Pert tg per met wines the debs? = fhe (peseue vans -tas 4 mvt % findes Pe mrwtes C oppo per wry jing prow vols, Pes + (pusnuey & prvita et- Fee code Unie) Vig Ik hamiseny re yrs wy “thes vidy trek wan a pret cumple. 2 hatch system at & constant — volume 2 Wing ec & flow see “east AMaB> C+D t>.0,D oy A, scene om Oa, out, Assume S Stage, WRU omit spe. vA -flow rage in = velafiny rage ee Pit mw change im conection xf an oa Spring Howe acupr 9 we ke ime. then fr A reactor WG-0 - too. ~ So -m: rmart — clrerihe flow system. The yonerad mek belance ef ivetion G j= F Sy Fem volts Fie Fle = mole flow rape of sprees j wunw 4a systim. moins itis Out of > = G + rate Rene ratmn Tn = Ot 4 Generation = Accumulation Nps nrkee of j nas Fe- Fp +G@j - 4b Hf te pos iy Cenc, esp. etc) Gre vou form. ene nyokine MH the system. YI. rast of fometin of |, KSEE Ge y Tee valuing rol/ing = (volume my woth ime. vol) whelin system Uolimt, ne mact HE ry vanes wlth posteion volumes mK which 7 3 wacforin Mate Consilar ih CREmental + Batch Karr, 613), SPAY sei Om rnolwsery for Smad scale pera © Mo flew of readctasts (Fp=0) 4 Mo ostflow of procucte of unreacted reactants CF, 0) =a v oly eB] ines Uf the OT mivune 5 Perketty mixes shen rj is net O function of Vcomp +he mle ance — he Comes CS IN Hg i prods Racants, ime Ispmerctpn a beth neActor A>B Apply ol balince tv A well= mized batch new ctor, Ay fit = taAV Isuthinusd [etal conshttin Hy Na ot t=O want Nagy How ling to Na? tN. ty CAL nemaanly Lnncatet A] TV” fe ° ue May te [° Pe = 4, TASS : ie fm Naina Ma RV Continwous flu nee Crs, (ey csTR Steely state, well- nivel. Seam te meperatins 2 concentrocmrs the exit Stree Come tha Stmg Wh PL aes es within the sitor yohune, CHE 3700/5011D Chapter 1 wmf | Rote (Ou) x mot blence/ Chapter 1 Learning Objectives + Define types of chemical reactions + Describe types of chemical reactors + Apply mole (material) balances to batch reactors, CSTRS, PFRs, and PBRs (see p. 24) What happens in a chemical reactor? Chemical Reactions + Ifa chemical species changes its identity, then a chemical reaction has taken place * 3 main ways that a chemical species loses its original identity 1. Decomposition 2. Isomerization 3. Combination Chemical Reaction Rates + The rate at which a particular reaction proceeds can be expressed as the rate of disappearance of a reactant or the rate of appearance of a product + Ex. Preparation of DDT from chloral and chlorobenzene in the presence of fuming H,SO, + Choose species A (reactant) to measure the rate of reaction = number of moles of A reacting (or disappearing) per unit time per unit volume = positive value Chemical Reaction Rates + In chemistry we learned But this is only true under a specific condition: a batch system at constant volume + Why? Let's look at a flow system... The General Mole Balance Equation Section 1.2 Perform a mole balance on species j located within the confines of a system with specified boundaries 0 i System volume Fj, = molar flow rate of species /into the system G, = rate of generation of by chem rxn within the system F, = molar flow rate of species j out of the system The General Mole Balance Equation Section 1.2 But if r, varies with position within the system volume, we must consider incremental volumes in which r, is uniform in each System volume Batch Reactors Section 1.3 + Typically used in industry for small scale operation + No inflow of reactants (Fj, = 0) + No outflow of products or unreacted reactants (F, = 0) + Ifthe reaction mixture is perfectly mixed, then r, is not a function of V and the mole balance becomes Batch Reactors Section 1.3 + Consider isomerization in a batch reactor AB A ceceneernen tine, ncsose win tne + Apply mole balance to A Continuous Flow Reactors Continuous Stirred Tank Reactor (CSTR), Section 1.4.1 + Common in industry. Also called backmix reactor, perpetually mixed reactor. + Normally run at steady state (no temporal variations) + Assumed to be well-mixed (no spatial variations) “Major assumptions thus the temperature and concentrations in the exit stream are the same as the temperature and concentrations within the Fie reactor volume ; Steacly Steohe. operation ( no vara wrt tine), wells wired (lwo yonccin gave } > Fy ae Fy C—. hot sae of the weet, . but Raha volume where +h mcm os happy Continuous Flow Reactors Plug flow reactor (PFR), Section 1.4.2 + Common in industry, often for gas phase reactions. Also callled tubular reactor. Basically a cylindrical pipe. + Normally run at steady state (no temporal variations) (+ w<| + Assumed to be well-mixed in the radial direction only (no radial variations in velocity, concentrations, . temperature, and reaction rate). novelist aang Orth + Reactants are consumed as they flow down the reactor length: axial variations in concentration thus reaction rate + Plug flow = ae oe "je? Vay — BV, OUT ey Vem perfect SE fo 2g) pdv = rjav steady siete operation ay oy C7 ime bone. Fil, Filveey_- File 2y av w Continuous Flow Reactors Packed bed reactor (PBR), Section 1.4.3, + Common in industry for heterogeneous reactions such as fluid-solid or gas-solid, where the solid Is a catalyst on which the reaction occurs + Normally run at Steady Statd,(no temporal variations) + (Plug flow) and assumed to be well-mixed in the radial direction only ee + Reaction rate r’, is based on mass of solid catalyst W rather than reactor volume Vr, =" rolls A/ goa + Mole balance for PBR is analogous to PFR bg I) “ld ys bev c. OV Example problem 78 ia The isomerization of cis-2-butene to trans-2-butene is a first-order isomerization reaction that will occur in a PFR._ AB -ta fl), y= kCy a. Derive an equation that relates the reactor volume V to entering concentration C,,, exiting concentration C,, rate constant k, and volumetric flow rate v. Assume vis constant (Vv, =v), State all other necessary assumptions. b. What PFR volume is needed such that C, in the exiting stream is 10% of Cys if k = 0.23 min’ and v = 10 dm‘/min? c. What CSTR volume is needed? \j.¢ ovdir enctivm. odes om Example 12 (stents pot 6 (Same) Le pH aw Bla GeV ve Me a In bas Pree Pees lent hate nea ete sw0 din? oad, with mixhne 7hfo AP Wh inert. he 50% phose peacton 3 Creed out isvekermadly Ory Syste Aste rf ee o, ’ 1 ey Ne aoe hy, a. east ioleal gas [ae is vabiol, how many moles of A amg the reactor ats ally > bs Hf mmf > fast oveler -Taz bla, k= 01a Dime to comune 7 A co Hm Dru ole 3 eka. be? HS Calentate Hime to Comsume Sof of AP PD at thst © 227% Ara: a. Pus PRT. ; , Supe 2 22xK2B x [08 Pa rr an? /jom —_ u n es B3F mPa fok-K - (2274 2B) K~ PEMLY mobos > 5 MQ: e7cn> Paap mt B with the first order rate law ‘ e pe a = thE kCy - Ewk is to be carried out in a CSTR. The entering volumetric Ve Ta flow rate v, = 1x 10° mis and k = 0.01 s1. Whatiis the T,_| reactor volume needed for 30% conversion? X= v.3 -iye Ra = RBS Beate Gl) k Vo ve Fox Fre (HO ie on , > wy zi ~ ae - a _ (te 15) (0 arene = 9K im ~ “Row = Bdm= BL. Applicomss of uke Bn Gases see pow Macey, Sizing Continuous-Flow Reactors Section 2.4 7 How can we size CSTRs and PFRs knowing ~r, as a function of conversion? 