Collection and Analysis 7 of Rate Data ‘You can observe a lot just by watching. Yogi Betra, New York Yankees Overview. In Chapters 5 and 6 we have shown that once the rate law is known, it can be substituted into the appropriate mole balance, and then through the use of the appropriate stoichiometric relationships, we can apply the CRE algorithm to analyze any isothermal reaction system, In this chapter we focus on ways of obtaining and analyzing reaction-rate data to obtain the rate law for a specific reaction. We discuss two common types of reactors used for obtaining rate data: the batch reactor, which is used primarily for homogeneous reac- tions, and the differential reactor, which is used for solid-fluid heteroge- neous reactions. In batch-reactor experiments, concentration, pressure, and/or volume are usually measured and recorded at different times dur- ing the course of the reaction. Data are collected from the batch reactor during transient operation, whereas measurements on the differential reactor are made during steady-state operation. In experiments with a dif- ferential reactor, the product concentration is usually monitored for dif- ferent sets of feed conditions Three different methods of analyzing the data collected are used: + The integral method + The differential method + Nonlinear regression ‘The integral and differential methods are used primarily in analyz- ing batch-reactor data, Because a number of software packages (¢.g., Polymath, MATLAB) are now available to analyze data, a rather exten- sive discussion of nonlinear regression is included. 243,244 Collection and Analysis of Rate Data Chapter 7 7.1. The Algorithm for Data Analysis For batch systems, the usual procedure is to collect concentration-time data, which we then use to determine the rate law. Table 7-1 gives the seven-step procedure we will emphasize in analyzing reaction engineering data. Data for homogeneous reactions is most often obtained in a batch reac- tor, After postulating a rate law in Step 1 and combining it with a mole balance in Step 2, we next use any or all of the methods in Step 5 to process the data and arrive at the reaction orders and specific reaction-rate constants. Analysis of heterogeneous reactions is shown in Step 6. For gas-solid heterogeneous reactions, we need to have an understanding of the reaction and possible mechanisms in order to postulate the rate law in Step 6B. After study- ing Chapter 10 on heterogeneous reactions, one will be able to postulate differ- cent rate laws and then use Polymath nonlinear regression to choose the “best” rate-law and reaction-rate-law parameters (see Example 10-3 on page 452) The procedure we should use to delineate the rate law and rate-law parameters is given in Table 7-1 Tats Tel Stuns ts ANALYaNG Ras Davi 1. Postulate a rate law. ‘A. Power-lav mvels for homogeneous reactions CAC B. _Langnuir-inshelwood models for heterogeneous reactions ROR, _ ye Wah FKP GE KPAH Pa) 2, Select reactor type and corresponding mole balance. ‘A. If batch reactor (Section 7.2), use mole balance on Reactant A ac, n= te rer ra > B. _ iferential PBR (Section 7.6, use mole balance on Product P(A. P) Fe =n = Fe -epyaw TEI-1.2) Aa geac oer '3. Process your data in terms of the measured variable (6. Nj. Cy, oF Pa). I nes= essary, rewrite your mole balance in terms of the measured vaziable (eB) 4. Look for simplifications. For example, if one of the reactants is in excess, assume its concentration is constant. I the gas-phase mole fraction of reactant A is small, set =O 8, For a batch reactor, calculate +, as a function of concentration C, to determine the reaction order. AL Diferential analysis Section 74) Combine the mole balance (TET-1.1) and power law mode! (TH7-1.3) re kCS (7E7.13)Section 7.1 The Algorithm for Data Analysis 245 gy Summary Notes ‘Tams T-L_ Stuns wy AsaLvaiye Ram Data, (Cosson) 6, For differential PBR, cal 7. Analyze your rate law acy sacs see ob e (-£2)=w-r9 ams (2). Graphical diteretial (b) Finite diferenial method or (©) Polynomial it (2) Bathe pl a slope ofthe line to the data or (3) Use nonlinear sepession o find e and &simultancously Integral method (Seton 7.3) For,” AC, the combined mole balance and rat aw is Hs di 3 [if —£6) ee yo nd ein ero tte rey rET-14) Guess «and integrate Equation (TBT-1.4). Rearrange your equation o oblain the appropriate function of Cy, which when ploted as a fonction of time should he linear IF ts Hnear, then the guessed value of ets corect and the slope is the specific reaction rate, IF ts not linear, guess egain for 0. If you guess = 0, 1, and 2, and none of these orders At the dala, proceed to nonlinear regression Nonlinear regression Polymath) (Section 75) Integrate Equation (TET-I.4) to obtain cfr? ~cte : p= YC CED pret crET-.6) | ci . {se Polymath repression to find cand kA Polymats tril on repression wih stenosis shown inthe Chaplet 7 Simmary Notes on he CRE Web Sie, wiumich.ch/-elemens/fndex hom ater wa of C, oF Py (Section 7.6) Cateutte 1 = ag stanton of reactant concentration, Cy of patil aw pressure Py Choose a model (see Chapter 10) HPs TRA Use nonlinear regression to find the best model and model parameters. See example on the CRE Web site Stmnmary Notes for Chapter 10, using data from heterogeneous catalysis. del for “goodness of fi.” Calculate a conelationcoeticint.248 Process data in tems of the “arble Assume that the rate law is of the n= hee ‘Method of excess Collection and Analysis of Rate Data Chapter 7 7.2. Determining the Reaction Order for Each of Two Reactants Using the Method of Excess Batch reactors are used primarily to determine rate-law parameters for homo- geneous reactions. This determination is usually achieved by measuring con- centration as a function of time and then using either the integral, differential, or nonlinear regression method of data analysis to determine the reaction order, o, and specific reaction-rate constant, k, If some reaction parameter other than concentration is monitored, such as pressure, the mole balance must be rewritten in terms of the measured variable (e.g., pressure, as shown in the example in Solved Problems on the CRE Web site), When a reaction is irreversible, itis possible in many cases to determine the reaction order e and the specific rate constant by either nonlinear regres- sion or by numerically differentiating concentration versus time data, This lat- ter method is most applicable when reaction conditions are such that the rate is essentially a function of the concentration of only one reactant; for example, if, for the decomposition reaction A Products ta = hace ay) then the differential method may be used, However, by utilizing the method of excess, it is also possible to deter- mine the relationship between rq and the concentration of other reactants. That is, for the irreversible reaction A+BoProducts with the rate law ary = ky Ch (7-2) where a and are both unknown, the reaction could first be run in an excess of B so that Cy remains essentially unchanged during the course of the reac- tion (.e., Cy= Cyy) and ary = CR (73) where B= kychm kc, After determining a, the reaction is carried out in an excess of A, for which the rate law is approximated as A= CE (7-4) where k"= kyCh=kxChoSection 7.3 Integral Method 2a7 ‘The integral method uses a il and-error procedure 1 ind