Corresponding Solutions for Chemical Reaction Engineering CHAPTER 1 OVERVIEW OF CHEMICAL REACTION ENGINEERING .................................................. 1 CHAPTER 2 KINETICS OF HOMOGENEOUS REACTIONS ...................................................................... 3 CHAPTER 3 INTERPRETATION OF BATCH REACTOR DATA ................................................................ 7 CHAPTER 4 INTRODUCTION TO REACTOR DESIGN ............................................................................ 19 CHAPTER 5 IDEAL REACTOR FOR A SINGLE REACTOR ..................................................................... 22 CHAPTER 6 DESIGN FOR SINGLE REACTIONS ...................................................................................... 26 CHAPTER 10 CHOOSING THE RIGHT KIND OF REACTOR .................................................................. 32 CHAPTER 11 BASICS OF NON-IDEAL FLOW ............................................................................................ 34 CHAPTER 18 SOLID CATALYZED REACTIONS........................................................................................ 43 Chapter 1 Overview of Chemical Reaction Engineering 1.1 Municipal waste water treatment plant. Consider a municipal water treatment plant for a small community (Fig.P1.1). Waste water, 32000 m3/day, flows through the treatment plant with a mean residence time of 8 hr, air is bubbled through the tanks, and microbes in the tank attack and break down the organic material (organic waste) +O2 microbes CO2 + H2O A typical entering feed has a BOD (biological oxygen demand) of 200 mg O 2/liter, while the effluent has a megligible BOD. Find the rate of reaction, or decrease in BOD in the treatment tanks. Waste water 32,000 m3/day 200 mg O2 needed/liter Waste water Treatment plant Mean residence time t =8 hr Clean water 32,000 m3/day Zero O2 needed Figure P1.1 Solution: rA dN A Vdt 1 m3 mg 1g 1000 L 32 g 32000 ( day ) (200 0) / 1 3 day L 1000mg m 3 mol 3 1 m 1 day 32000 day 3 day 3 18.75mol /( m 3 day ) 2.17 10 4 mol /( m 3 s ) 1.2 Coal burning electrical power station. Large central power stations (about 1000 MW electrical) using fluiding bed combustors may be built some day (see Fig.P1.2). These giants would be fed 240 tons of coal/hr (90% C, 10%H2), 50% of which would burn within the battery of primary fluidized beds, the other 50% elsewhere in the system. One suggested design would use a battery of 10 fluidized beds, each 20 m long, 4 m wide, and containing solids to a depth of 1 m. Find the rate of reaction within the beds, based on the oxygen used. 1 Solution: V (20 4 1) 10 800m3 N c coal kgc kgc 240 10 3 0.5 0.9 108 10 3 9000molc /(bed hr ) t hr kgcoal hr rO2 rc 1 N c 1 9000 11.25kmolO2 /( m 3 hr ) V t 800 1 dO2 12000 9000 1 12000mol /(bed hr ) dt 4 rO2 1 dO2 1.5 10 4 mol /(bed hr ) 4.17mol /( m 3 s) V dt 800 2 Chapter 2 Kinetics of Homogeneous Reactions 2.1 A reaction has the stoichiometric equation A + B =2R . What is the order of reaction? Solution: Because we don’t know whether it is an elementary reaction or not, we can’t tell the index of the reaction. 2.2 Given the reaction 2NO2 + 1/2 O2 = N2O5 , what is the relation between the rates of formation and disappearance of the three reaction components? Solution: rNO2 4rO2 2rN2O5 2.3 A reaction with stoichiometric equation 0.5 A + B = R +0.5 S has the following rate expression -rA = 2 C0.5 A CB What is the rate expression for this reaction if the stoichiometric equation is written as A + 2B = 2R + S Solution: No change. The stoichiometric equation can’t effect the rate equation, so it doesn’t change. 2.4 For the enzyme-substrate reaction of Example 2, the rate of disappearance of substrate is given by -rA = 1760[A ][E 0 ] , 6 C A mol/m3·s What are the units of the two constants? Solution: [rA ] mol [k ][ A][ E0 ] m 3 s [6] [C A ] [6] [C A ] mol / m3 [k ] 2.5 mol mol / m 3 1 3 3 3 m s (mol / m )(mol / m ) s For the complex reaction with stoichiometry A + 3B → 2R + S and with second-order rate expression -rA = k1[A][B] 3 are the reaction rates related as follows: rA= rB= rR? then how are they related? 1 1 Solution: rA rB rR 3 2 If the rates are not so related, Please account for the sings , + or - . 