0 Take a simple 1* order reaction “fq = KCq= KCg(1-X) As C, decreases the rate of reaction decreases. Equivalently, as X increases the rate of reaction decreases. ‘Therefore, ifr, becomes smaller, (1) becomes larger and we can make a plot... * Levenspiel plot I ep ane i) =ty Rea hor KD x ' Must be determined experimentaly hee rate. Note that as X->1 for an reversible reaction, and as X-+X, for a reversible reaction, [~~ Levenspiel plot 1 Why plot 4 as a function of X? Let's return to the CSTR design equation V = Pearroge v= te (=e f ) a of taconget Levenspiel plot Example: Suppose we have some data or a data table leading to the plot here If Fyq = 20 mols, what CSTR volume is needed to achieve X Aner singe < py = Ww x28 = 16 V= Faw CRY = wxib= 324 Levenspiel plot Now let's ort? the PFR design equation Ypre= Fre [2 te rN f wt l ff x ‘To approximate the area under the curve (AUG), use the trapezoidal rule, Simpson's 1/3 or 378 rule, eic. (Appendix A) or built-in MATLAB functions trapz, quad, quadi, etc. Oey 4 © Using a data table or a Levenspiel plot, the PFR volume to reach a , , “a esired Xan be calculated . >} PR TA, ya » CSTR. EEO rR tn XB ¥e. Reactors in Se: Section 25 S Let's connect reactors in series so that the output of one reactor is the input of another 0 Therefore, when we run the single identical reaction in each, we define conversion for a point downstream as Lomebehy nenctand Total moles of Areacted upto point mmoles ofA fed‘ rst reactor Conversion of A at point i = X; Only applies if the feed stream is fed(solel{to the first, reactor and there are no side streams cee Fas =u Fao Ki bow] ney le Reactors in Series Section 2.5 SHO Fa, = ho To = Fax = Fao ~ Faokr. Fa, = Fro- Fos, wale bel 1ST penctor PFR Fi veal mated rly, suns exte, y= (7 Fe dg yt CCSTRY, Wee mened veanily state Fr Fat Tash 22. Ue fn te = Frye Fook 2 mip me a -Tar rave balance 3%¢ PFR) % Fe tly Bag q ee \ i eel or an phos paweber of CTR Tee. will opperch vo PPR. ree L sane volene Bot -por PPR, no benef es, io Some Further Definitions Space Time and Space Velocity Section 2.6 + Space time (9) eerie TH Vi unt firwraee + Time necessary to process one reactor volume based on entrance conditions + Also called holding time or residence time * Space velocity (SV) sue Vy "Unt Ss tiny bse on eater enance onions Liou © SVL Volag tos. hardy 5Y Psy iis Vv Grsv . CHE 3700/5011D Chapter 3 Rate Laws Chapter 3 Learning Objectives Determine relative rates of reaction Describe the terms “reaction order” and “rate law” Interpret rate laws for irreversible and reversible reactions Apply the Arrhenius equation to find temperature-dependent rate constants Basic Definitions Section 3.1 + Homogeneous reaction- reaction that involves only a single phase eae + Heterogeneous reaction- reaction that involves more than one phase, usually takes place at the interface of the phases (6x. gas-solid catalyzed reaction) * Irreversible reaction- reaction that proceeds in one direction and continues until the reactants are exhausted + Reversible reaction- reaction that can proceed in the forward or reverse direction, depending on the relative concentrations of the products and reactants and the value of the equilibrium constant + Molecutarity- number of atoms/ions/molecules involved (colliding) ina reaction step. Unimolecular, biomolecular, termolecular refer to 1,2, or 3 molecules, respectively Relative Rates of Reaction Section 3.1.1 A+2B—Sc +40 + For every mole of A consumed, c/a moles of C are made teen) @ Ex. 2A+3B—4C+D A+iB > 2¢+ 40 Tes 2efay = -2Pa -T: 4re Relative Rates of Reaction Section 3.1.1 A+tp—tc+id + Similarly, Togo) rs a Ta= alto) Relative Rates of Reaction Section 3.1.4 + Ex 2NO +0, = 2NO, tye. fe LENO ee z Hf Pao = Amol /n- 5 Peps > beetle 5, for Os = Py = Yds, Reaction Order and the Rate Law Section 3.2 + The reaction rate law usually indicates the reaction rate's dependency on reactant concentrations (and temperature) “ta = [K(T)] [fn(Cy, Cp, ...)] Power Law Models and Elementary Rate Laws Section 3.2.1 + Reaction rate laws are determined experimentally (Chap. 7) * Powerlaw model i cs of + The exponents on the concentrations lead to the concept of “reaction order’ unclte wre A P croler wrt B. Mtb) order _merall Power Law Models and Elementary Rate Laws Section 3.2.1 + Ex, “th kC,2Cy Reaction order= 2 wrt (wrt 36 AA B. Power Law Models and Elementary Rate Laws Section 3.2.1 + Units for the rate constant k will depend on reaction order yon b= (cone n= Xn order wrt a aay ere eeee 0 ltt R= Wt iting | stoner ie ='/tme Zed vrler | 3 VIL adtions Nonelementary Rate Laws Section 3.2.2 + The reaction order does not have to be an integer ~TATRG G, tye AA AS VEO. Co an asiumptrs be made camignimint f am apparent react Gr Ga Corel Ta BY 3s apparent ist oroer wrt Nonelementary Rate Laws Soction 3.2.2 * If the rate law can be written such that the exponents on the concentrations correspond to the coefficients in the balanced chemical reaction, then the reaction is said to follow an elementary rate law H+], 5 2H1 Mon clumancttiny Warction TH RC, rete tam oy elementary + Elementary rate laws do not mean elementary reactions! The reaction may or may not be elementary, regardless of the rate law. Cad —2HBr ee ee abe Maud ’ Te Bon Ch Gh oR Ran omentiy ~ b+ Gbe/cn +t Gtr Ca, Nonelementary Rate Laws Section 3.2.2 * Note that heterogeneous gas-solid catalyzed reactions may be writen in terms of partial pressures spoluene + He Ee benzene + methane —T = kPa 4K foe CP “abs ra CRT hg IAaod 30s low where P= i Pye? A+B = 2¢ Sha i fwd: —TA* Pn ne teamemra caa (nar ee elomntny rae lw) ws: Tae bac 7 ‘ At qilib Tat = 0 = - RACE + bea Co pote law or Leireric Analy es ka. SO aareeat prevmsaruncy of rare oxprewscons Tharmodbynsan’© cd. Pra. Ker ake Py 2G He = Gato tHE 2B Es. D+‘ Ce iphsne pp vengne Gh Ais of ferret 0 nets Erne) te an, -forwnd = Tye be or bt -boe he = Reverse bool, Te wt = Tap +e = - BG + Bb Ooty et Keach terns of comsumaron. B, —Teat = RNG ets Se tee 2 GG) At eguctihnven: ae o= be (Ce bs go) kes GG be om pharma diynpanie> pees From emo ie ‘i — im) Bt att Olt DBE Ejubb. constfat = Fe = Cay ao, Reversible Reactions Section 3.2.3 + All rate laws for reversible reactions must reduce to a relationship describing the reacting species’ concentrations at equilibrium and the rate constants (eave space- los of board notes fortis socon) cae cow'stemcay = cede ere) CR Che a The Reaction Rate Constant Section 3.3 Reaction rate constant = specific reaction rate = k The reaction rate constant is not truly constant. It's just independent of the concentrations of the species in the reaction The value for k is almost always strongly dependent on temperature + Other factors like pressure or solvent may be Important, but temperature is normally the dominant factor There several relationships that allow calculation of k, but the most widely used is the Arrhenius Law kity= A exp(-Efy ) The Reaction Rate Constant Section 3.3 + Arrhenius Law states the temperature dependence of k kIT)=A exp - Een). where A= pre-exponential or frequency factor ictivation energy nwt. or OM. T= absolute temperature x vy °R. Note that the term (-E/(RT)) is dimensionless + Auseful form of the Arrhenius Law is the natural log form Wk: a ~& et sre = 4 Ine. 4 abe | | NS Wit it Ris known at some Ty, kit) = R(h) oe (E(t - +)] Cia ke Uh fen of T kT) = kU) exp Bette versal gas constant $3UF T/mdt-te. 1-737 CYP, CHE 3700/5011D Chapter 4 Stoichiometry Chapter 4 Learning Objectives + Derive stoichiometric tables for batch and flow systems + Calculate the volumetric flow rate (for a flow reactor) and the volume (for a batch reactor) for a gas phase reaction as a function of conversion Batch Systems Section 4.1 + Let's now combine the batch reactor mole balance with relative reaction rates and stoichiometry (and eventually temperature dependence of k) Attine: Attmet=t Naa Naw New Noo Mi Nu Nes Ne No + Species Ais the basis of our calculations Lutey <*4 moles of Aremaining: —Na-ninp - Nao X> Nao lI X) 2H where Na.X = moles A consumed (reacted) covet See Tab 4-1 forthe batch system stoichiometric able x ™ Nae (Im X) , c > Nav (OB~ Bx) oo it Nt Bay Br) . “Na (6yt Le. ‘Catan techs th umber fms gt Sy ston cums = Change oo sf woes perme A reacted Flow Systems ATR. PFR PRs Section 4.2 i + Stoichiometric table set-up is similar to batch systems, except we Use Fin place of N, Into the reactor i ee Leaving the reactor Fux Fan Foo Foo Fs LA ta BC + aD Fe Fes Fos Fi + See Table 4-2 for the flow system stoichiometric table For cewsting voles batch ancl crestanl volumetr © VeUy, yw get: ae gq: “e G* Go (8) Ke -kn Gs 4 «for prot — pom Mactan thin Ve or ve Vo, neal SL to demuat for volun vowintion, Lex) Flow Reactors with Variable Volumetric Flow Rate Section 4.2.3 + Equation of state. PV =ZN,RT where P= total pressure V = volume (or volumetric flow rate) Z.