the reaction order is important to "know how to generate linear plots f functions of Cy versus r for zero fst, and econd-order Zero ordet, Once @ and B are determined, ky can be calculated from the measure- ment of =r, at known concentrations of A and B ky = Zt& = (dmntmolys = 5) ag Both a and can be determined by using the method of excess, coupled with a differential analysis of data for batch systems 7.3 Integral Method The integral method is the quickest method to use to determine the rale law if the order turns out to zero, first, or second order. In the integral method, we guess the reaction order, a, in the combined batch reactor mole balance and rate law equation aC, = - key (7-6) at and integrate the differential equation to obtain the concentration as a function of time. If the order we assume is correct, the appropriate plot (determined from this integration) of the concentration-time data should be linear. The inte- gral method is used most often when the reaction order is known and it is desired to evaluate the specific reaction rate constant at different temperatures to determine the activation energy. In the integral method of analysis of rate data, we are looking for the appropriate function of concentration corresponding to a particular rate law that is linear with time, You should be thoroughly familiar with the methods of obtaining these linear plots for reactions of zero, first, and second order. For the reaction A> Products carried out in a constant-volume batch reactor, the mole balance is ts, a For a zero-order reaction, r, = —k, and the combined rate law and mole bal- ae, Hn _ yg 1A Fe oD Integrating with Cx = Cag at = 0, we have Cq= Cu ht 78)248 First order Collection and Analysis of Rate Data Chapter 7 A plot of the concentration of A as a function of time will be linear (Figure 7-1) with slope (—k) for a zero-order reaction carried out in a constant-volume batch reactor. If the reaction is first order (Figure 7~ mole balance and the rate law , integration of the combined a, {hey dt * withthe limit Cx = Cay at = 0 gives ¢ In = ke (7-9) a ¢ Consequently, we see thatthe slope of « plot af [ha(Co/Ca)] 8 8 Fetion of sme is linear with slope k Te the reaction is second order (Figure 7), then oo o noi ° | oto Figure TA Zor ton Figure 74. Historie retin ont Figure 72 Seconda esion gure 7-4 Pott eos encentaon as function oftSection 7.3 Integral Method 249 Integrating, with Cy = Cap initially (.e., ¢ = 0), yields Secand order (7-10) Ca Can We sce that for a second-order reaction a plot of (1/C,) as a function of time should be linear with slope k In Figures 7-1, 7-2, and 7-3, we saw that when we plotted the appropriate function of concentration (ic., Cy, InC4, or 1/C,) versus time, the plots were linear, and we concluded that the reactions were zero, first, or second order, respectively. However, ifthe plots of concentration data versus time had turned out not to be linear, such as shown in Figure 7-4, we would say that the proposed reaction order did not fit the data. In the case of Figure 7-4, we would conclude that the reaction is not second order. After finding that the integral method for first, second, and third orders do not fit the data, one ‘The idea is © should use one of the other methods discussed in Table 7-1. strange the data s0 I is important to restate that, given a reaction-rate law, you should be able ‘ata linest relaiosshps (0 quickly choose the appropriate function of concentration or conversion that chtained. yields a straight line when plotted against time or space time. The goodness- of-fit of such a line may be assessed statistically by calculating the linear cor- relation coefficient, °, which should be as close to 1 as possible. The value of P is given in the output of Polymath’s nonlinear regression. Example 7-1 Integral Method of CRE Data Analysis ‘The liquid-phase reaction ‘Trityl (A) + Methanol (B) — Products (C) ‘was carried out in a batch reactor at 25°C in a solution of benzene and pyridine in snes of mation (6,05 Be ed pnt ot ati ash tor was purchased at the Sunday market in Riga, Jofostan.) Pyridine reacts with HCI, which then precipitates as pyridine hydro-chloride thereby making the reaction inreversible. The reaction is fist order in methanol. The concentration of tiphenyl ‘methyl chloride (A) was measured as a function of time and is shown below Tams BTL Raw Data, 7 (aia) © 50 100 150-200-250 «300 x ovale) 0.05 0038 90305 00256 00222 a0195 O07 Use the integral method to confirm that the reaction is second order with regard to ‘wiphenyl methyl chloride Solution We use the power-law model, Equation (7-2), along with information from the prob- Jem statement that the reaction is frst order in methanol, (B), ie., = 1 to obtain kG, er)250 Collection and Analysis of Rate Data Chapter 7 Excess methanol: The initial concentration of methanol (B) is 10 times that of ttyl (A), so even if all A were consumed, 90% of B remains. Consequently, we will take the concentration of B as a constant and combine it with & to form FkCC yo = CE e712) where His the pseudo rate constant K” = kCyy and kis the true rate constan Substituting = 2 and combining with the mole balance on a batch reactor, we obtain era) Integrating with Cy any Rearranging ers, We see that if the reaction is indeed second order then a plot of (1/C,) versus should be linear. Using the data in Table E7-1.1, we calculate (1/C,) to construct ‘Table E7-1.2. ‘Taos BT-L2_ Paocessn Data rin) © 50 100 150 200 «280 +300 4 tele) 0.05 0038 00305 90255 00222 O0195 a0174 Cy (dono!) 2 23 327 tS SES STS In a graphical solution, the data in Table B7-1.2 can be used to construct a plot of Cy as 8 function of t, which will yield the specific reaction rate K’. This plot is shown in Figure E7-1.1, Again, Excel or Polymath could be used to find from the data in Table E7-1.2. The slope of the line is the specific reaction rate K. ey Figure E7-L1 Plot of the reciprocal of C, versus # fora second-order reaction We see from the Excel analysis and plot thatthe slope of the lin is 0.12 dn'/mol- min, = 012 e718)Section 7.4 Differential Method of Analysis 251 Constant-volume batch reactor Plot versus In Cy w find and ky ‘We now use Equation (E7-1.6), along with the initial concentration of methancl, to find the tue rate constant, k ko B= $12 dainlinin 94d ig Coo 0.5 motidm* mel / ‘The rate law is (dm 2¢, mr = fo.24{-) prin Jedey (87.1.7 [oar m] erin ‘We note that the integral method tends to smooth the data, Analysis: In this example, the reaction orders are known so that the integral method ean be used to (1) verily the reaction is second order in wityl and (2) to find the sp cifie pseudo reaction rate & = kCyq forthe case of excess methanol (B). Knowing k and Cyo, We can then find the true rate constant k 7.4 Differential Method of Analysis To oulline the procedure used in the differential method of analysis, we con- sider a reaction carried out isothermally in a constant-volume batch reactor and the concentration of A, recorded as a function of time. By combining the mole balance with the rate law given by Equation (7-1), we obtain dy dt After taking the natural logarithm of both sides of Equation (5-6) ) ~£5)- nky+amcy ay a} observe that the slope of a plot of [In(—dC4/dt)} as a function of (InC,) is the reaction order, a (see Figure 