2.6 A certain reaction has a rate given by mol/cm3·min -rA = 0.005 C2A , If the concentration is to be expressed in mol/liter and time in hours, what would be the value and units of the rate constant? Solution: (rA' ) rA' mol mol (rA ) 3 L hr cm min L hr mol 3 (rA ) 10 4 6 rA 6 10 4 0.005C A2 300C A2 mol cm min mol mol (C A ) 3 L cm L mol C A' 3 C A 10 3 C A mol cm (C A' ) (rA' ) 300C A2 300 (10 3 C A' ) 2 3 10 4 C A' 2 k ' 3 10 4 2.7 For a gas reaction at 400 K the rate is reported as - dp A = 3.66 p2A, atm/hr dt (a) What are the units of the rate constant? (b) What is the value of the rate constant for this reaction if the rate equation is expressed as -rA = - 1 dN A V dt = k C2A , mol/m3·s Solution: (a) The unit of the rate constant is [1 / atm hr ] (b) rA 1 dN A V dt Because it’s a gas reaction occuring at the fined terperatuse, so V=constant, and T=constant, so the equation can be reduced to 4 rA dP V dPA 1 3.66 2 3.66 ( A ) PA (C A RT ) 2 VRT dt RT dt RT RT (3.66RT )C A2 kCA2 So we can get that the value of k 3.66RT 3.66 0.08205 400 120.1 2.9 The pyrolysis of ethane proceeds with an activation energy of about 300 kJ/mol. How much faster the decomposition at 650℃ than at 500℃? Solution: Ln r2 k E 1 1 300kJ / mol 1 1 Ln 2 ( ) ( ) 7.586 3 r1 k1 R T1 T2 8.314kJ /(10 mol K ) 173K 923K 2.11 r2 1970.7 r1 In the mid-nineteenth century the entomologist Henri Fabre noted that French ants (garden variety) busily bustled about their business on hot days but were rather sluggish on cool days. Checking his results with Oregon ants, I find Running speed, m/hr 150 160 230 295 370 Temperature, ℃ 13 16 22 24 28 What activation energy represents this change in bustliness? Solution: r k0e E RT f (concentrat ion )let f (concentrat ion ) cons tan t ak 0 e LnrA Lnk ' E RT k 'e E RT 1E T R Suppose y LnrA , x so slope 1 , T E , intercept Lnk ' R 5 150 160 230 295 370 -3.1780 -3.1135 -2.7506 -2.5017 -2.2752 T /o C 13 16 22 24 28 1 10 3 T 3.4947 3.4584 3.3881 3.3653 3.3206 rA /( m h 1 ) LnrA 4 -y = 5417.9x - 15.686 R2 = 0.97 -Ln r 3 2 1 0 0.0033 0.00335 0.0034 0.00345 0.0035 1/T -y = -5147.9 x + 15.686 Also slope E 5147.9 K , intercept Lnk ' = 15.686 , R E 5147.9K 8.3145J /( mol K ) 42.80kJ / mol 6 Chapter 3 Interpretation of Batch Reactor Data 3.1 If -rA = - (dCA/dt) =0.2 mol/liter·sec when CA = 1 mol/liter, what is the rate of reaction when CA = 10 mol/liter? Note: the order of reaction is not known. Solution: Information is not enough, so we can’t answer this kind of question. 3.2 Liquid a sedomposes by first-order kinetics, and in a batch reactor 50% of A is converted in a 5-minute run. How much longer would it take to reach 75% conversion? Solution: Because the decomposition of A is a 1st-order reaction, so we can express the rate equation as: rA kCA We know that for 1st-order reaction, Ln Ln C Ao kt , CA C Ao kt1 , C A1 Ln C Ao kt2 C A2 C A1 0.5C Ao , C A2 0.25C Ao So t 2 t1 t1 C C 1 1 1 ( Ln Ao Ln Ao ) ( Ln4 Ln2) Ln2 k C A2 C A1 k k C 1 1 Ln( Ao ) Ln2 5 min k C A1 k equ(1) equ(2) So t 2 t1 t1 5 min 3.3 Repeat the previous problem for second-order kinetics. Solution: We know that for 2nd-order reaction, 1 1 kt , C A C A0 So we have two equations as follow: 1 1 2 1 1 kt1 k 5 min , equ(1) C A1 C A0 C Ao C Ao C Ao 7 1 1 4 1 1 3( ) 3kt1 kt2 , equ(2) C A2 C Ao C Ao C Ao C Ao So t 2 3t1 15 min , t 2 t1 10 min 3.4 A 10-minute experimental run shows that 75% of liquid reactant is converted to product 1 by a -order rate. What would be the fraction converted in a half-hour run? 2 Solution: In a dC 1 order reaction: rA A kCA0.5 , 2 dt kt 0.5 C Ao C A0.15 , 2 So we have two equations as follow: 1 0.5 0.5 0.5 0.5 C Ao C A0.15 C Ao ( C Ao ) 0.5C Ao kt1 k (10 min) , equ(1) 4 After integration, we can get: 0.5 C Ao C A0.25 kt2 k (30 min) , equ(2) 0.5 Combining these two equations, we can get: 1.5C Ao kt2 , but this means C A0.25 0 , which is impossible, so we can conclude that less than half hours, all the reactant is consumed up. So the fraction converted X A 1 . 3.5 In a hmogeneous isothermal liquid polymerization, 20% of the monomer disappears in 34 minutes for initial monomer concentration of 0.04 and also for 0.8 mol/liter. What rate equation represents the disappearance of the monomer? Solution: The rate of reactant is independent of the initial concentration of monomers, so we know the order of reaction is first-order, rmonomer kCmonomer And Ln Co (34 min) k 0.8Co k 0.00657 min 1 rmonomer (0.00657 min 1 )Cmonomer 8 3.6 After 8 minutes in a batch reactor, reactant (CA0 = 1 mol/liter) is 80% converted; after 18 minutes, conversion is 90%. Find a rate equation to represent this reaction. Solution: 1 1 Ln t k 1 X A2 Ln1 In 1st order reaction, 2 1.43 , dissatisfied. 1 1 t1 Ln5 Ln k 1 X A1 1 1 1 1 1 ( ) k C A2 C Ao 0.1C Ao C Ao 9 / C Ao 9 t In 2nd order reaction, 2 , satisfied. 1 1 1 1 1 t1 4 / C Ao 4 ( ) k C A1 C Ao 0.2C Ao C Ao According to the information, the reaction is a 2nd-order reaction. 