Numerical Techniques A.1 Useful Integrals in Reactor Design BP? 1330 see wimintegralscom Links * de 1 win. Ms ey Ee i T-x% I-x, 1-5 ie ,d- I=% fas x * de 1 fe wlegs [eigctacten : [Obeid atone ; = co [Ged Cees — gig ota =e T= y 2 I (texte _ 90014 eyin(l—x)+o% + Ut jy daaF =x 1009 (At a2 (A-3) (A-4) (A-5) (A-6) (A-7)1010 Numerical Techniques * dx =u Og-x [ a=ne@=57S-1"30=5 | fF! ‘ [fa-em'an 211-(-am)) f a. * dk 22 eee Bada [, mithte wate e 1 de 1 xe te inf f.2=2 B>4 I, avtbxte ap—a) n(a ang) Or dac where p and q ure the roots of the equation. attixte=0 ieapg = Eee 4ac shoe a [i ator gy = OX 4 ag be jot Ex 9 Ctr g g c ion A.2 Equal-Area Graphical Differenti App. A (A-8) (A-9) (A-10) (A-11) (A-12) There are many ways of differentiating numerical and graphical data, We shall confine our discussions to the technique of equal-area differentiation. In the procedure delineated here, we want to find the derivative of y with respect to x. 1. Tabulate the (y;, x;) observations as shown in Table A-1. 2. For each interval, calculate Ax, = x, — %q-) and Ayy = Yq — 3 Tame A+} ny ax ay a dy a a] \e) an en (8 oe Ar) hoy (e 2 dx), This method finds aie | use in Chapter 5. . As),See CD-ROM, Appendix A, for ‘worked example Links: ‘Sec. A2 — Equal-Area Graphical Differentiation 1011 3. Calculate Ay,/Ax, as an estimate of the average slope in an interval Xp-1 10%, 4, Plot these values as a histogram versus x,. The value between x, and X4, for example, is (y3 — ¥2)/(x3 — x2). Refer to Figure A-1 Figure A-IEqual-area differentiation 5. Next draw in the smooth curve that best approximates the area under the histogram. That is, attempt in each interval to balance areas such as those labeled A and B, but when this approximation is not possible, balance out over several intervals (as for the areas labeled C and D). From our definitions of Ax and Ay we know that wna > Bas (A-13) im The equal-area method attempts to estimate dy/dx so that a dy 1 — yim fe 14) MN Le (A-14) that is, so that the area under Ay/Ax is the same as that under dy/dx, everywhere possible. Read estimates of dy/dx from this curve at the data points xy, x3, -. and complete the table. a An example illustrating the technique is given in the CD-ROM, Appendix A Differentiation is, at best, less accurate than integration. This method also clearly indicates bad data and allows for compensation of such data. Differen- ation is only valid, however, when the data are presumed (0 differentiate as in rate-data analysis and the interpretation of transient diffusion1012 Numerical Techniques App. A A.3 Solutions to Differential Equations A3.A_ First-Order Ordinary Differential Equation yD See wiww.ucl.ac.uk/Mathematics/geomath/level2/deqn/de8.html and CD-ROM Appendix K, Lines aad dy & + gyy = : a FOv=8 (A-15) Using integrating factor = exp (a). the solution is -fa fw [ow yee Jew dt+Kye (A-16) Example A-1 Integrating Factor for Series Reactions De nyake aoe Integrating factor = exp i igdt =e s (ave) Mig Wang a i te pthoAn e yahfe D ky tape dt=—1~¢ +K, k- A.3.B Coupled Differential Equations Techniques to solve coupled first order linear ODEs such as dx eo ays a by Ye ext mnt are given in Appendix K in the CD-ROMSolutions of this, type are required in Chapter 12. Sec.A4 Numerical Evaluation of Integrals 1013 3.0 Second-Order Ordinary Differential Equation Methods of solving differential equations of the type (A-I7) can be found in such texts as Applied Differential Equations by M. R. Spiegel (Upper Saddle River, N.J.: Prentice Hall, 1958, Chapter 4; a great book even though it’s old) or in Differential Equations by F. Ayres (New York: Schaum Outline Series, McGraw-Hill, 1952). One method of solution is to determine the characteristic roots of which are m=+/B8 The solution to the differential equation is y= Ae-“Br+ Bet Br (A-18) where A, and B, are arbitrary constants of integration. It can be verified that Equation (A-18) can be arranged in the form y=Asinh /Bx + Bcosh./Bx (A-19) Equation (A-19) is the more useful form of the solution when it comes to eval- uating the constants A and B because sinh(0) = 0 and cosh(0) = 1.0. A.4 Numerical Evaluation of Integrals In this section, we discuss techniques for numerically evaluating integrals for solving first-order differential equations. 