= compressibility factor (1 for ideal gas) N; = total number of moles (or total molar flow rate) R = universal gas constant T= absolute temperature + Atthe entrance P,vo=Z.FuRT (1) + Atthe exit Py =ZF;RT (2) * Divide (1) by (2), assume Z=Z, and solve for v ay [Fr l[PolT ' ET = Flow Reactors with Variable Volumetric Flow Rate Section 42.3 + Recall F,=Fr + FF_X from Table 4-2 F, F, A ‘the as ato =1+ jen Be tt aK = 1+ Yao To Fr taf — where $= yroih 9.420420) + What does Erepresent? One explanation is in the book for the extreme case of X = 1. For situations of X # 1: ¢: tele - . FRX ¥ aa a feet [coe Flow Reactors with Variable Volumetric Flow Rate Section 4.2.3 + Sub the expression for (Fy/F;,) into 4-16 ee and when Z=Z, T vet6]] eae cag preMune ae. of By isoheric syste) Dowe have f PoP, Do we het an vovohicwrsd S45} owe FYI: Batch Reactors with Variable Volume + Analogous to flow reactors, except we use volume (V) instead of volumetric flow rate (v) and number of moles (N) instead of molar flow rates (F)) + Equation of state PV =ZN,RT where tal pressure lume mpressiblity factor (1 for ideal gas) total number of moles niversal gas constant solute temperature + Attimet=0, PV, =Z,NrRT, + Divide eq of state by the 2"4 eq, assume Z*Z,, solve for V vente FYI: Batch Reactors with Variable Volume + Recall Ny =Nyy+NoX from Table 4-1 N N, , then —D =1+ “8K =1+y,,5K en ue & Yo Ne Nr + Therefore V=V,(1 + oF] =1+& — where yo and when Z=Z, vou ofl Variable Volumetric Flow Rates or Variable Volume + Coneevrgmions a ViatscVorine Gos Bae Sree ANote on Reversible Reactions + Stoichiometric tables for reversible reactions are constructed the same way as for irreversible reactions (Example 4-4) + Use thermodynamic relationships and rate laws as in chapter 3 to obtain equilibrium values (e.g., X.) Pag Eesouctiods Le eee mt oth — Arb, Fest oh He Pe 164 atm. come. T= RPC dk. Stor Chiomem RTs eoby daha T+ BUND = OL mdf Se RCA feed POW (ECE : = fee Eo Eee PV GT : Sitar ere € * Wb OSC“ Ze 5. voniiele volume, Cd edahe concentrat¥r Corefuily C. Cn = Co at X06 iS cps Gol Git LB 1 Coe Cae Ute heplest posture dp reser Ga OF meld aoe \ % a Tay =~ MB > bay COn)™ (GH) =a, = 6( Na flow system I re Cost yt bate - AyhK - X~)4 i q xX pbb Cr 4 (i x) -Ty =- Gq -eemer Bx Apes (eS etl + Reversble reaction fil prose + 24 onter in Rae ok Fewrge decors + Ae Te Book shevelue for KiB. Difg, = -25 C00 call and Es 15,000 al vel TTrermedyrenies dels ws Ge soothe mabe las se thermedynamically iensistent ® ant Ko 2 ke Howe MI sesumgon Ais dh can ese trie SSO epeesion deen ey ss fed Storhamelry” ROR Siem net FoF Only hae GGG), ear RE port is the of Combine res aa wale of XK? Cs bs e000 ot Te200k W160 a = 3,755 nt Psuurne | Sredy-shabe, wollemoeed CSTR. Ei (een me ec Tae Goto ae | Ce iid deity, content wheres) w A, T+ 320k, = OW arsdant[s-osf: *, oa cd BULA * Page2 Be nes T oat nes be ond eo =| Pasergy “erin” expemsion for ab Te BOK ‘i host, op [ee - @® ee op Ee (Le beat Commas Laie Com ft Kas ep CE Ce - )) ee ae Kom 30 ool Ue Ei) @ mide neo ned te ques-ard-cheds using aug se alate’ X, or eee oth ap Br when wing mening The are many says te enuangtdh asta, Ber bot say “Rite + © costa @) os Bet cep [Ce - ® po) 4, VO EI 4 tie eee and Eon il Page 3 where 2 ig equation (8) = use FGA), 698), 09 (8) te she for Hin ounlnear equation eer of Pimdh SBEPR , Mebine TB piled Be Te 30S K e043 de mann = The framed ration trtton donates of T Pea fh ee ax s a 3 Series cal = ABB IO 2 = FETE v $8NL 68.76 5. = ST bm Ss we = 0.0876 ty, Figure 2 grt usb eoor Example problem Agas phase reaction / ane A—>BHC va that follows the rate law " Ys ostdact Mowe msn Mf s rte Lov is to be carried out in a PFR. What PFR volume is. fx» *!°/5 required to attain X = 0.5, if pure Ais fed to the reactor at 10 Lis? What is the space time of this reactor? Tt gaKk Po= oa 5.2 Batch Reactors + Use the algorithm in Figures 5-1 and 5-2 to obtain the atch reaction time (te) reqwinesl £2 perform KeActin to X oF G . Mole Balance Stoehomety (= Ya) «xy tines rH 5.2 Batch Reactors + Order of magnitudes to achieve X=0.9 Tyme $2 Buren Reyenos Tes Fira-Onder Second-Order Reuntion Te his) AC (5 1) é lo lo Hours lo? lo Minutes 1 10 Seconds conds 1000 10.000 i * Use flow reactors for characteristic reaction times (t,) of minutes or less 5.2 Batch Reactors + Consider batch cycle time t, te: tet tettytte Tyaue $3 Twn. Creve Tse For 4 Bart ocean Process Activin Time Thai Tea ae ear aa RE 2. Heat to eaetion temperate, 3. Cany out eatin. & 44 Empy and clean reactor, 1s.30 Tw ui + Optimize t, with other processing times to maximize batches per day (or other time period) 5.2 Batch Reactors + Refer to Example 5-1 to see how the solution algorithm can be applied to batch reactors and to see how batch reactors can be used to gather data to run reactions in flow reactors Oem 5.3 CSTRs ee VER + Fora first order irreversible, liquid phase reaction under isothermal operation Ratelaw -Mn= k@ Stoichiometry (A= Cay LIX) Tekh ry Design equation Combine ; 0, Ve’ ve (Gm) ( 5) -la Gath - = Gor tz4 cane a T= GX or Go = GX Us ta _ = 5.3 CSTRs 83.1.1 ASingle CSTR For a first order irreversible, liquid phase reaction under isothermal operation (continued) Solve forC, Cy = to (o-F) Solve for X x are 6-3) BUR ADa = Demkohlor minder of ist orolir ek The Damkéhler Number, Da + Da is a dimensionless term that gives a quick estimate of the degree of conversion that can be achieved in continuous flow reactors Da = 120M. 2 te ofreactonat enranes a “entering molar flow rate of A ‘a0 + Pay attention to the|reaction ordeil because Da is specific to 1st order, 2nd order, etc. (kGV 2 Eke tk=D Vote 2" order irrew > Sait Ao blr = TRO U% grote ire => The Damkéhler Number, Da + In general, a helpful rule of thumb is to make woctin +P J IfDa <0.1 then X<0.1 hood ee ifDa>10 then X>0.9 —> sect wets Mi + Once again, pay attention to — because Da is specific to 1% order, 2 order, etc. Yo mot whuse DA Dae PP pret The Damkéhler Number, Da Firstorder Sy —— ooh chop vk Sat xe gonne noler v H oot / kT) aan aradaderesw TY, Figure 6.3 Fest ender reacton ina CSTR Second order s2 pop pig ya yi ‘Figure 6-4 Comerson as a function the Damchlor number hCap romienine CST. Well mixer coe 5.3 CSTRs $ sin a ok S3.CoTREIN Sees Cre Sa Se % X s cme ™ ob ™ said se E 7. %, _ Cutie, | WM Gey wit bod. Foci | We (Ge) ce. Ws RF BCs Gy: AS: Ge otk. CFR UR) 5.3 CSTRs 5.3.2, CSTRs in Series + Ifthe reactors are the same size (V, = V;) then 1, = and if they operate at the same temperature (T, = T,) iSobherpod then k, =k, =k Ge thas C= Tere vee—aT + So forn equal sized CSTRS in series. Te “Vp, that operate/ at ihe same lemperatiye (Ui Tk =k) then Cn: A, Tete Da” (an? Caoltx) " xe 1 Uy 5.3 CSTRs 532. CSTR in Sores Conversion a into of umber of GTR, vig De sc ST ce eect Number