3.7 nake-Eyes Magoo is a man of habit. For instance, his Friday evenings are all alike—into the joint with his week’s salary of $180, steady gambling at “2-up” for two hours, then home to his family leaving $45 behind. Snake Eyes’s betting pattern is predictable. He always bets in amounts proportional to his cash at hand, and his losses are also predictable—at a rate proportional to his cash at hand. This week Snake-Eyes received a raise in salary, so he played for three hours, but as usual went home with $135. How much was his raise? Solution: n Ao 180 , n A 13 , t 2h , n A' 135 , t ; 3h , rAknA Ln So we obtain n Ao kt , nA Ln ' n Ao n Ao Ln( ) Ln( ' ) nA nA t t' n' 180 Ln Ao 13 135 , n ' 28 A 2 3 3.9 The first-order reversible liquid reaction A R , CA0 = 0.5 mol/liter, CR0=0 takes place in a batch reactor. After 8 minutes, conversion of A is 33.3% while equilibrium conversion is 66.7%. Find the equation for the this reaction. Solution: Liquid reaction, which belongs to constant volume system, 9 1st order reversible reaction, according to page56 eq. 53b, we obtain t t dt 0 XA 0 dX A k1 1 Ln k1 (k1 k 2 ) X A k1 k 2 k1 (k1 k 2 ) X A 1 t 480 sec 8 min , X A 0.33 , so we obtain 480 sec 8 min Kc k1 1 Ln k1 k 2 k1 (k1 k 2 )0.33 eq(1) eq(1) C k1 C Re M X Ae , M Ro 0 , so we obtain eq(2) k 2 C Ae 1 X Ae C Ao Kc X Ae k1 k 2 1 X Ae 2 3 1 2 3 2, k1 2k 2 eq(2) Combining eq(1) and eq(2), we obtain k 2 0.02888 min 1 4.8 10 4 sec 1 k1 2k 2 0.05776 min 1 9.63 10 4 sec 1 So the rate equation is rA dC A k1C A k 2 (C Ao C A ) dt 4.8 10 4 sec 1 C A 9.63 10 4 s e c1 (C A0 C A ) 3.10 Aqueous A reacts to form R (A→R) and in the first minute in a batch reactor its concentration drops from CA0 = 2.03 mol/liter to CAf = 1.97 mol/liter. Find the rate equation from the reaction if the kinetics are second-order with respect to A. Solution: It’s a irreversible second-order reaction system, according to page44 eq 12, we obtain 1 1 k1 1 min , 1.97 2.03 so k1 0.015 L mol min so the rate equation is rA (0.015 min 1 )C A2 3.15 At room temperature sucrose is hydrolyzed by the catalytic action of the enzyme sucrase as follows: 10 Aucrose sucrase products Starting with a sucrose concentration CA0 = 1.0 millimol/liter and an enzyme concentration CE0= 0.01 millimol/liter, the following kinetic data are obtained in a batch reactor (concentrations calculated from optical rotation measurements): CA, millimol/liter t,hr 0.84 0.68 0.53 0.38 0.27 0.16 0.09 0.04 0.018 0.006 0.0025 1 2 3 4 5 6 7 8 9 10 11 Determine whether these data can be reasonably fitted by a knietic equation of the Michaelis-Menten type, or -rA = k 3C AC E 0 C A CM where CM = Michaelis constant If the fit is reasonable, evaluate the constants k3 and CM. Solve by the integral method. Solution: Solve the question by the integral method: rA dC A k 3C Eo C A kC 4 A , dt C A C M 1 k 5 C A k4 k 3C Eo 1 , k5 CM CM Ln k t 1 5 C Ao C A k 4 k 4 C Ao t, hr C A ,mmol/L Ln C Ao C Ao CA CA C Ao CA CA t C Ao C A 1 0.84 1.0897 6.25 2 0.68 1.2052 6.25 3 0.53 1.3508 6.3830 4 0.38 1.5606 6.4516 5 0.27 1.7936 6.8493 6 0.16 2.1816 7.1428 7 0.09 2.6461 7.6923 8 0.04 3.3530 8.3333 9 0.018 4.0910 9.1650 10 0.006 5.1469 10.0604 11 11 0.0025 Ln Suppose y= t , x= C Ao C Ao C A 6.0065 11.0276 C Ao CA , thus we obtain such straight line graph CA 12 t/(Cao-Ca) 10 8 6 y = 0.9879x + 5.0497 4 R2 = 0.998 2 0 0 1 Slope 2 3 4 5 Ln(Cao/Ca)/(Cao-Ca) 6 7 k C 1 M 0.9879 , intercept= 5 5.0497 k 4 k 3C Eo k4 So C M k3 1 0.9879 0.1956(mmol / L) , k 5 5.0497 k 4CM 0.1956 19.80hr 1 C Eo 0.9879 0.01 3.18 Enzyme E catalyzes the transformation of reactant A to product R as follows: A enzyme R, -rA = 200C A C E 0 mol 2 C A liter min If we introduce enzyme (CE0 = 0.001 mol/liter) and reactant (CA0 = 10 mol/liter) into a batch rector and let the reaction proceed, find the time needed for the concentration of reactant to drop to 0.025 mol/liter. Note that the concentration of enzyme remains unchanged during the reaction.. Solution: 2 CA 1 dt 10 5 rA dC A 200 0.001C A C A Rearranging and integrating, we obtain: 12 10 t t dt 0 0.025 10 C 10 ( 5)dC A 10 Ln Ao 5(C Ao C A ) CA CA 0.025 10 Ln 10 5(C Ao C A ) 109.79 min 0.025 3.20 M.Hellin and J.C. Jungers, Bull. soc. chim. France, 386(1957), present the data in Table P3.20 on thereaction of sulfuric acid with diethylsulfate in a aqueous solution at 22.9℃: H2SO4 + (C2H5)2SO4 → 2C2H5SO4H Initial concentrations of H2SO4 and (C2H5)2SO4 are each 5.5 mol/liter. Find a rate equation for this reaction. Table P3.20 t, min C2H5SO4H, t, min C2H5SO4H, mol/liter Solution: mol/liter 0 0 180 4.11 41 1.18 194 4.31 48 1.38 212 4.45 55 1.63 267 4.86 75 2.24 318 5.15 96 2.75 368 5.32 127 3.31 379 5.35 146 3.76 410 5.42 162 3.81 ∞ (5.80) It’s a constant-volume system, so we can use XA solving the problem: i) We postulate it is a 2nd order reversible reaction system A B 2R The rate equation is: rA dC A k1C AC B k 2 C R2 dt C Ao C Bo 5.5mol / L , C A C Ao (1 X A ) , C B C Bo C Ao X A C A , C R 2C Ao X A When t , CRe 2C Ao X Ae 5.8mol / L So X Ae 5.8 0.5273 , 2 5.5 C Ae C Be C Ao (1 X Ae ) 5.5 (1 0.5273) 2.6m o /l L After integrating, we obtain 13 Ln X Ae (2 X Ae 1) X A 1 2k1 ( 1)C Ao t eq (1) X Ae X A X Ae The calculating result is presented in following Table. t, Ln X Ae (2 X Ae 1) X A X Ae X A Ln(1 XA ) X Ae C R , mol / L C A , mol / L XA 0 0 5.5 0 0 0 41 1.18 4.91 0.1073 0.2163 -0.2275 48 1.38 4.81 0.1254 0.2587 -0.2717 55 1.63 4.685 0.1482 0.3145 -0.3299 75 2.24 4.38 0.2036 0.4668 -0.4881 96 2.75 4.125 0.25 0.6165 -0.6427 127 3.31 3.845 0.3009 0.8140 -0.8456 146 3.76 3.62 0.3418 1.0089 -1.0449 162 3.81 3.595 0.3464 1.0332 -1.0697 180 4.11 3.445 0.3736 1.1937 -1.2331 194 4.31 3.345 0.3918 1.3177 -1.3591 212 4.45 3.275 0.4045 1.4150 -1.4578 267 4.86 3.07 0.4418 1.7730 -1.8197 318 5.15 2.925 0.4682 2.1390 -2.1886 368 5.32 2.84 0.4836 2.4405 -2.4918 379 5.35 2.825 0.4864 2.5047 -2.5564 410 5.42 2.79 0.4927 2.6731 -2.7254 5.8 2.6 0.5273 — — min Draw Ln X Ae (2 X Ae 1) X A ~ t plot, we obtain a straight line: X Ae X A 14 3 y = 0.0067x - 0.0276 2.5 2 R = 0.9988 Ln 2 1.5 1 0.5 0 0 100 200 Slope 2k1 ( k1 t 300 400 500 1 1)C Ao 0.0067 , X Ae 0.0067 6.794 10 4 L /( mol min) 1 2( 1) 5.5 0.5273 When approach to equilibrium, K c 2 C Re k1 , k 2 C Ae C Be k1C Ae C Be 6.794 10 4 2.6 2 1.364 10 4 L /( mol min) so k 2 2 2 C Re 5.8 So the rate equation is rA (6.794 10 4 C AC B 1.364 10 4 C R2 )mol /( L min) ii) We postulate it is a 1st order reversible reaction system, so the rate equation is rA dC A k1C A k 2 C R dt After rearranging and integrating, we obtain Ln(1 Draw Ln(1 XA 1 ' ) k1t X Ae X Ae eq (2) XA ) ~ t plot, we obtain another straight line: X Ae 15 3 -y = 0.0068x - 0.0156 2.5 R2 = 0.9986 -Ln 2 1.5 1 0.5 0 0 100 200 x 300 400 500 k1' Slope 0.0068 , X Ae So k1' 0.0068 0.5273 3.586 10 3 min 1 k 2' k1' C Ae 3.586 10 3 2.6 1.607 10 3 min 1 C Re 5.8 So the rate equation is rA (3.586 10 3 C A 1.607 10 3 C R )mol /( L min) We find that this reaction corresponds to both a 1st and 2nd order reversible reaction system, by comparing eq.(1) and eq.(2), especially when XAe =0.5 , the two equations are identical. This means these two equations would have almost the same fitness of data when the experiment data of the reaction show that XAe =0.5.(The data that we use just have XAe =0.5273 approached to 0.5, so it causes to this.) 3.24 In the presence of a homogeneous catalyst of given concentration, aqueous reactant A is converted to product at the following rates, and CA alone determines this rate: CA,mol/liter 1 2 4 6 7 9 12 -rA, mol/liter·hr 0.06 0.1 0.25 1.0 2.0 1.0 0.5 We plan to run this reaction in a batch reactor at the same catelyst concentration as used in getting the above data. Find the time needed to lower the concentration of A from C A0 = 10 mol/liter to CAf = 2 mol/liter. Solution: By using graphical integration method, we obtain that the shaped area is 50 hr. 16 20 16 12 -1/Ra 8 4 0 0 2 4 6 Ca 8 10 12 14 3.31 The thermal decomposition of hydrogen iodide 2HI → H2 + I2 is reported by M.Bodenstein [Z.phys.chem.,29,295(1899)] as follows: T,℃ 508 427 393 356 283 k,cm3/mol· 0.1059 0.00310 0.000588 80.9×10-6 0.942×10-6 s Find the complete rate equation for this reaction. Use units of joules, moles, cm 3, and seconds. According to Arrhenius’ Law, k = k0e-E/R T transform it, - In(k) = E/R·(1/T) -In(k0) Drawing the figure of the relationship between k and T as follows: 16 y = 7319.1x - 11.567 2 -Ln(k) 12 R = 0.9879 8 4 0 0.001 0.002 0.003 0.004 1/T From the figure, we get slope = E/R = 7319.1 intercept = - In(k0) = -11.567 17 E = 60851 J/mol k0 = 105556 cm3/mol·s From the unit [k] we obtain the thermal decomposition is second-order reaction, so the rate expression is - rA = 105556e-60851/R T·CA2 18 Chapter 4 Introduction to Reactor Design 4.1 Given a gaseous feed, CA0 = 100, CB0 = 200, A +B→ R + S, XA = 0.8. Find XB,CA,CB. Solution: Given a gaseous feed, C Ao 100 , C Bo 200 , A B R S X A 0 , find X B , C A , C B A B 0 , C A C Ao (1 X A ) 100 0.2 20 XB bC Ao X A 1 100 0.8 0.4 C Bo 200 C B C Bo (1 X B ) 200 0.6 120 4.2 Given a dilute aqueous feed, CA0 = CB0 =100, A +2B→ R + S, CA = 20. Find XA, XB, CB. Solution: Given a dilute aqueous feed, C Ao C Bo 100 , A 2B R S , C A 20 , find X A , X B , C B Aqueous reaction system, so A B 0 When X A 0 , V 200 When X A 1 , V 100 C 1 1 So A , B A Bo 2 bC Ao 4 X A 1 XB CA 20 1 0.8 , C Ao 100 b C Ao X A 2 100 0.8 1.6 1 , which is impossible. a C Bo 1 100 So X B 1 , C B C Bo 100 4.3 Given a gaseous feed, CA0 =200, CB0 =100, A +B→ R, CA = 50. Find XA, XB, CB. Solution: Given a gaseous feed, C Ao 200 , C Bo 100 , 19 A B R , C A 50 .find X A , X B , C B X A 1 XB CA 50 1 0.75 , C Ao 200 bC Ao X A 1.5 1 , which is impossible. C Bo So C B C Bo 100 4.4 Given a gaseous feed, CA0 = CB0 =100, A +2B→ R, CB = 20. Find XA, XB, CA. Solution: Given a gaseous feed, C Ao C Bo 100 , A 2B R , C Bo 20 , Find X A , X B , C A X B 0 , V 100 A 100B 200 X B 1, V 50 A 100R 150 150 200 0.25 100 0.25 , A 0.5 1 200 100 2 1 100 0.842 100 20 0.421 XB 0.842 , X A 2 100 100 0.25 20 B C A C Ao 4.6 1 X A 1 0.421 100 73.34 1 A X A 1 0.5 0.421 Given a gaseous feed, T0 =1000 K, π0=5atm, CA0=100, CB0=200, A +B→5R,T =400 K, π=4atm, CA =20. Find XA, XB, CB. Solution: Given a gaseous feed, To 1000K , 0 5atm , C Ao 100 , C Bo 200 A B 5R , T 400K , 4atm , C A 20 , A find X A , X B , C B . a C T 0 400 5 600 300 0.5 1 , B A Bo 2 , bC Ao T0 1000 4 300 According to eq page 87, 20 C A T 0 20 1 0.5 C Ao T0 100 XA 0.818 20 C A T 0 1 1 0.5 1 A 100 C Ao T0 1 XB bC Ao X A 100 0.818 0.409 aC Bo 200 C Bo b T X A ) 0 C Ao ( 200 0.818) 200 C a T 0 C B Ao 100 130 1 A X A 1 1 0.818 ( 4.7 A Commercial Popcorn Popping Popcorn Popper. We are constructing a 1-liter popcorn to be operated in steady flow. First tests in this unit show that 1 liter/min of raw corn feed stream produces 28 liter/min of mixed exit stream. Independent tests show that when raw corn pops its volume goes from 1 to 31. With this information determine what fraction of raw corn is popped in the unit. 31 1 1 1 Solution: A 30 , C Ao 1a.u. , C A C Ao a.u. 1 28 28 1 1 C Ao C A 28 46.5% XA 1 C Ao A C A 1 30 28 21 Chapter 5 Ideal Reactor for a single Reactor 5.1 Consider a gas-phase reaction 2A → R + 2S with unknown kinetics. If a space velocity of 1/min is needed for 90% conversion of A in a plug flow reactor, find the corresponding space-time and mean residence time or holding time of fluid in the plug flow reactor. 1 Solution: 1 min , s Varying volume system, so t can’t be found. 5.2 In an isothermal batch reactor 70% of a liquid reactant is converted in 13 min. What space-time and space-velocity are needed to effect this conversion in a plug flow reactor and in a mixed flow reactor? Solution: Liquid reaction system, so A 0 According to eq.4 on page 92, t C Ao XA 0 Eq.13, M .F .R C Ao C A C Ao X A , M .F .R can’t be certain. rA rA Eq.17, P.F .R C Ao XA 0 5.4 dC A 13 min rA dX A , so P.F .R t B.R 13 min rA We plan to replace our present mixed flow reactor with one having double the bolume. For the same aqueous feed (10 mol A/liter) and the same feed rate find the new conversion. The reaction are represented by A → R, Solution: -rA = kC1.5 A Liquid reaction system, so A 0 C CA X XA V A , Ao FAo C Ao rA C Ao (rA ) k[C Ao (1 X A )]1.5 Now we know: V 2V , FAo FAo , C Ao C Ao , X A 0.7 So we obtain 22 XA 2X A 2V 1 . 5 1.5 FAo FAo kC1Ao.5 (1 X A )1.5 kCAo ()1 X A ) V XA (1 X A ) 1.5 2 0.7 8.52 (1 0.7)1.5 X A 0.794 5.5 An aqueous feed of A and B (400liter/min, 100 mmol A/liter, 200 mmol B/liter) is to be converted to product in a plug flow reactor. The kinetics of the reaction is represented by mol liter min Find the volume of reactor needed for 99.9% conversion of A to product. A +B→ R, -rA = 200CACB Solution: Aqueous reaction system, so A 0 V t 1 FAo C Ao C Ao According to page 102 eq.19, V o C Ao 0 V C Ao o X Af 0 5.9 X Af X Af 0 X Af dX dC A A 0 rA rA dX A , o 400liter / min , rA 0.999 dX dX A A 0.1 400 124.3L 0 rA rA A specific enzyme acts as catalyst in the fermentation of reactant A. At a given enzyme concentration in the aqueous feed stream (25 liter/min) find the volume of plug flow reactor needed for 95% conversion of reactant A (CA0 =2 mol/liter ). The kinetics of the fermentation at this enzyme concentration is given by A Solution: enzyme R , -rA = 0.1C A mol 1 0.5C A min liter P.F.R, according to page 102 eq.18, aqueous reaction, 0 X A dX V A 0 FAo rA V FAo XA 0 1 0.5C A 1 dX A 125 2( Ln X A)\ 0.1C A 1 X A 23 125( Ln 1 0.95) 986.4 L 0.05 5.11 Enzyme E catalyses the fermentation of substrate A (the reactant) to product R. Find the size of mixed flow reactor needed for 95% conversion of reactant in a feed stream (25 liter/min ) of reactant (2 mol/liter) and enzyme. The kinetics of the fermentation at this enzyme concentration are given by A enzyme R , -rA = 0.1C A mol 1 0.5C A min liter Solution: o 25L / min , C Ao 2mol / L , FAo 50mol / min , X A 0.95 Constant volume system, M.F.R., so we obtain V o C Ao X A rA 2 0.95 199.5 min , 0.1 0.05 2 1 0.5 0.05 2 V o 199.5 min 25L / min 4.9875m3 5.14 A stream of pure gaseous reactant A (CA0 = 660 mmol/liter) enters a plug flow reactor at a flow rate of FA0 = 540 mmol/min and polymerizes the as follows mmol 3A → R, -rA = 54 liter min How large a reactor is needed to lower the concentration of A in the exit stream to C Af = 330 mmol/liter? C 330 1 1 A 1 1 C Ao 2 660 0.75 Solution: A 3 , XA CA 2 330 1 3 1 1 A 3 660 C Ao 0-order homogeneous reaction, according to page 103 eq.20 k k V o k VC Ao C Ao X A FAo So we obtain V FAo 1 0.75 C Ao X A 540 7.5L C Ao k 54 5.16 Gaseous reactant A decomposes as follows: 24 A → 3 R, -rA = (0.6min-1)CA Find the conversion of A in a 50% A – 50% inert feed ( 0 = 180 liter/min, CA0 =300 mmol/liter) to a 1 m3 mixed flow reactor. 