7-5). (0) Finding « (©) Finan ky Figure 7-5. Differential method to determine reaction order.282 Methods for finding 1 trom de os dat See Appendix A2. Collection and Analysis of Rate Data Chapter 7 Figure 7-5(a) shows a plot of [= (dC,/dt)] versus [Ca] on log-log paper (or use Excel to make the plot) where the slope is equal to the reaction order a. The specific reaction rate, k,, can be found by first choosing a concentration in the plot, say Cy, and then finding the corresponding value of [= (dC,/d8), ] on the line, as shown in Figure 7-5(b). The concentration chosen, Cay, to find the derivative at Cay, need not be a data point, it just needs to be on the line. After raising Cy, to the power a, we divide it into [—(dC4/dt),] to determine ky = (dC g/d, (Ca To obtain the derivative (—dC,/d) used in this plot, we must differentiate the concentration-time data either numerically or graphically. Three methods to determine the derivative from data giving the concentration as a function of time are (7-12 + Graphical differentiation + Numerical differentiation formulas + Differentiation of a polynomial fit to the data ‘We shall only discuss the graphical and numerical methods. 7.4.1 Graphical Differentiation Method ‘This method is very old (from slide rule days—"What's a slide rule, Grand- father?”), when compared with the numerous software packages. So why do wwe use it? Because with this method, disparities in the data arc casily seen. Consequently, it is advantageous to use this technique to analyze the data before planning the next set of experiments. As explained in Appendix A.2, the graphical method involves plotting (—AC,/Af) as a function of ¢ and then using equal-area differentiation to obtain (—dC,/dt). An illustrative example is also given in Appendix A.2. In addition to the graphical technique used to differentiate the data, two other methods are commonly used: differentiation formulas and polynomial fitting 7.4.2. Numerical Method Numerical differentiation formulas can be used when the data points in the independent variable are equally spaced, such a8 t,~ty = ft, ~ At Tawi 7-2 Raw DATA ine aad e]®]® [concenrration mover) | Cw | Cx | Cw | ew | em | Co ‘The three-point differentiation formulas’ shown in Table 7-3 can be used to caleulate dC,/dt B, Camahan, H, A. Luther, and J. 0, Wilkes, Applied Numerical Methods (New York: Wiley, 1969), p. 129.Section 7.4 Diferetial Method of Analysis. 253 “Thaus 7-4 Dunnxesrianioy Fombas >) initial point: r3Cy0 + 4C as — ) nial a) = Baa Aen Coe (7-13) Je Hcerior points at - . i Tap! Caurn— Cau— wT (7-14) Last point 1 (71s) Equations (7-13) and (7-15) are used for the first and last data points, respec- tively, while Equation (7-14) is used for all intermediate data points (see Step 6A.la in Example 7-2) 7.4.3. Finding the Rate-Law Parameters Now, using either the graphical method, differentiation formulas, or the poly- nomial derivative, the following table can be set up. ‘Taw Tet Process Dara 5 =e nate (S) C4) ‘The reaction order can now be found from a plot of In(—dC,/dt) as a funetion of InCy, as shown in Figure 7-5(a), since tof 224) - ney rorincy 16 dt ) Before solving the following example problems, review the steps to determine the reactonte aw from mse of date pint Cae 71). Example 7-2. Determining the Rate Law ‘The reaction of triphenyl methyl chloride (crityl) (A) and methanol (B) discussed in Example 7-1 is now analyzed using the differential method, ° ul (CiHl,), CCI+CH,OH—9(C,H,), CCH, +11 A+B > C 4D284 Following the Algorithm Collection and Analysis of Rate Data Chapter 7 ‘The concentration-time data in Table E7-2.1 was obtained in a batch reactor Tams E721 Raw Data Time (mi) 950100180200 250300 Concentation of A (movin?) x10" | 50 38 306 256 222 195 17a (atr=0, C= 005 a ‘The initial concentration of methanol was 0.5 mol/dm? Part (1) Determine the reaction order with respect to tiphenyl methyl chloride Part (2) Ina separate set of experiments, the reaction order wrt methanol was found to be first order. Determine the specific reaction-rate constant Solution Part (1) Find the reaction order with respect to trtyl Step 1 Postulate a rate law. CR e721) Step 2 Process your data in terms of the measured variable, which in this case is Cy Step 3. Look for simplifications. Because the concentration of methanol is 10 times the initial concentration of triphenyl methyl chloride, its concentra- tion is essentially constant G=Cw 7.22) 21) Substituting for Cy in Equation mn = heck ¥ 7.23) Step 4 Apply the CRE algorithm, Mote Balance er24 Rate Law: Hs BCR e723) Stoichiomenry: Liquid V = Vo aed % Combine: Mole balance, rate law, and stoichiometry ac, Meg 125 a e725) Evaluate: Taking the natural log of both sides of Equation (B7-2.5) of “4 Ink’ +e0ln Cy 7.26)Section 7.4 Differential Method of Analysis 255 ‘order ct with respect to tiphenyl methyl chloride (A). Step 5 Find [=] as a function of Cy from concentration-time data, a Step 5A-1a Graphical Method. We now show how to construct Table BT-2.2 ‘The derivative (Cyldi) is determined by calculating and plotting (CAC WAN as a function of time, , and then using the equal-area differ- entiation technique (Appendix A.2) to determine (~iCy/ld?) as a function of Ca, First, we calculate the ratio (-AC,/A#) from the fist two columns of Table B7-2.2; the result is written in the third column, Tawi 87.2.2 Process Dara BCs io! Ae so8 SE x 10 ox rtanin) C4 10* (movida) (omol/dm'- min) (mold - min) o so 30 2.40" 50 8 86 Las 100 305 12 1.00 150 256 os 008 200 22 os asd 250 19s oa a2 300 114 x 1078 = 24 x 10(motidn* min) Next, we use Table B7-2.2 to plot the third column as a function of the frst column in Figure E7-11 (ie., CACs/A#) versus 1]. Using equal-area differentiation, the value of CdCy/di) is read off the figure (represented by the arrows); then itis used to complete the fourth column of Table E7.2.2. Figure E721 Graphical diferentition,256 Collection and Analysis of Rate Data Chapter 7 ‘The results to find (IC, /dt) at each time, t, and concentration, Cq, are summarized in Table B7-2.3, Step 6A.1a Finite Difference Method, We now show how to calculate (dCyld#) using the finite difference formulas [i.e., Equations (7-13) through (7-15)] 2.86% 10- mol/dm! min £5 5.198 = 2,86 mold «min a Ex Cua _ (30.6 = 50) 107 1250 = Euro 2ar 100 71.94% 10+ moVlém* min (42x) _ Cus Cur _ (25.6~ 38) x 10 t= 00 (468) = Cas Cas (25.638) 107° ar) 2ar 100 =-1.24% 10 moliém! min 1-150 C 22.2 ~ 30.6) x 10) 2ar 00 084% 10+ moliém’ min 1=200 Cxs=Cuy _ (19.5 ~25.6) 107 2ar 100 5-061 x 10 motidm’ min Ca 22.2) x 10 +=250 (7422.2) 107 2a 00 5-048 10+ motidm’ min 1=300 Cua ACas + 3C ag _ (22.2 ~ 419.5) + 307 4] 2AF Too = 0.36 10 molidm? - min We now enter the above values for (—dCy/d*) in Table B7-2.3 and use Table 7-22 to plot columns 2 and 3 (-25 x 10,000) as a function of column 4 a J (Cx 1,000) on log-log paper, as shown in Figure B7-2.2. We could also substitute the parameter values in Table E7-2.3 into Excel to find a and K. Note that most of the points for both methods fall virtually on top of one another, This table is, in a way, redundant because it is not necessary to always find (-dC,dt) by both tech niques, graphical and finite differenceSection 7.4 Diferetial Method of Analysis. 