ne ) RoBLemM 4-@ GIVEN! Chbal reaction: Gihy + 20, > Pralucts Reactioh onler: butane O45 Or Le B= tle 107 (kml?) "1s Ens 125,300 BT/bmetk PinD: Expression Or dLGHs de SOLUTION): Ne qpply the definition of « goal rete. lars CG. 2) # He definition of an Frehenas rate coefGerent Cega. aa) + SEH. £ Fa.N" Ta)” er O.1S- /, y Neel pan Cenfp-r Veethal Cex Subshhtms fr Ag Gt lS Seite ig ap (BLE fea Toy MMe: Gre must te taken te use. correct unte in eval ALey Held: malar wncentrat ms must be expressed n tmot/m* 5 2, is 625 kT/tmol- K,ProBleMm 4-7 Given: Resulé fom problem 46 G09 7 (200K P= latn eur Pith + the, tho Souur7on) ¢ be First rte WA Ay = Cigag Mayle = Wey, ELM Yee. The. malar «ance rtratoAs rapairved E eveluate. Ileal te are. foond: Go + G(r 737eb) > Protects whan as4e =65 1/Cr+estate)ip] = 13537 ~ 0-02827 heon= OYE 1 6547/6] = 7.2% 537 = 0-204S As. = 1 = 0,02827- 0.20415 ~ 0.7676 converting WS Ley] Cea. 440) : :OK\~ Te.4e I> 2.02227 (104, 525) nasi) aus cS = 2.87110" tymot/m? To = 0.200011) > 2073-10 knot nt Poelyiny result from probs $64 (25,22 rig, = SBS (4168? erp (FE ie (ee) (2 ant. asf ans) 2 -5e123 (143#10""") (0.2942) (5.081107) = A249 fom" begs? ee _~.~~«:~~~-~-.-.—r...LC¢vOO: °°»”}}©= CC 2e PROBLEM 4-10 GED! b= 282 Texpl-9es/r] Fe Ct MS CHa + HPA Kp 61900) = 0.00369/ FIND + & @ 1500 & SouuTIoN + AE aqalilriom., Rep = FR, bee be Lote WY = ACs HIM] a ae | cele _ Co wd A Letty JIMA Ley. Recogaraing, Thod (4,1 = F/T 4 erg anf ; 4 eh 1 Lk ae a *F _ Thus ay = ke Ke PIRT | Eveboating @ 00 K : 2.82-05 (1500) exp ]-9835/1900) (0.003651) (01,325. | ~ 83/5 (/0) rea nt Reo tole sm ReR-S Comme: Neke hows Penta itl aur dervation Com the definition of the dia'less Ky (Epa 265). eo = 18.0 Lt2e PRogiem = 4-Il K Given: The reaction OF Ny > NOtK where the foruunh rate constont is given as! 4 -—_38320 ke = a2 «10" exp (“705 Fur: The rate constant as a Function of Pemperature over the range 15006 T< 280K. Plot Ke ve T , dahat conclusiont can be drawn From this exercise ? APaoncH Calealate K as a function of T and plot Oke ae ‘IS0q HIS: Koo Foor ey 109 100,545 W900 368,751 2000 #47, 484 | 2100 a. xs | 2200 YAS x 10% 2300 10.38 x06 2400 20.74 x10 2900 34.3 x10 woo 1f80 tee 2200 Too 2haa T (kK) Cousctustons Mud comments: From the ahoe ple it 1s apparent that ie formation due f the react O +N, AKOTA increases ramatically as the mockure temperature increases, particular at temperatures above ~ 000K. This behavior “explains, in we thy exhaust qas cecireulation is used in spark ignition engines see Exnwple * 2-9)PROBLEM 4/2 GIVE + the allowing mechanism for oBone Ke Oo, 0,40 x, o+ 0, & 20, Kae Find: the coeFficiest matrices Vii’ and (03) production Ye" using the Convention that species | is Oy 1 SPeies Z is Oy and species 3 is O, Startmg with the compact notes’ express the rafe progress Variables wo, Far the specity AvPRORCH Reactim 1% 103 +O, + BO = Doz + 10, +10 Reachion % 10; +90, + 10 F Doz #20, +GO y;" ) ai A QA 0 a Gh Gh ©) Reach. | 1 8 @ © 1 I React 2 1 @ 4 @ 2 @ 0 6 2 rr en ee ee wy OF HI] g 12 1 ge -} 2 -] ger Ref OT ~ kB OY putty in matt frm far the tro reactions: . [fr Beal’ Deel OD" a DT xed Ox]! ] Kea Pal Pe) O0! - koa oP OT xT looking at the rews ard columns of i yop js ist fer 4 I! ist iQ [el 2 -l i*2 and 9: (+ | Continued) i iPRoBLEM 4-7 (continued) for Oy (j=) biog, # CD (Ke [Xy) De) [0] ~ ko es? Fea T1! ) OD (Ke Eq] Dog} [0] ~ Kin Ley Y" free, PLY) for A, (j+2) fangs (DK eq) es} Ge) ~ ky Fx) 2] (XT ) + (2) (re TOLD Dre) -beelXaT Cee OT) for O (53) og + (O[ is [%a4) [20 T° BGT =e, v0, ¥ q)'061') + CD CRaL%ea} [xe] DeT - ken Beg T° (Xe, 67°) Commeors: This simple example illustrates how easy bs 1B cast a mechadiim ina generel framework. fer Corpucter appliachans ,2.9. CHEMEN beuctines.Progen 4-3 Gives: the thy: reaction mechanism CH.1-H.20) in Chapter S pnd: the coefFicient matress, Vii and vii". do net inelde radical destruction ot the walls Acsummens: all #hel-body molecules, M, have the same effect during collisions APPROACH: There are 20 reackons fisted im the H,7Q, mechanism avd these reaches invelve 7 species, resulting in a x20 mate for both the reactants avd products. species? Hy, H, HO, OK, thr, HO,, 0,0, ,M for reackants vit 5 = ° ~ Reaction Bg cee aoe =°00%c09- 99 oon 008KKCOCODEG~CO°C GO ©2090000-00 © O-mo-C-209g Bi = ao 80 00- Clog C2000 OC0e 000-99°°0900~9000~c0000 Q 92 DOD OO WOU UDI OO OGs 9000-90000000C°~-0--= (conbirued) 3 -9090°0000 O9-----0 SeOOL adits tien eidfor products y, Reaction Ay H 1 o2 2 ol 3 ° oO 4 fou s fo. if Qo ° ? ' o 3 °° 9 |o © 10 ° ° ” oO ° a ° ° B [oo 4 o 0 iS oO }° 6 oO 1 nm oOo wiflo io a [toe 20 9° ° PeoBiem 4-/3 (continued) ° BO OOO 0-010 Cli G ° Be-000-~onoo-90n0-~o09 P ~8S00Q000 00000 9F Ooog Ho, ° Oz 0 © Oo ' oO ° 10 0 9 © ° 9 (O nr) eo 8 0 o 08 1 oe 0 6 6 0 1 9 0 o 0 6 ° ! ° oo 1 oo 1 oo ° te ° eo 8 6 leo ° o 0 o ~ 720000 ' ' ' ° ° ° ° ° ° ° ° 1 Comments: Note that one check to determine whether the matrices are corcect is to ptcform an Chment inbnee behveen fach reackon. For exanple : Reaction S* ” Mit 1H Io 3H 10 So is Consistent in balancony elements and Vi fr terms ofPROBLEM 4-16 Gwen: The Fallowmg chain ceactan mechanism fer NO Formation Or Bow 0 N+0r Noto @ Find: a) expressions For aka avn ae) Da simplified expression for aoa assuming Steady-state (5) and equilibrium ©,0,,Wz , and “reverse Peachons negligible <)an expression for the steady-state (00) 4) the time ta focm So ppm KO under the Fallowrng comditions * T= 2lok Loyal * 7.6 «10% 0 0:67 Fipna Xe opel * 3.025 y/o"? Muwd= 29.778 "Yende Hay quit * O76 2) He reverse reschin rate coeFicient Kip F)uskether neglect of reverse reaction rates is reasonable ) 9) &) ad my AssuuProns* ideal 2s heavier APPROACH: 4) ceachin ts ABN Ke Co) LUI-Kr- fre) 0] cenchin 2+ Es ee 004) ho 01L0 SE) A) fle) kp (Go) -teL ole] +e ATA a HAG] reackon 4+ we 2K [)QO.)-K-[ve]fu) reachon 2! 40 2 Kp HIG) + he Ld2L6] , at) + Kg (1G) -£, Cael) 0) ~ Ky LD.) + he Loa) Lo] ented)ze Proc 4-16 (continued) 8) at steady -stahe 4c) 20 * Kp BVO) Ke (ALE) - Keg HW Mox) +4, Lue) C0) neglecting reverse ceackmns and selvag for CO) fu)= Kel Gx) Ke [o,) This expression can be substihded inh) died w)Cox) = +b, Ke lob Te 7 Ke ln +Mae ¥1Co2] = Ke lox) ae FLEE [0] | so tee lor) + Ke [oQ0,] = [2K COOr ) From Fiest part of bh [w)= Ke 069 Ke fo.) A) how lang to farm 0 ppm NO git condibens: on - MD. ake [Ifo] —> Satu) > eke lellmedat Leo) 22K C02) t fer constant (0 and (Xx C0 3K eID 00) = Xeo BF * Xoetho Cais _ Xe (2% trek xX (KE) Bhp % Xo, () | (05) + So fe c 7 t “3 ne Kir 192110" exp ( ir \ Stet = [82210 e9( ) ae 50 x10" = 37x16": tiling EE (easton (2B) continued)Peo@iern H-I6 (continued) 2) the reverse ceachon coefFicient, tie OF, BNOHN 4D so, fortwyd + K, (0041 & at “ryan 4.0 Ke LO} Luy] * Kir God (N) Ke , C0000. Xunfead Xabi) xy, Kir aXe Col (Nal Xe (Gu) Xo, (Your) Xy oon Ky shwe? Ks exp(- SE) "Shoo +6 ~ Fhe — LHR #1630) + 1(339738) -1 (users . 