of tanks, n Coheewe X20-6, + When Da is large, then fewer tanks are needed to achieve a selected X + When Da is small, X increases significantly with each added reactor Tenens rake at enfin ce” (Tome 5-2 De book), Dax 5.3 CSTRs 5.3.2. CSTRs in Series + For CSTRs in parallel, the conversion X obtained with n identical reactors with the same volume Vis the same conversion X that would be obtained with one large reactor of volume V = sum of all individual tank volumes = nV, (see problem 5-2) + See Example 5-2 for comparisons of CSTR performance MA fod on amy 4 identi CSTR, Fail Se) Tai 5.4 Tubular Reactors + The differential form of the PFR design equation must be used when there is pressure drop or heat exchange ee. dh oi Fes Gy =f Fro Gig =~ TR + The integral form of the PFR design equation can be used in the absence of pressure drop or heat exchange * dh vs Ta w= Pri oh 5.4 Tubular Reactors + Effect of e on conversion Mae EY. Y= Vol it 2X), serve) ADW, “Ae aly scien rs a seo e=0) fore Curpengesheeviunesiou mn demnetngnattenece, P -4‘:5.5. Pressure Drop in Reactors 8.1, Pressure Drop and the Rato Law + In iquid phase reactions, pressure drop can generally be ignored because concentrations are largely unaffected by total pressure changes — + In gas phase reactions, concentrations are proportional to total pressure. + Accounting for pressure drop is especially citcal in packed bed reactors : D TP Wi Get (stoichroAv)X \) Po TE? | z Get (stoic x = Oe Rex ) Po 7 wd balance Frwy 2 -Ta2 FOE pp * P dep om pipes typcaty 5, wl, Honeprne Prep] “Paras XL, nage ge . wae of adecntes StH peocter ) 5.5 Pressure Drop in Reactors. 5.5.2. Flow through a Packed Bed (noon flow tute) os [ik tino = vn fiw = (9. Asbums idea 34% lw Ya CPPEK . pt Pe) Gustine and Solve for pe BE Uy (FE) ae. 5.5 Pressure Drop in Reactors 5.52. Flow through a Packed Bed simplifying yields 5-24. + But now we have to express the change in pressure with respect to the catalyst weight Reloe w to 2, woe WP Az) By 6-26. ere Cp “t ‘sobivla, soli ciel > erro eae NC & = Vobank of seach fr) guy ed 5-22, Day if kaye a) Ac @fe PS ES Tre t, ols 2 al Si commer CaN) Xx 1B (c-ys = a Fe ee Fret Faxdk = Fe C+ ~ Fy 52? 5.5 Pressure Drop in Reactors 2/. 554, Analytical Solution for Reaction with Pressure Drop ww £20. Figure 6.8 Etec pressure drop on Pa). Cy). ~a (0X (2. hv. Ssh as Sema ere 5.6 Synthesizing the Design of a Chemical Plant Figue E 8 Proouten ot enyene ea. ce ~ Fp Cr (¢-30) For isp horned operocton ougle wetor ik PBR ch. - do * (Pp) as FOL Hf E20, isrthermat. solve Hf. Crolyricrly Pp Y= Cb aw) 27, In class Crammple Packet hed rector cnet pressure bryp. Aion eo a bg? will be performent revekermatly om AL cabilar fret kel reer wrek Gohp of Selsq chaps parents pure A 8 fed co reactor wth Fae = & olf Go2nb/tns > {oat a be wk no op? LAssumprim Sop dew &= 244. Yr e214 rete low @ “TA = RG mel tlmct EK 2 w= Tro fF =i) St e+) a Ce (HAY Ta ds = Maas ko (fp) MC) we GB) d= ion lw. x ex Oo ae = [A be (+6) ln (a) - ex = AG ww alan - x= Ai = 25x py = bbs > x= 0b th What 7s rhe comversia 7f parm chop i » Sposa CLS a gps tm Srtaiek V= vob eb A Fre Rate law. Tale b Ca. 8 o UD C) 0 a 7 PIF _dadh = = atu of 2 -HorxX, 5 ey olX Re EXO) nem ha Tue (Pe ) accoustel-for ee owe. Gne ~ Fax. Fa Frio g thax. FX Yr +Tax Fax. | CHE 3700/5011D Chapter 6 Isothermal Reactor Design: Molar Flow Rates Chapter 6 Learning Objectives * Solve isothermal reactor design problems by combining lessons from Chapters 1-5 (mole balances in terms of molar flow rates, rate laws, stoichiometry, pressure drop) * Discuss unsteady state operation of stirred tank reactors * Solve semi-batch reactor problems Figure 6-1 lotnermal reaction oosign algorithm fr mole balances 6.5 Unsteady-State Operation of Stirred Reactors + Start-up of a CSTR is an unsteady state operation, ell — maxed, Tethered A = Tip Fy ATAV Accum = [in — Out + Rare porononin, Mast ist oNin rind, Steady sont. he Gre Hnk, 6.6 Semibatch Reactors + Typically for liquid phase reactions * a4 + Add some other reactant(s) to a vessel containing another reactant(s) eee) * Well-mixed Figure 65 Somat ace + Operate at unsteady state. DO NOT ASSUME STEADY STATE Mea bolrmee A. Flow ~ Flaw ont + rate penenativn = Acc. - dA(@y _ Ww a F ee DueroWd mans balance om Sy Steen. In — Ow + Rar gen = Accomm fio ~ 0 i Be as gm Contant olemrrey Liquid. f= fe Sy ee mete Ovo ve Mtwt. oy Sub sb) nto dA, - Veg Mery - Veen. ml be lane for Pe dCgv) Oh ren team Vole-@ , dl tet Wicea , Se yen [gnct om © ¢. vole. ee a doe re aie CHE 3700/5011D Chapter 7 Sections 7.17.5, Read sections 7.6-7.7 on your own Chapter 7 Learning Objectives * Determine reaction rate parameters using reactor data (see Table 7-1 for algorithm) + Analyze reactor data using the method of ‘excess, integral method, and differential method. (Other methods will also be explored.) Method of Excess + When a reaction i reversible, we can often determine the reaction order «and the specific rate constant k by ‘numerically difereniating concentration vs. time data + Usually this type of analysis can be performed when the reaction conditions are essentially a function of only one reactant: A— products Assume -t,= ky C; to use the differential method Method of Excess + Method of excess- run in excess of one or more of the reacting species Method of Excess ‘een 72 “oti tet ton em ay 4 mag) ee + Usualy collect concentration as a function of ime data in batch reactor, then analyze data by differential method Integral Method + Most often used when rescton order is known but the value for k needs to be calculated + Guoss acon order (or use krcwn reaton ode) + Itgrate appropriate sore equation Pot ata to get Inesr lations for concentration te ta 1 ioe nt inear, hen proposed reatonorer coos Sts “Try anether reaction oer ory dferentansyae method A — products Constant volume batch reactor (V = V,), wellmixed, et Mole balance 14> “MG Integral Method * Zero order rate law -1,=k + Combine eek + Integrate fac, = feat Ont Colt ys btm Ve + Plot a8 function of, sone = kag, Integral Method 4 Seon + tstorderrate law 14 kCy {+ Combine, integrate, sotve 7 : or Ula) | nen ; [Heaters teens re OW nG ~Ta= kCa da LO tin = b&w es Ph -bq Lagu prow. A>BHC m® GTR wMuinr well ouxat Stuady sade, Comper f eve V=Vs ~The & ka (42-0 Cao, = Coo Cox vec ae le X, = = ph Golx 2 - Bo-& aba ea ete Foes fe 2-¢a keg = Coe Wnkid = in (Si) es Le BSc 2 slat tel ae! . t acon ee ual (nk SH. 6981 b= 0.0077 ret [clin frm ERC mh elf, in. Differential Method of Analys + Diferentate the concenzation-ime data + Gratien 1 Netcare {Beason pont ta pyc + Graphical: Pot “22 as a function of tin, then use equal area diferentiaton to obtain “4 (Appendix A2) oG. Ae at Ne Differential Method of Analysi Sexton 19 when f~ ty At Tes po ln eon Sn at i wont (eg 2 eT ast pant + 2nd order rate law 142k? + Combine, integrate, solve + Pot 2 as afinction oft, slope =k Integral Method estan 723 dott % oop 2 — + + Perform the reaction in a constant volume batch reactor fawtdrn Differential Method of Analysis, ‘Seaton " charveel ready culos “Aarvakiys Dm dada 1 be isotheraly, record concentration asa function of ime nes (Tae Ratetew Ta = does bn 4g), tn“) sink + olny ba Gy wc] — TAG Differential Method of Analysis ‘Seaton + Polynomial t= Fit the concentration-time data to n order polynomial using Excel, Polymath, MATLAB, etc. Gta tats age tt ae doy t a+ 2nd Haye +. nae we + Diferanial Method of Anahi of Prssur-Tine Dat (Ex 61,36) b AC ott Nonlinear Regression ‘ieton 78 + Search for parameters that minimize the sum of squares of differences between