257 ‘Tamu B7-2.3_ SuaoMARY oF Processun Data Geaphical ‘nite Difference £4 50.000 — 254 x 10,000 di a 4% 1.000 1 min) (onlin mis) (meld? i)’ ° 30 286 50 50 186 194 8 100 120 1a 308 150 080 oss 256 200 oss os: ma 250 oss oss 19s 300 042 036 na Bagot el an min shee=198 ssc" x1 (elim Figure E7-22 Excel plot to determine « and & From Figure E7-2.2, we found the slope to be 1.99, so thatthe reaction is said to be second order (0 = 2.0) with respect to triphenyl methyl chloride. To evaluate & ‘we can evaluate the derivative in Figure B7-2.2 at Cy, = 20 x 10~' moldm’, which is (-458) = 015% 10-4 mova’ in ern chen 7-28) 95 107" mol/dm’ min _ 9 195 drm? / mol - min (20 x 107 mol/dm’) As will be shown in Section 7-5, we could also use nonlinear regression on tion (B7-1.5) to find &” 0.122.dmm'/mol - min 7.29)288 S ‘Summary Notes Invegral method normally used ro find F when order is known Collection and Analysis of Rate Data Chapter 7 ‘The Excel graph shown in Figure E7-2.2 gives «= 1.99 and k= 0.13 dim¥/mol - mi, ‘We now set c= 2 and regress again to find K’ = 0.122 din'/mol- min, ODE Regression, There are techniques and software becoming available whereby an ODE solver can be combined with a regression program to solve differential ‘equations, such as ay a kee 5.7.25) to find fy and from concentration-tme data, art (2) The reaction was said to be frst order with respect to methanol, 9 Cok = Cask (72.10) Assuming Cyo is constant at 0.5 molédm? and solving for & yields? =0,244 (domo) min ‘The rate law is rq = (0.244(dm' fmol) amin] C3 Cy 72.1) Analysis: In this example, the differential method of data analysis was used to find the reaction order with respect to trityl (0 = 1.99) and the pscudo rate constant @ = 0.125 (dmVmo!)min). The reaction order was rounded up to «= 2 and the data was repressed again (o obiin X= 0.122 (dm“mol)/min, agen knowing X” and Cap: and the tue rate constant is k = 0.24 (dm/mol) "ain. By comparing the methods of analysis of the rate data presented in Examples 7-1 and 7-2, we note that the differential method tends to accentuate the uncertainties in the data, while the integral method tends to smooth the data, thereby disguising the uncertainties in it, In most analyses, it is imperative that the engineer know the limits and uncertainties in the data. This prior knowledge is necessary to provide for a safety factor when scaling up a process from lab- coralory experiments to design either a pilot plant or full-scale industrial plant. 7.5 Nonlinear Regression In nonlinear regression analysis, we search for those parameter values that minimize the sum of the squates of the differences between the measured val- ues and the calculated values for all the data points, Not only can nonlinear M. Hoepfner and D. K. Roper, “Describing Temperature Increases in Plasmon-Resonant ‘anoparticle Systems.” Journal of Thermal Analysis and Calorimetry, 98(1), (2009), pp. 197-202.Section 7.5 Nonlinear Regression 259 regression find the best estimates of parameter values, it can also be used to discriminate between different rate-law models, such as the Langmuir- Hinshelwood models discussed in Chapter 10. Many software programs are available (o find these parameter values so that all one has to do is enter the data. The Polymath software will be used to illustrate this technique. In order to carry out the search efficiently, in some cases one has to enter initial esti- mates of the parameter values close to the actual values. These estimates can be obtained using the linear-least-squares technique discussed on the CRE Web site Professional Reference Shelf R7.3. We will now apply nonlinear regression to reaction-rate data to determine the rate-law parameters. Here, we make initial estimates of the parameter val- ues (e.g, reaction order, specific rate constant) in order to calculate the concen- tration for each data point, C,., obtained by solving an integrated form of the combined mole balance and rate law. We then compare the measured concen- tration at that point, C,,, with the calculated value, C,., for the parameter values chosen, We make this comparison by calculating the sum of the squares of the differences at each point ¥(C,,—C,.)~. We then continue to choose new parameter values and search for those values of the rate law that will minimize the sum of the squared differences of the measured concentrations, Cjq, and the caleulated concentrations values, C,.. That is, we want to find the rate-law parameters for which the sum of all data points ¥(Ci,— Cis @ minimum. It we carried out NV experiments, we would want to find the parameter values (eg. E, activation energy, reaction orders) that minimize the quantity 2a 8B Gn CP OO N=K ~ > NEK (a7) where 8 = Ge CF N = number of runs K = number of parameters to be determined Cyq = measured concentration rate for run i ¢ = calculated concentration rate for run i One notes that if we minimize s* in Equation (7-17), we minimize o? To illustrate this technique, let's consider the reaction A ——> Product for which we want to learn the reaction order, e, and the specific reaction rate, k =r = CR ‘The reaction rate will be measured at a number of different concentrations. We now choose values of & and a, and calculate the rate of reaction (C,,) at each concentration at which an experimental point was taken, We then subtract the260 Collection and Analysis of Rate Data Chapter 7 calculated value (C,) from the measured value (C,,). square the result, and sum the squares for all the runs for the values of k and e that we have chosen. This procedure is continued by further varying a and k until we find those values of k and a that minimize the sum of the squares. Many ‘well-known searching techniques are available to obtain the mininwum value G2yq? Figure 7-6 shows a hypothetical plot of the sum of the squares as a function of the parameters « and k: o? = fk,a) (7-18) Figure 7-6 Minimum sum of equares Look at the top circle. We see that there are many combinations of «and & (eg, © = 22, k= 48 or a= 18, k = 5.3) that will give a value of a? = 57. The same is true for o? = 1.85. We need to find the combination of ct and k that gives the lowest value of 6? In searching to find the parameter values that give the minimum of the sum of squares 02, one can use a number of optimization techniques or solt- ware packages. The searching procedure begins by guessing parameter values and then calculating (C,,, ~ C;,) and then 0? for these values. Next, a few sets of parameters are chosen around the initial guess, and 0 is calculated for these sets as well. The search technique looks for the smallest value of o? in the vicinity of the initial guess and then proceeds along a trajectory in the direction of decreasing a? to choose different parameter values and determine the corresponding o?. The trajectory is continually adjusted so as to always proceed in the direction of decreasing until the minimum value of a is reached. For example, in Figure 7-6 the search technique keeps choosing com- binations of o and k until a minimum value of 6? = 0.045 (mol/dm')? is reached. 