1. Trapezoidal rule (two-point) (Figure A-2). This method is one of the simplest and most approximate, as it uses the integrand evaluated at the limits of integration to evaluate the integral: i [feoae= Sym) +f (A20) % when h =X, — Xo.1014 Numerical Techniques App. A 2. Simpson's one-third rule (three-point) (Figure A-3). A more accurate evaluation of the integral can be found with the application of Simp- son's rule: (A-21) where £060) in Chapters 2.4.8, ' and = | 1%) t [xweina 1——+ in Chapter 13 «© tg x Figure A-2 Trapezoidal le illustration. “Figure A-3_ Simpson's three-point rule illustration, 3. Simpson's three-eighths rule (four-point) (Figure A-4). An improved version of Simpson’s one-third rule can be made by applying Simp- son's three-eighths rule: * { ° 9X0) aX = EAU) + 37%) + 30) + FOG) (22 Xo where nao eX th X= Xp + 2h 1x) Xo Xe Ks Figure A-4 Simpson's four-point rule illustration, 4. Five-point quadrature formula. [senar=taranr mires to (A23) XoLinks Sec.A5 Software Packages 1015 -% where he tow 5. For N + 1 points, where (W/3) is an integer, ty * f(X) aX = hfe + 3h + 3h + 2h Ja Fit Yet Bot + 3fva (A-24) where h = Xo N 6. For N + 1 points, where N is even, [roe LAA + AM ABW t ot ust he) Xo (A-25) where These formulas are useful in illustrating how the reaction engineering integrals and coupled ODEs (ordinary differential equation(s)) can be solved and also when there is an ODE solver power failure or some other malfunction A.5 Software Packages Instructions on how to use Polymath, MATLAB, FEMLAB, and Aspen can be found on the CD-ROM. For the ordinary differential equation solver (ODE solver), contact: Polymath Aspen Technology, Inc. CACHE Corporation 10 Canal Park P.O. Box 7939 Cambridge, Massachusetts Austin, Texas 78713-7379 02141-2201 Web site: www,polymath- Email: info@aspentech.com software.com/fogler Web site: /Avww.aspentech.com MATLAB FEMLAB The Math Works, Inc. COMSOL, Inc. 20 North Main Street, Suite 250 8 New England Executive Park, Suite 310 Sherborn, Massachusetts 01770 Burlington, Massachusetts 01803 Tel: 781-273-3322; Fax: 781-273-6603 Email: info@comsol.com Web site: www.comsol.com A critique of some of these software packages (and others) can be found in Chem. Eng. Educ., XXV (Winter) 54 (1991).%)Ideal Gas Constant B and Conversion Factors See wwmonlineconversion.com. Links Ideal Gas Constant p= 0:73 faim a= 1987 Btu Tb mal -°R Ib-mol -°R pa 8314 kPa-dm? p= 83144) mol -K mol-K dm’ atm _ 0.082 m}-atm L987cal 82 0.082 mivatm p= L.987cal RNR li kmolK mol" K Boltzmann's constant ky = 1.381 x 10 ——2___. molecule * K 1.381 x 10 kg m?/s*/molecule/K Volume of Ideal Gas | Ib-mol of an ideal gas at 32°F and | atm occupies 359 ft° (0.00279 Ibmol/ft*). 1 mol of an ideal gas at °C and | atm occupies 22.4 dm? (0.0446 mol/dm’). Pa _YaP C, =A = MA “RE RT where % = concentration of A, mol/dm} T= temperature, K = pressure, kPa mole fraction of A i ideal gas constant, 8.314 kPa- den’/mol- K 10171018 Ideal Gas Constant and Conversion Factors App. B Volume lem? = 0.001 dm? lin’ 0.0164 dm 1 fluid oz — = 0.0296 dm? 1 ft = 28.32 dm* 1m = 1000 dm? 1 US. gallon = 3.785 dm? liter (L) = 1 dm? 1 f = 28.32 dm? x —! £8! _ — 7.489 gat ( . a7es am “8? 8 Pressure Energy (Work) 1 torr (1 mmHg) = 0.13333 kPa J 1 in. HO 1035.06 J 1 in. He 3 1 cal = 4.1868 J 1 atm 101.33 kPa 1L-atm = 101.34) 1 psi 6.8943 kPa 1 hp-h 2.6806 10° J 1 megadyne/om? = 100 kPa 1kWh 3.6 x 10°] Temperature Mass F 18 x °C + 32 1b 454g R °F + 459.69 1kg 1000 g K °C + 273.16 1 grain 0.0648 ¢ R =18XK 1 oz (avoird.) = 28.35 g Réamur = 1.25 x °C Lton = 908,000 g Viscosity 1 poise = 1 g/cm/s = 0.1 kg/mv/s 1 centipoise = 1 cp = 0.01 poise Force 1 dyne = 1 g- cm/s? 1 Newton = I kg m/s? Pressure 1 Pa = | Newton/m? Work A. Work = Force x Distance 1 Joule = 1 Newton - meter = | kg m?/s? = 1 Pa - m? B. Pressure x Volume = Work 1 Newton/ m?- m3 = 1 Newton: m = | JouleApp. B Ideal Gas Constant and Conversion Factors Time Rate of Change of Energy with Time 1 watt = 1 I/s Lhp = 746 Js Gravitational Conversion Factor Gravitational constant g = 32.2 fus? American Engineering System g.= 32.174 2a) (S')(Iby) SWcgs System = 1 (Dimensionless) ‘Tame B.l Typicat Property VALUES Liguid Gas (water) (air, 77°C, 101 kPa) Density 1000 kg/m 10 kein Concentration 55.5 moVidm? 0,04 mova? Diffusivity 10% ms 103 ms Viscosity 10° kg/mis 1.82 x 10-5 kg/mis Heat capacity 431 gk 40 SemoVK ‘Thermal conductivity 1.0 Ws/v/K 10? WsinvK Kinematic viscosity 10% mis 1.8 x 10% ms Prandtl number 4 07 1019 Solid 3000 kg/m™ 10" ms 0.45 Jig 100 JstmiK Schmidt number 200 ai ‘Tame B.l TyPicat. Transport VALUES Liquid Gas Heat Transfer Coefficient, b 1000 WimiTK 65 Wink Mass Transfer Coefficient, ke 10 mis 3 ms