42 Solution: V 1m 3 , M.F.R. A 1 2 According to page 91 eq.11, V o C Ao X A rA C Ao X A 1 X A 0.6C Ao 1 X A X A (1 X A ) 1000 L 0.6(1 X A ) 180 L / m i n So we obtain X A 0.667 25 Chapter 6 Design for Single Reactions 6.1 A liquid reactant stream (1 mol/liter) passes through two mixed flow reactors in a series. The concentration of A in the exit of the first reactor is 0.5 mol/liter. Find the concentration in the exit stream of the second reactor. The reaction is second-order with respect to A and V2/V1 =2. Solution: 1= V2/V1 = 2, V1 01 C A0 C A1 , rA = CA0=1mol/l , CA1=0.5mol/l , -rA2=kC2A2 (2nd-order) , 2× 2 = V2 02 C A1 C A2 rA2 = 01 02 , -rA1=kC2A1 , C A0 C A1 kCA1 2 = C A1 C A2 kCA2 2 2×(1-0.5)/(k0.52)=(0.5-CA2)/(kCA22) So we obtain CA2= 0.25 mol/l 6.2 Water containing a short-lived radioactive species flows continuously through a well-mixed holdup tank. This gives time for the radioactive material to decay into harmless waste. As it now operates, the activity of the exit stream is 1/7 of the feed stream. This is not bad, but we’d like to lower it still more. One of our office secretaries suggests that we insert a baffle down the middle of the tank so that the holdup tank acts as two well-mixed tanks in series. Do you think this would help? If not, tell why; if so calculate the expected activity of the exit stream compared to the entering stream. Solution: 1st-order reaction, constant volume system. From the information offered about the first reaction, we obtain 1 = V1 01 C C A1 A0 kCA1 1 C A0 C A0 7 1 k C A0 7 If a baffle is added, 2 21 22 V21 V22 = V1 021 022 01 = C A0 C A21 C A2 C A22 kCA21 kCA22 6 C A0 7 = =6/k …… 1 kC A0 7 ① 26 1 V C A0 C A21 2 1 C C A22 =3/k= A21 kCA21 021 kCA22 …… ② Combining equation ① and ② we obtain: CA21= 0.25CA0 ; 1 C A0 16 So it will help, and the expected activity of the exit stream is 1/16 of the feed. CA22=0.25CA21= 6.3 An aqueous reactant stream (4 mol A/liter) passes through a mixed flow reactor followed by a plug flow reactor. Find the concentration at the exit of the plug flow reactor if in the mixed flow reactor CA = 1 mol/liter. The reaction is second-order with respect to A, and the volume of the plug flow unit is three times that of the mixed flow unit. Solution: m Vm p Vp = 0 0 Constant volume system and 2nd-order reaction: C A0 C A1 C A0 C A1 4 1 = > =3/k 2 k rA1 kCA1 3Vm 0 =9/k= - CA f C A1 …… ① …… ② 2 C Af C dC A 1 1 A 1) = - dC A = ( 1 k C Af rA k Combining equation. ① and ② we obtain: CAf= 0.1 mol/liter 6.4 Reactant A (A → R,CA0=26 mol/m3) passes in steady flow through four equal-size mixed flow reactors in series ( total =2 min). When steady state is achieved the concentration of A is found to be 11, 5, 2, 1 mol/m3 in the four units. For this reaction, what must be plug so as to reduce CA from CA0 = 26 to CAf = 1 mol/m3? Solution: m m1 m2 m3 m4 = C A0 C A1 C A1 C A2 C A2 C A3 C A3 C A4 = = = rA1 rA2 rA3 rA4 CA0=26mol/liter, CA1=11 mol/liter, CA2=5 mol/liter, CA3= 2mol/liter, CA4=1mol/liter So we abtain: 15/(-rA1) = 6/(-rA2) = 3/(-rA3) = 1/(-rA4) We postalate the reaction rate is 1 unit when CA4=1 mol/liter So we obtain 27 CA, mol 11 5 2 1 -rA 30 12 6 2 1/(-rA) 1/30 1/12 1/6 1/2 C A 0 dC dC A A = C A0 r C Af r A A p C Af So we obtain p 2.63 min. 6.6 At 100℃ pure gaseous A reacts away with stoichiometry 2A → R + S in a constant volume batch reactor as follows: t, sec 0 20 40 60 80 100 120 140 160 pA, atm 1.00 0.96 0.80 0.56 0.32 0.18 0.08 0.04 0.02 What size of plug flow reactor operating at 100℃ and 1 atm can treat 100 moles A/hr in a feed consisting of 20% inserts to obtain 95% conversion of A? Solution: FA0= 100 mol/hr = 0.0278 mol A/s, CA0 = (1 atm×101.3)/(8.314×37.3)=0.0327mol/l t, sec 0 20 40 60 80 100 120 140 160 pA, atm 1.00 0.96 0.80 0.56 0.32 0.18 0.08 0.04 0.02 CA,mol/l 0.0327 0.03136 0.0261 0.0285 0.01045 0.00588 0.00261 0.001307 0.0006533 Now , p A0 =0.8 atm, C A0 =0.0261 mol/l When the conversion of A is 90%, C A =0.001305mol/l , p A =0.04 atm 6.7 So = 0.04 0.8 =140-40=100 s So V = 0 = FA 0 =100×0.027/0.0261=106.4 L C A0 We wish to treat 10 liters/min of liquid feed containing 1mol A/liter to 99% conversion. The stoichiometry and kinetics of the reaction are given by A → R, -rA = CA mol 0.2 C A liter min Suggest a good arrangement for doing this using two mixed flow reactors, and find the size of the two units needed. Sketch the final design chosen. 