measured and calculated values forall data points manag Z Cinay ~ Gy y* for oot + Particularly useful in pharmacokinetic analysis fpr pow » Method of Initial Rates Particularly helpful when there is a signieant reverse reaction (Le, reversible reactions) Ratois measured a a varey of nial concentrations of Species Aoniy Atthese inital times reacion behaves ais ieverible Experimental intense method, Need ~fy a ach Cy, + Hale of a reaction (ty) = ime required for the + Can be used to ind reaction order an k Method of Hal concenivation ofthe reactant to fal to % ofits inital value Consider Sonate taereacer cpp ert aed * (Ch (using metnod of excess i needed) Ek aaekey Meare ty fora variety of Coo, Ssutherepl Find that fits data 3 | SSS ‘Rt Sete hermano on seatie mt pt Integral Method of Analysis Erampi 2 Fogee sed + Ex. 5:2 (Fogler, 3% eq) Use integral method to confirm = 1 Some HiR, SOML ARH AA ty VK S-1, A> Btr¢ Bes pe oap-Py Lat fel Potegratt anh te ont Pf, o> pitt Jip (neg) =k * Integral Method of Analysis ample 2, Fog 308 CHE 3700/5011D Chapter 8 Slides for Sections 8.1 - 8.3 Other sections as board notes Chapter 8 Learning Objectives * Identify different types of multiple reaction systems as parallel, series, complex, or independent * Solve reactor design problems to maximize the generation of a desired product and minimize the generation of the undesired product based on selectivity and yield * Solve reactor design problems involving muttiple reactions by writing net rates of reactions (formation), rate laws, and stoichiometry using relative reaction rates, followed by use of mathematical software to arrive at the solution 8.1 Definitions Section 8.1.1 Types of Reactions TIT]A SB me sey eect + Parallel (AKA competing) ane. AB AC * Series (AKA consecutive) ABC * Complex A+B—C+D A+C—E * Independent A>B+C DE +F 8.1 Definitions ection 8.1.2 Selectivity and undesired reactions hy ex APs D sens ASD y t aSu + Want to maximize D and minimize U, which allows us to keep separation costs low * Selectivity- ratio indicating how one product is favored over another ; Fo. _rate of formation of D Instantaneous selectivity = Spy = +f = ate srtomatoratU Fo. _ Exit molar flow rate of D Fy = Exit molar flow rate of U No Nu Boch neucror Overall selectivity 8.1 Definitions Section 8.1.3 Vield * Yield: Ratio indicating how much desired product is generated relative to a specific reactant (eg 4 i fo _ _rate of formation of D Instantaneous yield = Yow, = =.= fate of consumption of A Overall yield = Yon =wachi= “FmaiA consumed PMO F, Fon = FF, flow he ctor * Note: ForaCSTR = Sy = Spy veonvou J 8.2 Algorithm for Multiple Reactions * See Table 8-1 (Mole Balances for Multiple Reactions) for quick reference to mole balances for batch, PFR, PBR, CSTR, and semi-batch reactors + The solution algorithm for multiple reactions is similar to the algorithm for single reaction with the following modifications (Table 8-2): + Arate law is needed for every reaction * Net rates of reaction must be written for each species + Relative rates must be written for every reaction Rates step 8.2 Algorithm for Multiple Reactions + Rate law needed for each reaction (for one species) y= Kj f(Ca, Cp, --. CG, -.. Cy) + Net rate of reaction is written as formation for each 5 Os co tat Cat loat tant tty = By 5 featathe thet. tie = Bt In general 55%; where i= reaction #., j= species I * If the species does not appear in the reaction then the rate of formation for that species will be zero E42F—>G —— reactiong For species A, .,= 0 8.2 Algorithm for Multiple Reactions * Relative rates of reaction * Recall =A+2B—>£C4 D per mrole A bene 28-8 -B, poms debssle rence * In terms of rates of formation for multiple reactions e-¥ * Example Reaction 1: A+B — 364+D Reaction 2 A +20 — 3E Rares 5 . SS a qune dm pak wh Ge I AtB HAs 3040. Mia saben Ca Cy iy " De A oor aig =- BA Ca CE ZCin Pant . Mw c arte Fur nm t 2 Tint Pag = ~ BAC ~ be Rae Kia = tq = - bana, Ne = 3l-Tia) = 3k, toe - Tins kn Qe re? By, Bes BE Te = 2a = - hea lace Pat Pens Fa - Ty Not Be =~ ben CaCa, Te = Tre + Tac = Bhim Cala ~2Ran aC? Ty= T+ hp > knca®. 5° : Vee We +tee= FRealale - % camplse set of eapresiom reve baddam cn. (oops mh "S861 “HO “¥OPTY “HoH soup ou, ‘OM “STW “FAEUS HO UTEASNY pur sams poy. LiaseG JO soneund ssoorg paw sotauy ston “a -W “Kpsog wou) 295 alLs)9 Z = 214 my u/,91 = 243 Sue sau OF + OC— = == ‘youd “Suompuo> se d2ons aprow wogs> puE u=BoM Jopun aEUS ems Jo siskioud yo wounmesow an2ury USBHOSTON “Ot TUADU, cove ooet ° ° 2 ° ooz 3 $ 3° é $ 2 o 3 oor f 3 o coe ® coe uopsnmad nia “S361 HO “Bory “WOO “sso 9 9 ‘otegS HO UeNEAEAY pue sams pau Way og s2ooig pur snoUry BARA “W'S WOK) "2541S = ams oy suic,or = ames Taney sau oF +02 = aN ase “Saoypnoo re dans aso uoqies pur uSBas}u J9pun =e PUTO quo Jo s86eu6d Jo awamRseRD DUT UBHIOSTION 6 SPHNDLL spucses ‘outs coor cose 0008 seunaeasdues 8.3 Parallel Reactions Section 8.3.1. Selectivity be ASD tp = koe Au Ty=KyCR where, and are positive “a= fo + tu Aya Koh + KC — bot ko Ao Spy ~ 2 = 92 en Sou = Te tek 8.3 Parallel Reactions Section 8.3.2. Maximizing the Desired Product for One Reactant + Case1 a, >th Jer AOR whne 05D, thon Som = HR > BR CR nohe Sifu Wefe Bash Ca ay gh oo fren *Case2 O>%, barra. where 615.0), ee - T Te Oe bah hep Cy 5 lo oy por 8.3 Parallel Reactions Section 8.3.2. Maximizing the Desired Product for One Reactant * Case 3 E, > E bp (ths Br) menense “POSCrr hom by Cth wih Incnomse T, ot highest poss sncetienae, Sips’ ct 9p safety IK mand) + Cased — Ey>Ep Operate a (owes prosibte ~~ wiprtimde Sopa but T immst be Kh enagh pr nin to pres bie temp +? 8.3 Parallel Reactions Section 8.3.3, Reactor Selection and Operating Conditions * Consider safety, selectivity, yield, temperature control, and cost Figure 2 Oiernt actors and schemas ler minimizing ne unwanted Example Problem Consider the following parallel quid phase reactions AB with -ry.=k,Cy kats! 2A—>C0 SrReECH kp = 10 Lmol-s) in which Bis the desired product and C is the undesired waste product. The entering volumetric flow rate is 1 L/s and the entering concentration of Ais 1M. ‘a. What is the overall yield of B? b. What is the overall selectivity of B? ©. What is the volume of a PFR required for 95% conversion of A? fore) | ARSE) - Tab -TR= RG Undssred AC. AL canes rash pO Coes een cal iad eas my Tse thermal x75, ee a dp, de. rake balen Bem Grek Geek -taz Tat (- Ba) 5 Tre Tatha ler Tete reobd the. m=: NB. g2-Ta easel magedicoy = -bs (-AG) = OFhG. dijav = ra CC hta- BC, mn Ww (ae a ” l. Sharkey * bs a ence ol CA, o Vey So Me ones eee! 1) Selle ee vr = Ow Bia f-Fa df = ba vw | a eo bOtkG ain > —aka Ww bela - - aa. tana aCe. & bole s° [° do, |e * a wg A ej enl 4 Col) 2” = -@ GroHim. y Pz Ve rae | C. Quorad enective] Bal Cc. Sore. = Fe Co. bh. d Similarly to pat B. See =e oie ye RL oe dee ae eG ae thGQ c= ("Ske da SRA WS — Consilin “tree, Boatehp, Semi —bevtoh (umrteury sradg) ~ eo Pee. CSTR) — "PRA TNS ; ba Mad dime. G L + G11 Eleminns — (rmodrfiot, a, BASE. 1g phose. Botch — neater V= lo dw’. bus Fol mat. at Yo Kk, E 2 PR thm, a= 468 mat ct SK. Bs 70 CH /od, Pepe ee an al Hane 2-790 Thm. 9% Assume SHR One — OPPOK OMS Omt Jos Wek Che 203M. Mi Gy > CAatGrceyV (>?) GE] Te - Assam weut= wwived, elemortowy rote lov Osten, Vi, Constant elon ey no pho change. A. Aoliatweric operation ta, bo, Cor % fens of TT. tpi), b. Uas tao TAK UA = Go.0ve T/uin XK. UA = [00,070 Thmmrk, Tas Wo K oastont. aks ; : a B= 0. aglirbotic, Assume Weed, Rose low Tas ~ BQ. To: kyCa- be Ce Te Cpe Be. Md bolima 2 - lathe. : Q@. Ao Ms ot ta Ce oem ces Re * Airhomus . be boop LE (q- be be op ld (ew ce AL. B-Ws + SryjvoHeat ) /zavepr. CHE 3700/5011D Chapter 11 Sections 11.1 — 11.3 Chapter 11 Learning Objectives Explain the need for the energy balance in chemical reactor design Explain how the various forms of the energy balance for adiabatic reactions are derived Solve reactor design problems involving non- isothermal adiabatic reactions and interstage cooling/heating Rationale Section 11.1 + Ex. 11-1. Whatis the PFR volume needed for 70% conversion for the following liquid phase reaction A—B if the reaction is exothermic and the reactor is operated adiabatically? + Mole balance (design equation) + Rate law — clemitony pote lover but because the reaction is exothermic, k is changing Tas Rexp(& Rationale Section 11.1 Stoichiometry \p= Vv, Ca= Casttx) + Combining lk _ ah th + Energy balance TT, +S2x The Energy Balance Section 112 The First Law of Thermodynamics Section 11.21 + Continuous flow systems are open systems (mass crosses the system boundary) + Energy balance for only one species in and out ast ensttorct —Rawatvok sere taba sey Seere Dene ea ees ecae g , poe = Q-w nbin ~ Pout Bowe F, a 4 a Se --W+ Fer EFL ac Which will become eq. 11-27 Q = We ~ Fag? OC F(T-Tie)— [AHaa(Ta) + AC(T-Te)IFaoX = 0 But how exactly? Replace terms in 11-3 with relationships from thermodynamics... Evaluating the Work Term Section 11.2.2 + Start with W, which can be separated into flow work (work needed to move mass into and out of system) and shaft work W, (commonly stirrer in CSTR, turbine in PFR) SrPvl,+ BrrtL, + we a + Combine with eq. 11-3 to obtain Spe =O -W, + SF(E, + PV, -ZR(E+ PW), cv + Eis essentially equal to internal energy U, + Recalling from thermo the expression for enthalpy H, H.=U, + PV, Evaluating the Work Term Section 1.2.2 + Enthalpy into or out of the system by mass flow FH, =F,(U, + PV) * Combining i at Q-W, + SFM, - SAH ear + We can use eq. 11-9 as the new starting point for developing expressions for the energy balance for specific reactor set-ups with heat effects Overview of Energy Balances Section 11.23 + See Table 11-1, which lists forms of the energy balance that will be used with mole balance, rate law, and stoichiometry + Eq. 11-9 is the starting point for developing expressions for the energy balance for batch reactor, PFR, PBR, and CSTR with heat effects + Following from Ex. 11-1 ~ra= kiero (a, - t)]Caolt-X) Overview of Energy Balances Section 1123 + Now we can generate (-Fa,/t,) as function of X, or equivalently a Levenspiel plot _ wm X-— Ae T — PU RIT) -m =i eet eae rat te 7 + Better yet, use MATLAB or Polymath to dolve coupled ODEs or systems of non-linear equations Dissecting Steady-State F, to Obtain Heat of Reaction Section 1.31 + Atsteady state, “S22 =0 + Now use the generalized reaction At+gB—3C +3D Ia 2 ZHivFie = Aa Fae tHiokay tHeoFeo t 4 owt? ZH = HalatHe ht rbot Hoh Hy Fr swickemiseg Fas Pe (40, ee G Ene Fre ( Bp- BY, et" Ene (Bitvy) Dissecting Steady-State F, to Obtain Heat of Reaction Section 11.3.1 + Sub into the flow work term Hy= he | Hie , (Az, -Hi) 01) + (Hor Hy Oo TH ~ - (et Sey- & He - Ha) Fox & oR T) + Steady state energy balance (eq. 11-16) We ~ Fao, OHH) — [AHae(T)] FacX = 0 Ha)+ Her He68 + Ho “HOP. lfbe ‘po be Geld Dissecting the Enthalpies Section 11.3.2 Neglecting any change in H from mixing allows us to equate partial molal enthaipies to molal enthalpies of pure components H, = Hi(Ta) + AHoy For single phase reactions No p!vst hay H, =Hi(T,) + [[CpaT (1-19) + But we need (H,— H,.) H.-H, = Cy (T-Te] Steady state energy balance now becomes eq. 11-22 Q -We ~ Fao3,@Cpl T-Til - [AHp(T)] FaoX = 0 Relating AH,,(T), AHa,(T,), and AC, Section 1.23 + Heat of reaction AH,(T) in equation 11-14 is given by ‘summation of enthalpies of each species Hy = H(Tp) + Cp (T-Tr) SH pq T) =H MbtT) + Set) — RAD Hac G PHT - HRY) + a ma fer — Kop +e 5 Ope ~ 46> - Go] TT Si + Steady state energy balance Sas eq (11-2? Q- -Ws - Fag OCF (T- Te) — [AHp,(Tp) + AC (T See Oo ertegTed. @. set ‘en Adroborre rectors ae ye ws? Ofte. wy 7. Ke ; wally Cp (T~Te) gig. ey te = Gi Ge (Tb) / ea ar) Advabeie guts beam Qo: Reworsbie noms, Hipst Cope puersbia nny 3 Xe Xe r wel TP Saledtrmic mii, Kel wth TP. evotherme mma - Fist orley wk Ne UI), nN ae Erwthernie, ke fen 1 ’ Uptibrem. -_. > Te oF fet sonapirot. . Ses ar Ke 5 Bed 116 Te a * fe “Teta Es rasta mares are Bp. a Kanan} — engl di i bse TSimnian rte, 6 Adiaberic guid P : SH pg = 767% You bots, fered Gpustema 40 sso butane A= DB G4 FD ao 0.6 8/h3 Fg oe a 21h Yhek : weve Gu = Wh Tt, lo bed ht. Ge = 1 Taal Keo mh od 60°C E= 687 Vou % Assume staatty — STM | wel) mrcesl wala, thin rede (ows, Wo phos change Umer Villon, V = magn be Ws, magigihe Fecicaamcmcan i ar Mat badge In my =U Rose low ~ Vas kia-&) be bo ep Cte 7) s i » tie, I ber cb op Be eh Seaiohe C= @ (rx Ca? ox = Cy, combine? Pye bow i te) Ms Tarrpy bebnee. & = we ~ Fro 563 Opi (TG )- PX Heal Te) 7 +6GCT- BY D> Go Ga 79. ports tl Teh Leb Hey 1X =r Cpi Fro 2 OP Fr, of (1 OA) = 16 Pht, SOG = Gat Or Or = HI +> Ta cyan reer - pe tet (6%2 Youn) ISP, f he 34K orp [O22 1 P(e GeO) a ; bie k Cet cia gu «(3D a)! At epulitriens —Yaezo = Re Lim (HE )X] . Ke Ye tk dk CE Fame C8 onan Me = CD Adiobaciolly om PRRs ih sues witch intecstape colty GpPes, 3 calers, mA wfor Koo PPI a) bre, = 32 Moa, Ke = Sumo oA SPC, dn Bk Pie On? Gaz Ge = One 26 oy 0 paninumn 7 227°C .= Te. Tae Foo = lomaifinrn, Assumption Toleed fas, noghs ble Pao fe danpeoes atjueptom Stenoly roe, roid ma wrY Asretactomy meten lots Seo ichsowd bp: oe - Cae Cpe Ke> Keverp | Het sp - 7) EAY4mS = PS x9 0 7 G= Gel eX) = (= Cm (6-4) CorCe = BOW er peg Goke CaM x Cho (YD oirte) ee Noe (eo: Be Sealy SR amenos Tray botnet. 7. oe Pa aS - Gt T= Fey See Ton afpiT TO 8p lp Sas +4 < oe a SE Cp (T-P) = (Ca 4% 6) (TT) > Mi twmevator mm om bad Zorg (TB) = fe CT 300k) 3/23/16 1 Suadly - se than AUT wre hoot orekonnpe oe bolance om By wh Ws 20, (axums $5. welomixel OV ), _ aE) ab rZhrily- FH lee Fron Hat tor aR = pap (Te 7) we wansh CS garde SBN amb at Ceres oe oe. oacS OV = aay. b@ = UaeV (Ta~T) Sub moo 2-1. Divide by OV, take OV >? yatta) - a2 cho S & = -! T NI Io = ' i uf & He > HC Ta 4s q- Te? ZVI gs aH fy dcp T dG aor) amo ay 1 om Be yes or Gab eo 1 aad nasrrenpa// ay | TA OHey ~UatT- Ts) shGi By >Or. chen TT o vt x Pasetyn, QE Bg, dee TL os UP (Qql >[Brl, eT Lo vi aa eee wher [hr] > 18g) she T Pow vif de Renmwry — penotion Expl rsa. (mre vethenaic: mac Ga. 22 3/16 - ee cad ewes ne pe 2 oh a 1, Ta. Dug ulted vo het tranefer a spewed, gaat alloted all) =BQi Heat evckooge —_ Ge. dia . Ua T~ bd pe hae ae ea 1c ; the hot vie yp rac lons! fiat» vis flow t POA of “coven Cowdin cursing? AT oe eR Ta 7 Costing wher Me jg vey fange Brgy bee ge bo Tey, prettier Ee gongs, Wet asicmchoeee Of gas phae> ae fey. 7) Me bakin ce CHE 3700/5011D Chapter 12 Board notes for 12.1-12.3 Slides for sections 12.4-12.6 Chapter 12 Learning Objectives ° Solve steady state, non-isothermal reactor design problems involving heat exchangers and single or multiple reactions ° Identify multiple steady states and... * ...Solve for the operating conditions in non-isothermal CSTRs Example Problem The following liquid phase reaction is to be performed in a 4 liter CSTR: A+B—C The entering volumetric flow rate is 1 Us, and C,,=Cg,=3 M Additional information for the system: AHp, = 60 kJ/mol A C, = 4.2 ku/(mol-K) k= 10"(-AE/(RT)) Li(mol-s) AE = 100 ku/mol a. What is the operating temperature T to obtain X = 0.6? b. How much heat must be added to or removed from the CSTR at steady state if the feed stream temperature T, is 290K? CSTR with Heat Effects