5 (a) B. Camaan and J. O. Wilkes, Digital Computing and Numerical Methods (New York: Wiley, 1973), p. 405. (b) D. J, Wilde and C. S. Beightler, Foundations of Opti ‘ization, 2nd ed. (Upper Saddle River, NJ: Prentice Hall, 1979). (c) D. Miller and M. Frenklach, Int. J. Chem, Kinet, 15 (1983), p. 677.Section 7.5 Nonlinear Regression 261 ‘Reference Shelf The combination that gives that minimum is o = 2 and k = 5.0 dm’/mol-min as shown in Figure 7-6. If the equations are highly nonlinear, the initial guesses, cof ct and & are very important ‘A number of software packages are available (0 carry out the procedure to determine the best estimates of the parameter values and the corresponding confidence limits. All we have to do is to enter the experimental values into the computer, specify the model, enter the initial guesses of the parameters, and then push the “compute” button, and the best estimates of the parameter values along with 95% confidence limits appear. If the confidence limits for a given parameter are larger than the parameter itself, the parameter is probably not significant and should be dropped from the model, After the appropriate model parameters are eliminated, the software is run again to determine the best fit with the new model equation, Concentration-Time Data. We will now use nonlinear regression to deter- mine the rate-law parameters from concentration-time data obtained in batch experiments. We recall that the combined rate-law stoichiometry mole balance for a constant-volume batch reactor is ds = kg 7-19) at Ch ory) We now integrate Equation (7-6) to give 1—a)kt Rearranging to obtain the concentration as a function of time, we obtain Cy = (CAS (ae (7-20) Now we could us ether Polymath or MATLAB to find the values of and k that would minimize the sum of squares of the diferences between the mea- sured concentrations, Cyyy, and calculated concentrations, Cau That is, for N data points 2 = Cam Cnc) = [Cam [Cua pang} 7-21) we want the values of and k that will make ? a minimum, If Polymath is used, one should use the absolute value for the term in brackets in Equation (7-16), that is, se [eam {(abstCs* (1 = a) &t,1}" my (722) ‘Another, and perhaps easier, way to solve for the parameter values is to use time rather than concentrations, rearranging Equation (7-20) to get (7-23)262 Collection and Analysis of Rate Data Chapter 7 ‘That is, we find the values of k and @ that minimize Santo = y [' (7-24) Finally, a discussion of weighted least squares as applied to a first-order reac- tion is provided in the Professional Reference Shelf R7.5 on the CRE Web site. Reference Shelt | Example 7-3. Use of Regression to Find the Rate-Law Parameters We shall use the reaction and data in Examples E use regression to find cand E (C\U,),CC1 + CHOU (C,H1,),COCH, + IC A+ B > c€ 4D 11 and E7-2 to illustrate how to “The Polymath regression program is included on the CRE Web site. Recalling Equa- tion (E5-15) 7.25) and integrating with the intial condition when # = 0 and Cy = Cyo for a # 1.0 er. Given or assuming K’ and of, Equation (7-2.5) can be solved to calculate the time 10 reach a concentration Cy of we could calculate the concentration Cy at time 1. ‘We can proceed two ways fiom this point, both of which will gye the same resylt ‘We can search for the combination oc and & that mini To = 3 — th.) 1 fo we could solve Equation (E7-4.3) for Cy and Gnd ct and & that minimize [o" = 3 (Cig Cie)" ]- We shall choose the former. So, substituting for the ini- tial concentation Cys = 0.05 mold into Equation (E7-3.1) 1 1005/92 Wray ‘A brief tutorial on how to input data in Polymath is given in the Polymath link in the Summary Notes on the CRE Web site for Chapter 7. The Polymath tuto- rial on the CRE Web site shows screen shots of how to enter the raw data in Table 187-2.1 and how to camry out a nonlincar regression on Equation (E7-3.2). For Cy. 0.05 mol/dm’, that is, Equation (E7-3.1) becomes e732 733) ‘The result ofthe first and second Polymath regressions are shown in Tables and E:Section 7.5 Nonlinear Regression 263 Trews ETA. Researe oP Ist Recess Tams: E732 Rests ob 2N0 Ruckesi0 POLYMATH Results ‘Nanna regression LM) POLYMATH Results ‘Nomina sersson LM Mode: = (084 ta}Cer rant a) Modal (05402-0341 2)C(0.2) Neniner pression stihgs Nonna reson setngs Iioce teraione= Eon Sora Taaas 1 Somes oad” opeataat Variance = 02965618 Wertance = MS25868 aaa 3=30 0.147 dm’ /mol min k’ = 0.125 dm /mol-min| ‘The first regression gives «= 2.04, a8 shown in Table E7-3.1. We shall round off to make the reaction second order, (de., = 2.00). Now having fixed ot at 2.0, we must do another regression (ef. Table E7-3.2) on &’ because the &’ given in Table E7-3.1 is for «= 2.04. We now regress the equation ele ea) ‘The second regression gives H = 0.125 dm’/mol - min, We now caleulate & k= E925 (8) rnin Go (mot ) Analysis: In this example, we showed how to use nonlinear regression to find X and ‘1. The first regression gave ct = 2.04, which we rounded to 2.00 and then regressed again forthe best value of & for & = 2.0, which was F’ = 0,125 (dm’/mol}/min giving a value of the true specific reaction rate of k = 0.25 (moV/dm')*/min, We note that the reaction order is the same as that in Examples 7-1 and 7-2; however, the value of k is about 8% larger. The 72 and other statistics are in Polymath's output. Model Discrimination. One can also determine which model or equation best fits the experimental data by comparing the sums of the squares for each ‘model and then choosing the equation with a smaller sum of squares and/or carrying out an F-test, Alternatively, we can compare the residual plots for each model. These plots show the error associated with cach data point, and one looks to see if the error is randomly distributed or if there is a trend in the error. When the error is randomly distributed, this is an additional indication that the correct rate law has been chosen. An example of model discrimination using nonlinear regression is given in Chapter 10.264 Most commonly ‘wed catalytic reacior to obtain ‘experimental data Limitations of the dlfeental reactor Collection and Analysis of Rate Data Chapter 7 7.6 Reaction-Rate Data from Differential Reactors Data acquisition using the method of initial rates and a differential reactor is ilar in that the rate of reaction is determined for a specified number of predeter- ined initial or entering reactant concentrations. A differential reactor (PBR) is normally used to determine the rate of reaction as a function of either concen- tration or partial pressure. It consists of a tube containing a very small amount of catalyst, usually arranged in the form of a thin wafer or disk. A typical arrange- rent is shown schematically in Figure 7-7. The evterion for a reactor being dif ferential is that the conversion of the reactants in the bed is extremely small, as is the change in temperature and reactant concentration through the bed. As a result, the reactant concentration through the reactor is essentially constant and approx {mately equal to the inlet concentration. That is, the reactor is considered to be sgradientless and the reaction rate is considered spatially uniform within the bed. The differential reactor is relatively easy to construct at a low cost Owing to the low conversion achieved in this reactor, the heat release per unit volume will be small (or can be made small by diluting the bed with inert solids) so that the reactor operates essentially in an isothermal manner. When operating this reactor, precautions must be (aken so that the reactant gas or liquid does not bypass or channel through the packed catalyst, but