27E4 94 “9 OGz = 2984 > Kz exp (éz¢a09) = 6.77 x10 Ke Gr = " 33370 ke a4 Kg _ bRxb" ep 7i00—) } Ket 699K ————> Kee gt Zea po — 5 Kirt 364 x10” "Yoade-g} Kips LUO" fades FY Is neglect of reverse reacten rates reasonakle Kell] vs Ke Dou] Kes WNL] vs Kee frvo)Lo} From part t Kap = LR HIT ep) oY, 5 = 1.0" Redes t THE J FT my = 4.57 x10" "pg acim pet dt bit ps Xue% . = Kp Se = exp (- SS" Ker Xe Xe xp (- =) it +146, 13, 13s 1(63782)+1 (18012) - 339735: -IkoT30 = - GSS 38) Ga) = 10.057 x10 9 Koy = 9941 id kag Kae 4O4.57 0! Yfmoe-§ Continued)ze proBiem 4-16 (continued) summary & reaction rate coe Ficienty # Kes 2llalo® Vhrle-s Kiet 364 210" Yemlens kag © 4.07 x10" MYkmde=s Kar ® 44.57 x107 *Ykmdle-s concentrotion, LN) + fags ERO. Ke a (é) zibuO™ (26065)(072) Kel] kee 4.07410) 3.25 x10? [wr] = 64.47 «10° Kes 2 ) RI looking at forward and reverse teachons Reackon 1+ Ke CoTDAD = Kek.%, (Eh (zuas (ows ory « ze fe Ke (ue) [N= fr FoI a) 31640 (sou) (s1a16) (210) « 503.7 x10" Sel _ BRw* é ee sayiga? 278 Peocion * 5) 3) 0.102, a6 Kap oor = ag bod %(£.)= 09 0 Nort V(sasnst (2 )= 392x16 Kgp lM L0} = bar Kee % (By Got stantoai (neni VI) = sir t64 ff 2 392° . 7, he 32, 57 from the Fp radios we can See that neglecta the reverse reactions is appropriate, especially considering the reaches were calculated using the Final value oF 50 ppm no, AE lower 100 concentrations, the Fife mntics would he even greater y &) and Xu From akoe + [ri)= 9.17 46H : a 3 Ny? wee s4.x10™ BF £4.46 1S" = 9.4 x8" ppm ecProgiem 4-17 Given: the Reldovich reaction (prablem 416) and the Following additional reactien? % N+oH > Ko +H Find: a) the steady-state N-odom concentrakan expression 8) the expression fir NO faration rahe, daw Vat fareeased 0,02, NaH, and OH , negligible reverse reactions, AppeancH = Ke Breaches! OrNa > Ao+N Nt0,—~? No tO N+ 0H “5 No +H 3 AED 5 ie [50009 ~ kar GO] L011 ~ Hr GWILOH] = 0 at sey stoke sng fr 0: [gaye Ke lSIONT Kyelox) + Kap [oH] D dla «ee (IO + eDDLO + Hye DCO] substituting for (01) as found in. park a: ae = ke [AW] + 6a (Slate \ea vto(el bu) (or) Keg 0x} + Keg foul] Keg (Oy) +Bey ot Sieapli fying * ; en ( belo) + 6 abe Ke (oun | ‘merece ( ay Cox} + ton) di AD 26, (ADM COnMEGTS | Nate thet the abe expression For AO ig He Sosme as that decvel in problem 4-16 without the Ntol > Noth Feackon,ze PROBLEM 4-20 Gwen: H+dr = O#+O Rt o+H = on +4 Bw otek = hotk Bs Fina + Algebraic relations fer £01, (#1, 2OHI in Perms of BS, Ks, 8 OAD Col SKC. Asomenous $B), 2.2, 823 ore in partiek qurlibriom SOLUTIONS BR = Fh, ou Rte Tos] = &, Co#Yo] ze = fev. 4 * Be? trey "Be @ Similarly for Re other 2 beachon gairs + eee Tor Lteleee kee Bo2* ‘Totti Ar @ Es - ollH] _ be 3 Tor] * Cm) Fer We tobe LA Simultenooushs fr [oT CH1,4 Lor] : = i. Dl- 2, Bes Tusy) PROBLEM 4-20 as [HI- fs LKR CoH Thol and . fowl = [8 Ee. BMA. Commenstss The partied aguilbriom eae aininates Tha Ws ter Te rati for exanple, we Gld. adel. the bike keesmbrnation (slows) ty RI-R3: ) Ot0tTM > On 7M RE 73 hekrmne Mh tecconbloatisn rate, = & Lolo] | we con uce The results tom abwe., 2.2, Cn beers SHEET |