Section 12.4.1 Heat added to the reactor Section 12.41 Energy balance on coolant/heating medium in heat exchanger (jacket): peas" homity . Ramaaty (> Saati 9g wresu' regu tow (=) Seseeon, = ee 1bng = M_Cre(Tar-Ta) - MCpe(TasrTa) - 9 1215, Now solve and get Tay = T- (T Ta) exp( ree ) A Lee Solve far & Os AtTB—> Cc, assume YoY, welmmre Sus SOA. Convent PP Lead. Cbementony rate [ws MwA bad 2 pate law, vetek | Fak ~Ta RG Frye Ge Vo ve poe be Getege + (0°%p( et T= 36s k. Ab Hf Te = 2K. pow mach haat cho we newt to sel En Bodan 2. RW ~ Fay EEG: TT) ~ [4H 2x (Te) td CUT ~Tal)Fix 20 eeeerertieree cee eecenenenane (Te Psy: = DH Re (O56 ey 407), oy meet arstnom, — G2 Fp (To To) +0 Hex Fok ds 2h ( er BE) abo ae EB has Fi af. If wa want ‘sottemoly, To36o%, whek Q we nawledl» Heat added to the reactor Section 12.41 * But for large Mg, Tay = Typ = Ty thus Asse lOnpe wik $e Q= UA(T,T) eq 12-20 + Now with this Q expression, and if W, = 0, eq 11-27 becomes eq. 12-22: cnol Ooo, a Ah) + 30i Ge (T-B ~ T -oHe (Te)) * Use this expression for X with the CSTR mole balance to size reactors. See Table 12-3 for algorithm. Multiple Steady States Section 1235, + Consider a 1* order reaction in a CSTR at steady state + There may be more that one set of reaction conditions that simultaneously satisfy the mole balance and energy balance equations Xe - Tal, combing artle iy & A + When more than one set of conditions satisfy the two equations, then multiple steady states exist and the reactor could be operated at any one of them aca tale KTat Te eee Xe GLK) =o He Multiple Steady States Section 125 + For the sake of simplicity, consider the situation in which the following quantities are negligible, or W, = 0, AC, = 0, and AHp, = AHp, (because AC, = 0) + Thus the energy balance eq 12-22 AA T-1) +20 C,(T-T) AH (Tadl becomes pry —X SHpx =Gcirtye T- Te) Multiple Steady States (BY) Certs) = (tO (ET) Tee @ ct) = ROT) hast gen = hat Remove by Ea or het enchay? se Operoie GTR at pes wher? fivtirseer OF Ore fomient 40 ak think Heat-Removed Term, R(T) Section 12.5.1 * Vary entering temperature T, + R(T) increases linearly with temperature (straight line) and slope = C,a(1 +) Bev) = GalttOT> Ret) bp Ren * Vary non-adiabatic parameter « ‘+ By changing Fy, or heat exchange area A, slope of R(T) changes ‘as does the intercept with x-axis ee. Rit) | | xno by Fm ofA Heat-Generated Term, G(T) Section 125.2 G(T) = (AHA) (-t,V/Fag) = (-AHB,)X 9.12.31 For da boltmee Be. dep orelin Wngwid plow TS vs Fuk. WGK pas Th ba bGolepy GiT)= ~eHi TA eHp Mr) 147A op (- 7) riven = Bxhyotm Curve Section 12.5.2 Am.6e Fe. ocr i eel eatcenesaey mee Contr Peterman ered! meee Iga Bence OR Heat-Generated Term,.G(T) Section 12 5 ommmeee wet emen Task «ooh J 34 x ape Figure 1218. Tenpsreue liter exten cans. Heat-Generated Term, G(T) Section 125.2 oaeras coe Figure 2-4 Stub of mut steady state omperanres 5 Non-isothermal Multiple Chemical Reactions Section 12.8 + For q independent reactions\and m species ¢ dt 2 CMP [-oHpe T)] ~ US HT) PRR Gps _| ZAG re = al costa O- Ws Fu 2,8) GiCT-Te) + VEEN 23T Chane crate, buntt Why 13 Guswe + Use MATLAB or Polymath to solve systems of ODEs or non-linear equations BHpy (T) 0. i 5 i i H : f i i PER Volume (a?) | Ia pomntily i-a | A+B 320. Nic = be (AG. 2B4+C—2D Poa = 20 Cpe. MPFR wth het onchange ot Toor. Cys nt Cpe or. Cora dS. CG =tt. matfy Un = Patz. Lk. Fro lomed/'s, | Cn = Goel. = 32 OL/ mae Ca Yo AM fmatf . Cpg 2 1°? WU / rate, OMPyin = — 581 299 Ch fet Spy OPV A/ rt | Tas SYK. cfm grap be be (@® PA By Enirgy bem At. WaT) + ZV (oH) L dy LAG. r di. Uatja- 1) + TA Opa) t 6 SHewp) Cg SFr; [oeeecnns rea i) a DT oe : En hetane AT Uai Ta T) + Mg AH ex + Re SHowro oly A mae has - te Ny = -2he hyp 20% Umats exp Lowk (be -=) kp (Sok) = OW L/int. tha = [+ Ualfa-T) - Peottens | / ota = (lo Ma Lek. (grr) + 2x KO. 2KO.E X57 ) /_ ovo 2-0 mAs, @ 0k, 7 Ln = 2x 0003 TascheA = -tkeG > bet Ge aa ae he (979 bre 4) 743 Lfroet-5) & CHE 3700/5011D Chapter 13 Chapter 13 Learning Objectives * Solve unsteady state reactor design problems involving non-isothermal reactions and heat exchangers The Unsteady State Energy Balance Section 13.1 & aoe P dt =O -We + Fits ~ AFH, (19) + We can use eq. 11-9 as the starting point for unsteady state reactor operation + Apply assumptions: w0ll pixel nag lagrble hangs De prteatiod or Bnet 2nenpy” Sol Pv 3 nagtgrble, Cp VMUts ort vonstants, And the energy balance becomes... The Unsteady State Energy Balance Section 13.4 aGn T= Ta) 1AM (T) soy TRG . ., where DCp ~?. SINGQr Mio pt = Nw BOOP! = Nie P= ste T+ [AMP a Tat, The Energy Balance on Batch Reactors Section 13.2 af OH Wem (Mig =PF) a gone (3-10) balance when the number e.tather than the conversion. X. The species ata Ne Nau(@, + ¥.X) Consequently. in terms of conversion, the enessy bal OAM Ta) asin dN EOG,t SGN Equation (13-11) must be coupled with the mole balance a Nag = =ryh a6 wo Gt = nr 8 Adiabatic Operation of a Batch Reactor Section 13.2.4 Gs 0 awd Fiv2o, omdcssume Ws +0 G - Sco Te Sop x2 GD 2HGITH WH 9 ee Exangy boomct T= Tex f vette (JX By ZG Gr + Foep. MA bed Nn = -IaV + Use Polymath or MATLAB to solve a system of ODEs Non-Isothermal Multiple Reactions Section 13.5, + Batch or semibatch: RG Ts TH UAE WS FV Mgt S, “a £q 13-17 a Bec, + For large coolant flow rates wie cost pad WH on Og - Or ja + Use Polymath or MATLAB to solve a system of ODEs CHE 3700/5011D Chapter 9 Sections 9.1 - 9.3 Chapter 9 Learning Objectives * Explain the pseudo-steady state hypothesis (PSSH) * Apply the PSSH to biological reactions involving enzymes Active Intermediates and Nonelementary Rate Laws Section 9.1 *+ Many reactions do not follow a simple power law model 3 Ex. ~ bCH Cr Tbe i Cue, t ba Cor. * Such rate laws usually involve several elementary rate laws and an active intermediate(s), high energy molecule(s) that react(s) almost immediately as formed + Presentin very small concentrations ‘+ Formed by colliding or interacting with other molecules thereby transferring translational kinetic energy to interns Pseudo-Steady-State Hypothesis (PSSH) Section 9.1.1 * Because the reactive intermediate reacts virtually as fast as it is formed: ss ay ° which is referred to as the PSSH * Experimental observations are used to propose rate laws and test postulated rate laws — bh Gee) Cl Bs(B Goo +") Pseudo-Steady-State Hypothesis (PSSH) bh. AGie Section 3.4.1 C42 Boe! Tom 9 _Sitrsvo Dep A Rare Lae T Propose moive nomena k Gre i > 2. Propose a mech, ing he ite aw tie fro experimen 2 Ae 4 Afr wing ris forte of Fama of dosed prs, wr he aes fo b'caze t 1 <5, Wie ent rac of ai rhe sive nemo an te PSH. 7th oa spss brite avs by Sling tes = > TAR, pent ebervaion. same ew mcs mt covers. * Ex. Decomposition of azomethane (AZO) to ethane and Np (CHs),Ne—* CzHe + Na AZO —> GHerNe. From eypes Pe ABO ae Py 1atm oni % Geof; Trsrts = Ro Cag, at P< Sommty Porte = Rr? Cadp Relative pares ~Treo = Peng thao = PGA obeenved rae lly Troe +R Gao Ae haghe P tape Conc). k Gao >?! 0 PN roy Pa ocd (cone ae Rn Cae I. Propese cotive Intermashiont An Gi, Take of formes ef Proelact oan a echamas in Pok= b Car Rant. A201 ADD Ay Aro sazgt, 5 Apply PSH. ash =0 Re 2 A2o¥ +20 4S azo +20 tabo =0 = bh GS -A Cao Ciao Revd. Arg* _& Nb ~bs Cao Caps: Rearrange t? jet Wo . 