instead flows uniformly across the catalyst. Ifthe catalyst under investigation decays rapidly, the differ ential reactor is not a good choice because the reaction-rate parameters at the start of a run will be different from those at the end of the run. In some cases, sampling and analysis of the product stream may be difficult for small conver- sions in multicomponent systems } fab Seon Figure 7-7 Differential reactor. Figure 7-4. Differential catalyst bed, ‘or the reaction of species A going (o product (P) AoP the volumetric flow rate through the catalyst bed is monitored, as are the enter- ing and exiting concentrations (Figure 7-9). Therefore, if the weight of cata- lyst, AW, is known, the rate of reaction per unit mass of catalyst, —r,, can be calculated, Since the differential reactor is assumed to be gradientless, the design equation will be similar to the CSTR design equation. A steady-state mole balance on reactant A gives TB. Anderson, ed., Experimental Methods in Catalytic Research (San Diego, CA‘ Academic Press, 1976)Section 7.6 Reacton-Rate Data from Diferentil Reactors 265 Disferential reactor design equation Flow] [Flow Rate of Rate of rate |—| rate |+ jeneration ~ | accumulation in out, fs - Rate of reaction | gas of catalyst) |= [aol — [Fae (Resese oo f catalys »| ° Fy - Fy + (AW) = ° The subscript ¢ refers to the exit of the reactor. Solving for —r, we have From Fac “ar (7-26) The mole balance equation can also be written in terms of concentration 1 = PCa VC ae z nro (7-27) or in terms of conversion or product flow rate Fp = FaoX _ Fe z Th eo AP (7-28) The term FyoX° gives the rate of formation of product, Fy, when the stoichio- metric coefficients of A and of P are identical, Adjustments to Equation (7-28) must be made when this is not the case. For constant volumetric flow, Equation (7-28) reduces to apt = PolCao7 Cre) _ Yor a AW aw (7-29) Consequently, we see that the reaction rate, ~r,, can be determined by mea- suring the product concentration, Cp By using very litte catalyst and large volumetric flow rates. the concen- tration difference, (Cag ~C4,), can be made quite small. The rate of reaction determined from Equation (7-29) can be obtained as a function of the reactant concentration in the catalyst bed, Cg, a= —rAlCap) (7-30) by varying the inlet concentration. One approximation of the concentration of A within the bed, C,,, would be the arithmetic mean of the inlet and outlet concentrations (731)268 Pag, 48 constant in Runs 12,3 Po is constant in Runs 45,6 Collection and Analysis of Rate Data Chapter 7 However, since very litle reaction takes place within the bed, the bed concen- tration is essentially equal to the inlet concentration Can Coo, so rh is a function of Cag th = —tA(Cn0) (7-32) As with the method of initial rates (see the CRE Web site, PRS R7.1), various numerical and graphical techniques can be used to determine the appropriate algebraic equation for the rate law. When collecting data for fluid-solid react- ing systems, care must be taken that we use high flow rates through the differ- ential reactor and small catalyst particle sizes in order to avoid mass transfer limitations. If data show the reaction to be first order with low activation energy, say 8 kcal/mol, one should suspect the data are being collected in the ‘mass transfer limited regime. We will expand on mass transfer limitations and how to avoid them in Chapters 10, 14, and 15, Example 7-4 Using a Differential Reactor to Obtain Catalytic Rate Data ‘The formation of methane from carbon monoxide and hydrogen using @ nickel cat- alyst was studied by Pursley The reaction 3H,+CO>CH, +11,0 was carried out at S00°F in a differential reactor wisere the efiluent concentration of ‘methane was measured, The raw data is shown in Table B7-4.1 ‘Tame ET-41 Raw Data Ran Poo (atm) Py, (atm) Cy (old 1 10 173 x 10-* 2 Ls 10 4.40 x 10~ 3 408 10 loo x 10-# 4 10 o4 195 x 10- 5 ° 05 247 x 1o~* 6 0 © 75 x 10-# ‘The exit volumetric flow rate from a differential packed bed containing 10 g of cat- alyst was maintained at 300 dimY/min for each run. The partial pressures of H, and ‘CO were determined at the entrance to the reactor. and the methane concentiation was measured at the reactor exit, Determine the rate law and rate law parameters. (a) Relate the rate of reaction to the exit methane concentration. The reaction-rate law is assumed to be the product of a function of the partial pressure of CO and a function of the partial pressure of H, rou, = CO): BCH) ery 53. A. Bussey, “An Investigation of the Reaction between Carbon Monoxide and Hydrogen ‘on a Nickel Catalyst above One Atmosphere,” PhD. thesis, University of Michigan.Section 7.6 Reacton-Rate Data trom Differential Reactors 267 (b) Determine the rate-law dependence on carbon monoxide, using the data gen- crated in part (a), Assume that the functional dependence of ry, 08 Poo is of the form e742) (©) Determine the rate-law dependence on H,. Generate a table of the reaction rate as a function of partial pressures of carbon monoxide and hydrogen. Solution (a) Calculate the Rates of Reaction, In this example the product composition, rather than the reactant concentration, is being monitored. The term (—r5) can be ‘written in terms of the flow rate of methane fzom the reaction Substituting for Foy, in terms of the volumetsic flow rate and the concentration of methane gives r-43) Since ve, Cen, and AW are known for each run, we can calculate the rate of reaction. For run I mol CH, eat X min 5.2% 107 ‘The rate for runs 2 through 6 can be calculated in a similar manner (Table E7-4.2) Tams E742 Raw axo Cazernann Data, _(moVdn') ren, (aa) Run Peo (atm) — Pp, (at) Feat am, 10 10 LTS x 10-* 52x 10-) 2 18 Lo 4.40 X 10-* 12x10" 3 408 Lo 0.0% 1 3000 10? 4 10 04 165 10~* 4.95 x 107) 5 10 05 247 x 10-4 742 X - 6 10 40 175 10~* 525 10") (b) Determining the Rate-Law Dependence in CO. For constant hydrog centration (runs 1, 2, and 3), the rate law Fey, = Ro #(P,) can be waiten as ea, =F Pho (7-44) ‘aking the natural log of Equation (H7-5.4) gives us In(rén,) = Ink? +6 InPoo268 1 we had used more data (not sven here) we ‘would have found «= 1 Collection and Analysis of Rate Data Chapter 7 ‘We now plot In(ri,) versus InPoo using runs 1, 2, and 3, for which the H con- centration is constant, in Figure E7-4.1. We see from the Excel plot that = 1.22 0.100 vem, Yeny= 0.0056P.3" o.010 mol Teat min 0.001 04 1 10 Peo (atm) igure E7-4.1. Reaction rate ata function of concentation, Had we included more points, we would have found that the reaction is essentially first onder with of = 1, that is area = K'Poo ers, From the frst three data points where the partial pressure of H, is constant, we see the rate is linear in partial pressure of CO c1,=# Peo 8H) Now let’s look at the hydrogen dependence () Determining the Rate-Law Dependence on H,, From Teble E7-4.2 it appears that the dependence of réq, on Py, cannot be represented by a power law. Compar- ing run 4 with run 5 and then run’ S with ran 6, we see that the reaction rate first inereases with increasing partial pressure of hydrogen, and subsequently decreases With increasing Py, That is, there appears to be a concentration of hydrogen at ‘which the rate is maximum, One set of rate laws that is consistent with these obser- vations is: 1. Atlow H, concentrations where rin, increases as P; may be of the form increases, the rate law sig, # r-46) 2. Achigh 1, concentrations where ry, decreases as Py, increases, the rate law may be of the form 1 : rag eranSection 7.6 Reacton-Rate Data trom Differential Reactors 269 ‘Typical form of the rate law for heterogeneous catalysis gS ‘Summary Ni Polymath and Excel regression tutorial fae given inthe Chapter 7 Summary ‘Notes on the CRE Web site We would like to find one rate law that is consistent with reaction-rate data at both high and low hydrogen concentrations. After we have studied heterogeneous reactions in Chapter 10, we would recognize that Equations (B7-4.6) and (E7-4.7) ean be combined into the form e748) ‘We will soe in Chapter 10 that this combination and similar rat laws that have reac- tant concentrations (or partial pressures) in the numerator and denominator are com- ‘mon in heterogeneous catalysis. Let's see if the resulting rate law (E7-4.8) is qualitatively consistent with the rate observed. 