28 Solution: 0 =10l/min , CA0=1 mol/l, when Vi = (1) two for equal-she M.F.R. 0 -rA1=CA1/(0.2+CA1) , So we obtain = ZA=0.99 CAf =0.91mol/l C A0 C A1 C A1 C Af = rAf rA1 -rAf = CAf/(0.2+CAf) = 0.0476, i=2.333min CA1=0.121mol/l, Vt=2Vi=2 i 0 =2×2.333×10=46.65 L (2) -/rA L K N M 0 Z2 Z1 ZA When the area of rectangle KLMN is maximum, the volume of reactors needed its minimum. = So V1 0 V2 0 = C A0 C A1 C A1 C A 2 =2.7+1.89=4.59 rA1 rA2 V =4.59×10=45.9 1 ) rA =0.2/(1-ZA)2 dx d ( Slope of curse = ( Slope of So when slope of curse = slope of LN = 1 ) rA Z A1 0.2 21 ( 1) 1 Z Ai = Z Ai LN, ZA1=0.9, CA1=0.1 mol/L, -rA1=1/3 , 1/(-rA) = 3 6.8 From steady-state kinetics runs in a mixed flow reactor, we obtain the following data on the reaction A → R. 29 , sec CA0, mmol/liter CA, mmol/liter 60 50 20 35 100 40 11 100 60 20 200 80 11 200 100 Find the space time needed to treat a feed of C A0= 100 mmol/liter to 80% conversion (a) in a plug flow reactor. (b) in a mixed flow reactor. Solution: From the data offered, we obtain (a) in a P.F.R: So (b) CA0=100 mmol/L, XA=0.8 p =area of the shaded CA=20 mmol/L in a M.F.R. m C A0 C Af rAf =(100-20)/(-rA20)=2×80=160s. 6.20 Reactant A decomposes with stoichiometry A → R and with rate dependent only on CA. The following data on this aqueous decomposition are obtained in a mixed flow reactor: , sec CA0 CA 14 200 100 25 190 90 29 180 80 30 170 70 29 160 60 27 150 50 24 140 40 19 130 30 15 120 20 12 110 10 20 101 1 Determine which setup, plug flow, mixed flow, or any two-reactor combination gives minimum for 90% conversion of a feed consisting of CA0 = 100. Also find this minimum. If a two-reactor scheme is found to be optimum, give CA between stages and for each stage. 30 Solution : Draw a 1 ~ CA curse rA CA0=100, ZA=0.9, From the so CA=10 1 1 ~ CA curse, we know that when CA∈(10,70), increases as CA rA rA increases and that when CA∈(70,100), 1 decrease as CA increase. rA So when CA∈(10,70), we plan to use a P.F.R p = area of the shaded region followed with a M.F.R. to treat the feed CA∈(10,70), m = area of the shaded region. 31 Chapter 10 Choosing the Right Kind of Reactor 10.1 Given the two reactions 1 A+ B R -r1 = k1CACB 2 R+B S -r2 =k2CACB Where R is the desired product and is to be maximized. Rate the four sohemes shown in Fig. P10.1 ---either “good” or “not so good,” please, no complicated calculations, just reason it out. Solution: Number (d) is good for the formation of intermediate –R which causes no maximum occurring there. rR (r1 ) (r2 ) (k1 k 2 )C AC B , the same order, so R can’t affect the D. 10.2 Repeat Problem 1 with just one change -r2 = k2CRC2B Solution: -r1 = k1CACB n1=2 -r2 = k2CRCB2 n2=3 n1< n2, therefore, low CB favors the reaction of lowest order, mixed flow reactor should be used. So (a) Not so good. (c) Not so good. (b) Good. (d) Not so good 10.3 Repeat Problem 1 with just one change -r2 = k2C2R CB Solution: -r1 = k1CACB n1=2 -r2 = k2CR2CB n2=3 32 n1< n2, and the order is 2 for R, low CB and low CR is helpful to get more desired product R. So (a) Not so good. (c) Good. (b) Not so good. (d) Not so good 33 Chapter 11 Basics of Non-ideal Flow 11.1 A pulses input to a vessel gives the results shown in Fig.P11.1. (a) Check the material balance with the tracer curve to see whether the results are consistent. (b) If the result is consistent, determine t , V and sketch the E curve. Solution: (a) Act 0.05 5 0.25 , Ac t M 1 0.25 , 4 , so the results are consistent. 5 0 0 tCdt t 0.05dt 2.5 min t Cdt 0.05dt (b) 0 t M V E 5 0 , so V t 2.5 min 4L / min 10L C pulse M / 0.05 4 0.2 min 1 11.2 Repeat problem P11.1 with one change: the tracer curve is now as shown in Fig.P11.2. Solution: Ac t 0.05 6 0.30 M So the results are not consistent. 11.3 A pulse input to a vessel gives the results shown in Fig. P11.3. (a) Are the results consistent? (check the material balance with the experimental tracer curve.) 34 (b) If the results are consistent, determine the amount of tracer introduced M, and the E curve. Solution: 1 9 h (25 16) h , 2 2 19C 25 C 19 25 max max ( t 16 ) tdt (t 25)tdt tCdt tCdt 16 19 3 6 19 t 1619 20 sec 25 19C 25 C max max 16 Cdt 19 Cdt 16 3 (t 16)dt 19 6 (t 25)dt C C 16 19 19 25 3 max 6 max 2 2 2 2 20.5 sec or C max (25 16) 2 V 60 t' 15 sec t , 4 So the results are not consistent. (a) Ac t 11.4 A step experiment is made on a reactor. The results are shown in Fig. P11.4. (a) Is the material balance consistent with the tracer curve? (b) If so, determine the vessel volume V, t ,the F curve and the E curve. Solution: (a) If C max m 0.5 1 3 0.125mol / L , A C max t C max 2C max 4 2 so t 2 min (b) F m C C , C max 35 0, t [0,1) 1 then F curse is F (t 1), t [1,3] 2 1, t (3, ) A 2 16 V 2 0.125 8liters m 0.5 0, t [0,1) (3, ) dF , so E 1 E dt 2 , t [1,3] E curse is 0.8 E 0.6 0.4 0.2 0 0 1 2 t,min 3 4 5 11.5 A batch of radioactive material is dumped into the Columbia River at Hanford, Washington. At Bonneville Dam, about 400 km downstream the flowing waters (6000 m3/s) are monitored for a particular radioisotope (t1/2>10 yr) and the data of Fig.P11.5 are obtained. (a) How many units of this tracer were introduced into the river? (b) What is the volume of Columbia River waters between Bonneville Dam and the point of introduction of tracer? Solution: (a) Ac t 1 r M , 10 6 105 5.25 10 5 3 day 2 m so we obtain M 5.25 10 5 r m3 day 6000 27216units of radioisotope s m3 36 (b) t 0 tCdt Cdt 35 20 t 125 10 6 10 6 (t 20)d t (t 125)dt 35 35 20 35 125 1 (125 20) 10 6 2 3.15 