3p. welte FOR fins cation element nat on the Wee blaze > Go = TB. , he = 7 abt Are, 6b Gado ot mae laos ( proclnct oe 7 te Be ~& OS ore = by (BG) ft. Searching for a Mechanism Section 9.1.2 Speci tv ncenaion(s) appearing ths door oe ae Tw profubly ele with he active rmsrmia for sarge A+ 1 — [Collin procs 2L1Fs consant appears inthe denominator. ne of Sa easton ssi probe ‘by the sponancousdaompositon othe activ incrmedate for example AY —+ (Decomposition prods) 3. Species ating the concetasin() appearing inthe mimeo of he rate Tam probly peace the atv rma a of the eae sep, or tam, {rectant] At + (Other pra Enzymatic Reaction Fundamentals Section 9.2 * An enzyme acts on a substrate (in other words, a reactant molecule) to chemically transform the substrate much faster than the uncatalyzed rate * Critical for performing biological functions to sustain lite Michaelis-Menten Equation Section 9.2.3 Assiant (WI re mm ORC cosh Umre~ comtnD~ heat = blw = turnover mandir. ene rere 2 Michaelis comstone. \ Subsorate + Emoyme Ly Big (octet nternleberte 2. BS Bs 4s 3 E-Stw Bs P+E. kor (E*)\5) st Kun is: Fue Mh eis or Let Vox = Reat> Ex (be come $ is 90 lange, lat omourt *F UnZymrr Michaelis-Menten Equation Section 92.3 + The Product-Enzyme Complex Batch Reactor Calculations for Enzyme Reactions Section 9.2.4 Final Comments on Enzymatic Reactions * The effect of temperature on enzymatic reactions can be complex. * Most enzymes work well at physiological temperatures, pH, etc. Outside of the physiological range, enzymes may unfold or denature and lose its, catalytic ability. * Enzymes can be inhibited through several mechanisms * Competitive (Section 9.3.1) ~ substrate and inhibitor are substantially similar and compete for the same binding site on the enzyme + Uncompetitive (Section 9.3.2) inhibitor deactivates E'S + Noncompetitive (Section 9.3.3) ~ inhibitor attaches to one binding site and the substrate to another site on an enzyme that has at least two different binding sites CHE 3700/5011D Chapter 10 Chapter 10 Learning Objectives ° Define terminology important to the use of catalysts * Describe catalyst properties * Describe steps in a catalytic reaction * Develop rate laws for heterogeneous reactions * Apply the above to reactor design Definitions Section 10.1.1 * Catalyst. “substance that affects the rate of reaction but emerges from the process unchanged” * Different catalysts can result in different yield and selectivity + Can either accelerate OR decelerate rate of reaction * Does NOT affect the equilibrium ‘+ Homogeneous catalysis: “catalyst isin, the reactants" + Heterogeneous catalysis- more than one phase, usually @ solid ‘catalyst with reactants and products in liquid or gas phase ‘For fluid-solid systems, "reaction occurs at or very near fluid- solid interface” ution with at least on Catalyst Properties Section 10.1.2 + Porous catalyst: inner porous structures provide a lot of surface area for reaction ‘+ Si-Al cracking catalyst with pore volume 0.6 cm%g, average pore r=41nm has a surface area of 300 m2/g + Molecular sieves have sufficiently small pores to allow certain ‘small molecules to enter but exclude other larger molecules (ex. zeolites) ont cages cure KR-LW qa) Figure t0-b Catayc packos bes ractr—schomate Catalyst Properties Section 10.12 *+ Porous catalyst- inner porous structures provide a lot of surface area for reaction a 'Si-Al cracking catalyst with pore volume 0.6 omg, average pore r= 4:nm has a surface area of 300 m#/g + Molecular sieves have sufficiently small pores to allow certain ‘small molecules to enter but exclude other larger molecules (ex. zeolites) ‘+ Monolithic catalyst- one type of common non-porous catalyst, but there are porous and non-porous varieties + Supported catalyst- catalyst is dispersed over a less-active substance. Characterized by the dispersion (D), the fraction of catalyst atoms deposited on the surface of the support + Promoters can increase catalytic activity Catalyst Properties Section 10.12 + Most catalysts do not retain their activities forever ~ lu act! y af. (auseal —Agn3. ( physteed stmnctons — Por somap - deparinon of mater en ertalgt = Touley cokty— carbonaceons beposseon, % Com be fost or slow. Catalytic Gas-Solid Interactions Section 10.1.3 * Focusing on gas-solid catalyzed reactions... * Atleast one or perhaps all gas reactants must become attached, or adsorbed, to the solid catalyst surface * Physical adsorption + Chemisorption * Active site- point on the catalyst surface that can form strong chemical bonds with an adsorbed atom or molecule + Tumover frequency (TOF; f) -the number of molecules reacting per active site per second under defined experimental conditions Classification of Catalysts Section 10.1.8 + Catalysts are frequently classified based on the type of reaction catalyzed ‘Taate 1041 Tyres oF REACTIONS AND RETRESESTATIVE CATALYSTS Reaction Carayts 1, Halogenation-dehalogenation CuCl, ASC. Pa yaration-dehyation AO, MgO) Alkylation-deatkyation ANIC, Pa, Zeolites Hydhogenation-dehydeogenation Co, Pt, Cr.0,. Ni 5. Oxidation Cu, Ag. Ni. V.0, 1 Komerization AICI, PUALO), Zeolites Steps in a Catalytic Reaction Section 10.2 + See Table 10-2 and Figures 10-5 through 10-10 for illustrations of some basic principles was che] tne A a ae gue 195 Suna ages aarti cues ¥ OverAA PCH rate 7% [mdbed the rr Steps in a Catalytic Reaction Section 10.2 Difwon of he recta fom the poe mouth rong the cats es tothe nei 5} Decaion of he pot ext pile ace 0 te balk ad ‘Frgure 10 Ceheceg radon cla recto cesar ref mel mos flows ids of peut Step 1 Overview: Diffusion from the Bulk to the External Surface of the Catalyst Section 10.2.1 fet wie, wo waegh gon 02Earitracrbe conto ene ite etter ‘Step 2 Overview: Internal Diffusion Section 10.2.2 aes 10 sto.tpael bein ve cnr.) Bang tae pi ‘acme Grou ni ran ag pre amend OVE Sage 2) Step 2 Overview: Internal Diffusion Section 10.2.2 * Select pellet size and external fluid velocity such that neither external diffusion nor internal diffusion is limiting + Therefore, by carefully selecting catalyst and flow conditions, it can be assumed that either Step 3 (adsorption), Step 4 (surface reaction), or Step 5 (desorption), or a combination of these steps, limits the overall rate of reaction : Diffusion from the Bulk Step 1 Over to the External Surface of the Catalyst Section 10.2.1 Figure 1010 vacantans cine sos ‘Synthesizing a Rate Law, Mechanism, and Rate-Limiting Step Section 10.3, or om tenths — Dsl - tots - chime fame Is the Surface Reaction Rate-Limiting? ‘Section 103.2 $ Is the Adsorption of Cumene : Rate-Limiting? Section 10.3.1 i Figue 10-16. Suraceteactonimtes = i Is the Desorption of Benzene Figure 10-18, Adoption ted reac. 8 gsi eaporra ” ‘Synthesizing a Rate Law, Mechanism, and Rate-Limiting Step Section 10.3 Figure 1018 Atal inal eles neon of pari pressure of cane. The surface reaction is rate limiting for the decomposition of ‘cumene on a solid Pt catalyst. Note that the model proposed for surface reaction matches the experimental data. However... ‘A model and mechanism can be proposed that appear to describe the experimental rate data, but another set of experiments must be performed to confirm the presence of the adsorbed species (or proposed active intermediates). Temperature Dependence of the Rate Law ‘Section 10.37 + As temperature increases, it is expected that the rate constant k will increase exponentially with temperature Heterogeneous Data Analysis for Reactor Design Section 10.4 * Develop an algebraic rate law consistent with experimental observations * Analyze the rate law in such a manner that the rate law parameters (e.g., k, K,) can readily be determined from the experimental data * Find a mechanism and rate-limiting step consistent with the experimental data * Design a catalytic reactor to achieve a specified Gonversion old er solectiote

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