1, For condition I: Atlow Py,, (6(Py,)°#€1] and Equation ( 8) reduces to Ye, ~ Pa, (7-49) Equation (E7-49) is consistent withthe trend in comparing runs 4 and 5 2, For condition 2: Atbigh Py,, (B(Py,)"°® 1] and Equation (5-58) reduces to (E7-4.10) where >. Equation (B7-4.10) is consistent with the ends in comparing runs 5 and 6 Combining Equations (E7-4.8) and (E7-4.5) (74.11) ‘We now use the Polymath regression program to find the parameter values a, b, By and 8. The results are shown in Table B7-4.3. Tha B7A13 Finer Recess ‘Nonlinear reeesson L-M) ca"Pravbtat (148 Ph2%ela2) Beale kaa | gins | oat Beat i dvereeses | 623023206 5 i 2ce72s69 | Sa00a548 Nonlinear regression setings Max herbone 284 ‘The corresponding rate law is 0.025 Pea PQs! rg, = Seo 74.12) TR,270 Lincaizng the rate law co deermine the Tate law parameters Collection and Analysis of Rate Data Chapter 7 ‘We could use the rate law given by Equation (B7-4.12) as is, but there aze only six data points, and we should be concerned about extrapolating the rate law over a wider range of paral pressures. We could take more dala, andlor we could carry out 4 theoretical analysis of the type discussed in Chapter 10 for heterogeneous reac- tions. If we assume hydrogen undergoes dissocialive adsorption on the catalyst surface, we would expect a dependence on the partial pressure of hydrogen to be to the 's power. Because 0.61 is close to 0.5, we ae going to regress the data agin, setting f = #2 and fy = 1.0. The results ate shown in Table B7-4.4 Tame BT-44 Secon) REGRESSION ‘Nonlinear regression LM) Model: ate = a°Peo"PR2OSI(48"PH2) peaiae phous loctieniy | eoloetae 5 i Gaaseaes| 114797481 ‘The rate law is now 0.0187 oP Po TT aeP a, where roy, is in (mol/g-cat- s) and the partial pressures are in (atm). We ‘ould also have set B, = ‘ and 8, = 1.0 and rearranged Equation (E7-4.11) in the form Poo 1 Lada es A plot of PooPi?/ray, a8 a function of Py, should be a straight line with an inter cept of Ia and a slope of bfa. From the plot in Figure E7-4,2, we see that the rate law is indeed consistent with the rate-law data 00 ony 200 100 Pa ten Figure E742 Linearized plot of data Analysis: The reaction-rate data in this example were obtained at steady state, and a8 a result, neither the integral method nor differential method of analysis can be used, One of the purposes of this example isto show how to reason out the form of the rate law and to then use regression to determine the rate-law parameters. Once the parameters were obtained, we showed how to linearize the rate-law le... Equa- tion (E7-4.13)] to generate a single plot ofall the data, Figure (27-4.Chapter 7 Summary ant 2 7.7 Experimental Planning i Fou to sx weeks inthe lab can save you an hour in x the library. 6.€. Quarderer, Dow Chemical Co Retreace Set So far, this chapter has presented various methods of analyzing rate data, It is just as important to know in which circumstances to use each method as it is to know the mechanics of these methods. In the Expanded Material on the CRE Web site, we give a thumbnail sketch of a heuristic to plan experiments (o gen- crate the data necessary for reactor design. However, for a more thorough dis- cussion, the reader is referred to the books and articles by Box and Hunter. Closure, After reading this chapter, the reader should be able to analyze data to determine the rate law and rate-law parameters using the graphical and numerical techniques, as well as software packages. Nonlinear regtes- sion is the easiest method to analyze rate-concentration data to determine the parameters, but the other techniques, such as graphical differentiation, help one get a feel for the disparities in the data. The reader should be able to describe the care that needs to be taken in using nonlinear regres- sion to ensure that one does not arrive at a false minimum for 62, Conse- quently, itis advisable to use more than one method to analyze the data. SUMMARY 1. Integral method 4. Guess the reaction order and integrate the mole balance equation, ®. Calculate the resulting function of concentration for the data and plot it as a function of time. IE the resulting plot is lineat, you have probably guessed the corsect reaction order. . If the plot is not linear, guess another order and repeat the procedure. 2. Differential method for constant-volume systems - (St-1) a. Plot —AC,/At as a function of &. Determine —dC,/dt from this plo. «. Take the In of both sides of ($7-1) to get dcx \ af ‘=e anc, ($7.2) Plot In(—dC,/dt) versus InC,. The slope will be the reaction order a. We could use finite-difference Formulas o software packages to evaluate (—dC,/df) as a function of time and concentration. ©G. BP Box, W. G. Hunter, and J. §. Hunter, Statistics for Experimenters: An Insroduetion to Design, Data Analysis, and Model Building (New York: Wiley. 1978).272 Collection and Analysis of Rate Data Chapter 7 3. Nonlinear regression: Search for the parameters of the rate law that will minimize the sum of the squares of the difference between the measured rate of reaction and the rate of reaction calculated from the parameter values chosen. For N experimental runs and K parameters to be determined, use Polymath 2_ & (P(measured) ~ P, (calculated) }? of = 5p Pitreasured ~ Fi (caleuleted) S7-3 = N-K rs (7-4) ‘Caution: Be sure to avoid @ false minimum in o° by varying your initial guess. 