10 3 60day 52.5 10 6 m3 V t 60day 6000 3.11 1010 m 3 s 11.6 A pipeline (10 cm I.D., 19.1 m long) simultaneously transports gas and liquid from here to there. The volumetric flow rate of gas and liquid are 60 000 cm 3/s and 300 cm3/s, respectively. Pulse tracer tests on the fluids flowing through the pipe give results as shown in Fig.P11.6. What fraction of the pipe is occupied by gas and what fraction by liquid? Solution: t g 2s , t l 100s , so Vg g t g 6000 2 1.2 10 5 cm 3 Vl l t l 300 100 3 10 4 cm 3 Vtotal 4 D2 L 4 10 2 19.1 10 2 1.5 10 5 cm 3 1.2 10 5 So we obtain %G 100% 80% , %L 20% 1.5 10 5 A liquid macrofluid reacts according to A → R as it flows through a vessel. Find the conversion of A for the flow patterns of Fig.P11.7 to P11.11 and kinetics as shown. 0.5 11.7 CA0 = 1mol/liter, -rA = kC0.5 /liter0.5·min A , k = 2 mol 37 Figure 11.7 Solution: CA C Ao CA 1 dC A C Ao C A C Ao (1 ) rA C Ao CA 2 (1 ) (1 ) 2 C Ao C Ao So we obtain X A 1 11.8 C L CA 1 1 ( A ) batch Edt (1 t ) 2 dt 0 0 C Ao C Ao 2 6 1 0.833 6 CA0 = 2mol/liter, -rA = kC2A, k = 2 liter / mol·min Figure 11.8 Solution: According to page274 eq.15, CA 1 C Ao 1 kCAo t 4t 1, t [0,0.5] AE t 1, so Emax 3 min 1 , E 0, t (0.5,) So C 0.5 CA 1 ( A ) element E dt (4t 1)dt 0.5 , 0 C 0 1 4t C Ao Ao X A 1 0.5 0.5 11.9 CA0 = 6mol/liter, -rA = k, k = 3 mol/liter·min 38 Figure 11.9 Solution: kt , t 2 min C A 1 C Ao C Ao 0, t 2 min AE t So 1 , t [0,3] 1 , so E 3 0, t (3,) C 3 CA kt 1 1 ( A ) e Edt (1 ) dt , 0 C 0 C Ao C Ao 3 3 Ao X A 1 1 0.667 3 11.10 CA0 = 4mol/liter, -rA = k, k = 1 mol/liter·min Figure 11.10 Solution: kt t 1 , t 4 min , t 3 C A 1 4 C Ao , E C Ao 0, t 3 0, t 4 min So C CA 3 1 ( A ) e E d t (1 ) E d t , 0 C C Ao 4 0 4 Ao X A 1 1 0.75 4 11.11 CA0 = 0.1mol/liter, -rA = k, k =0.03 mol/liter·min 39 Figure 11.11 Solution: For the zero-order reaction, ( 1 0.3t , t 3.3 min CA kt ) element 1 C Ao C Ao 0, t 3.3 min ( X A ) element 1 ( So 0.3t , t 3.3 min CA ) element C Ao 1, t 3.3 min X A (X A ) 0 element E (t )dt (liquid macrofluid reacts) From Fig11.11, we know 0,0 t 4 min 0.1(t 4),4 t 6 min E (t ) 0.025(14 t ),6 t 14 0, t 14 min 14 X A 1 E (t )dt 1 4 Thus, the conversion of A is 100%. 11.12—11.14 Hydrogen sulfide is removed form coal gas by contact with a moving bed of iron oxide particles which convert to the sulfide as follows: Fe2O3 → FeS In our reactor the fraction of oxide converted in any particle is any particle is determined by its residence time t and the time needed for complete conversion of the particle and this is given by t 3 1 – X = (1) when t < 1 hr, and with = 1 hr and X=1 when t 1 hr Find the conversion of iron oxide to sulfide if the RTD of solides in the contactor is approximated by the curve of Fig.P11.12,P11.13,P11.14. 40 11.12 Figure 11.12 Solution: From Fig.11.12, we know 1,0 t 1hr E (t ) 0, t 1hr When t<1hr, 1 ( X A ) element (1 t ) 3 So 1 0 0 X A ( X A ) element E (t )dt 1 [1 (1 t ) 3 ]dt 0.75 11.13 Figure 11.13 Solution: From Fig.11.13, we know , t 0.5hr E (t ) 0, t 0.5hr When t<1hr, 1 ( X A ) element (1 t ) 3 also ( X A ) element 1 (1 t ) 3 So 0 0 X A ( X A ) element E (t )dt [1 (1 t ) 3 ] (t 0.5)dt 0.875 Thus, the conversion of A is 87.5%. 11.14 41 Figure 11.14 From Fig.11.13, we know 0, t 0.5hr E (t ) 1,0.5 t 1.5hr 0, t 1.5hr When t<1hr, 1 ( X A ) element (1 t ) 3 also ( X A ) element 1 (1 t ) 3 When t>1hr, ( X A ) element 1 So 1 1.5 0 0.5 1 X A ( X A ) element E (t )dt [1 (1 t ) 3 ] 1dt 1 1dt 0.9844 Thus, the conversion of A is 98.44%. 42 Chapter 18 Solid Catalyzed Reactions 18.22 In the absence of pore diffusion resistance a particular first-order gasphase reaction proceeds as reported below. - rA = 10-6 mol/cm3cat·s at CA = 10-5 mol/cm3, at 1 atm and 400℃ what size of spherical catalyst pellets (e = 10-3 cm-3/cm cat·s) would ensure that pore resistance effects do not intrude to slow the rate of reaction? Solution: The rate expression of first-order reaction is rA k C A And with rA , CA replaced by numerical values, we obtain k 10 6 0.1s 1 5 10 To judge what type of the pore resistance, we need to calculate the Thiele modulus k dp 10 1 5 MT L dp De 6 10 3 3 When MT, the pore resistance effects could be neglected. 3 Thus, dp 0.4 , also dp 2.4mm 5 So the diameter of spherical catalyst pellets should be less than 2.4mm. 18.24 The first-order decomposition of A is run in an experimental mixed flow reactor. Find the role played by pore diffusion in these runs; in effect determine whether the runs were made under diffusion-free, strong resistance, or intermediate conditions. dp W CA0 XA 4 1 300 60 0.8 8 3 100 160 0.6 Solution: For the first run, rAout 1 rAout A→R C AoX A o u t W 300 60 0.8 14400 1 43 For the second run, 2 rAout 100 160 0.6 3200 3 1 14400 rAout 4.5 2 rAout 3200 While R2 dP2 2, R1 dP1 Thus, the runs were running under intermediate pore resistance. 44