4. Modeling the differential reactor ‘The rate of reaction is calculated from the equation w= eh Be (75) AW AW In calculating the reaction order, o the concentration of A is evaluated either al the entrance conditions or al a miean value between Cap and C,,. However, power-law models such as =n =Kexch (S7-6) are nol the best way to describe heterogeneous reaction-rate laws. Typically, they take the form , WP TE KAP + Ka ‘ora similar form, with the reactant partial pressures in the numerator and denominator of the rate law. CRE WEB SITE MATERIALS Expanded Material 1. Bvaluation of Laboratory Reactors 2, Summary of Reactor Ratings, Gas-Liguid, Powdered Catalyst Decaying Catalyst System 3. Experimental Planning 4, Additional Homework Problems Learning Resources 1. Summary Notes 2. Interactive Computer GamesChapter 7 CRE Web Site Materials 273 A. Ecology Interactive B. Reactor Lab (wwwreactorlahnet). See Reactor Lab Chapter 7 and P7-3,, 3. Solved Problems Living Example Problems 1, Example 7-3 Use of Regression to Find the Rate Law Parameters + FAQ (Frequently Asked Questions)—In Updates/FAQ icon section Solved Problems + Professional Reference Shelf RIL Method of Initial Rares R72 Method of Half Lives RT. Least Squares Analysis of the Linearized Rate Law The CRE Web site describes how the rate law mn oki ch is inaized Incr) =In k+ 0.1m C,+ Bln Cy and put in the form Y= ay+ OX, + BX, and used (0 solve for a, B, and &. The etching of a semiconductor, MnO,, is used as an example to illustrate this technique, RIA A Discussion of Weighted Least Squares For the case when the error in measurement is not constant, we must use a weighted least-squares analysis. RIS Experimental Planning ‘Why perform the experiment? ‘Are you choosing the correct parameters? ‘What is the range of your experimental variables? Can you repeat the measurement? (Precision) Milk your data for all it's wort ‘We don't believe an experiment until i's proven by theory ‘Tell someone about your result RT.6 Evaluation or Laboratory Reactor ammoap>274 Collection and Analysis of Rate Data Chapter 7 QUESTIONS AND PROBLEMS ‘The subscript to each of the problem numbers indicates the level of difficulty: A, least dif- ‘cut; D, most dificult, © B=m C=4 D=0e Home Wark Problems Questions Q7-1y (@) Listen to the audios ee the CRE Web site and pick one and say why it could be eliminated, (Goose sige le ted or Capra (2 Denn stint ort asad tht donee te psp fen Sica Nec Ss Chap Coopeion Rae es pened oe CRE We Se co) RB Bopermen Pc mb ae nlc pos com woke Tin Re gues fan poviltesmped ane cae St Mee ahah ef ttn aoe tear“ Problems rea, Mh TCM Bong Perfomance # 7754 Goto oto tes Reactor Lab ens Web a yarn Be Gh ne GOTOH zes from Division 1. When you first enter ¢ lab, you see all input values and can vary them. In a lab, click on the Quiz bution in the navigation bar to enter the quiz for that lab. In a quiz, you cannot see some of the input values: you need to find those with “97” hiding the values. In the quiz, perform exper {ments and analyze your data in order to determine the unknowo values, See the bottom of the Example (Quiz page at www: reactorlabnet for equations that relate E and k. Click on the “722” next to an input and supply your value. Your answer will be accepted if itis within #20% of the correct value. Scoring is done with imaginary dollars to emphasize that you should design your experimental study rather than do random experiments. Each time you enter a quiz, new unknown values aze assigned. To reenter an ‘unfinished quiz at the same stage you left, click the [i] info button in the Ditectory for instructions, Turn in copies of your data, your analysis work, and the Budget Report.Chapter 7 PI-4, PIS, @) (b) © ‘Questions and Problems 275 ‘When arterial blood enters a tissue capillary, it exchanges oxygen and carbon dioxide with its environ- ment, as shown in this diagram, & ‘The kinetics of this deoxygenation of hemoglobin in blood was studied with the aid of a tubular reactor by Nakamura and Staub (J. Physiol, 173, 161). k HO, <4 Hh+0, ky Although this is a reversible reaction, measurements were made in the initial phases of the decompo- sition so that the reverse reaction could be neglected, Consider a system similar to the one used by Nakamura and Staub: the solution enters a tubular reactor (0.158 cm in diameter) that has oxygen elec trodes placed at 5-cm intervals down the tube. The solution flow rate into the reactor is 19.6 cm/s with Cao = 2.33 x 10 mol/em >[*,[>5]* |? aaa | sae | 7a | 925 | too Blectode positon 1 0.00 Persent decomposition of HOO, 195 (a) Using the method of differential analysis of rate data, determine the reaction order and the forward specific reaction-rate constant k, forthe deoxygenation of hemoglobin, (b) Repeat using regression, ‘The liquid-phase irreversible reaction ABC is cartied out in a CSTR. To leam the rate law, the volumetiic ow rate. vp. (hence = Vv) is var- Jed and the effluent concentrations of species A are recorded as a function of the space time t. Pure A enters the reactor at a concentration of 2 mol/dm*. Steady-state conditions exist when the measure ‘ments are recorded. ‘a (moiiém) [15 Determine the reaction order and specific reaction-rate constant. If you were to repeat this experiment to determine the kinetics, what would you do differently? Would you run at a higher, lower, or the same temperature? If you were to take more data, where would you place the measurements (e.g., 2)? Tis believed that the technician may have made a dilution factorof-10 error in one of the conce ration measurements. What do you think? How do your answers compare using regression (Poly ‘math or other software) with those obtained by graphical methods? Note: All measurements were taken at steady-state conditions276 PTI-64 PTI-T4 PTB, Collection and Analysis of Rate Data Chapter 7 ‘The reaction ASB+C was carried out in a constant-volume batch reactor where the following concentration measurements were recorded as a function of time, (in) os 9 Is 2m 3 4 60 Catmavamy [2 16 135 11 087 070 053 035 (a) Use nonlinear least squares (ie., regression) and one other method to determine the reaction order, «and the specific reaction rat, f (b) Nicolas Bellint wants to know, if you were to take more data, where would you place the points? Why? (©) Prof. Dz. Sven Kottloy from Jofostan University always asks his students, if you were to repeat this experiment to determine the Kinetics, what would you do differently? Would you run at a higher, lower, or the same temperature? Take different data points? Explain (@) This believed that the technician made a dilution error in the concentration measured at 60 min, ‘What do you think? How do. your answers compare using regression (Polymath or other software) with those obtained by graphical methods? ‘The following data were reported [from C. N. Hinshelwood and P. J. Ackey, Proc. R, Soe. (Lond). IIS, 215] for a gas-phase constant-volume decomposition of dimethyl ether at S04°C in a batch reac tor. Initially, only (CH,),O was present. Time (9) 390 777 L198 3155 Toial Pressure (owmtig) | 408 488 562799981 (a) Why do you think the total pressure measurement at ¢ = 0 is missing? Can you estimate it? (b) Assuming that the reaction (CH),0-9CH.=H, co is irreversible and goes virtually to completion, determine the reaction order and specific reaction rate k (6) What experimental conditions would you suggest if you were to obtain more data? (@) How would the data and your answers change if the reaction were tun at a higher temperatuse? A. lower temperature? In order to study the photochemical decay of aqueous bromine in bright sunlight, a small quantity of liguid bromine was dissolved in water contained in a glass battery jar and placed in direct sunlight. The following data were obtained at 25°C: Time (win) | 10 20-040 ppm Br, 245 174 123 088 062 oad (a) Determine whether the reaction rate is zero, first, or second order in bro- mine, and calculate the reaction-rate constant in units of your choice, (b) Assuming identical exposure conditions, calculate the required hourly rate of injection of bromine (in pounds per hour) into a sunlit body of water, 25,000 gal in volume. in order to maintain a sterilizing level of bromine of 1.0 ppm. [Ans.: 0.43 Ib/]