Chemical Reaction Engineering Handbook of Solved Problems Walas PDF

CHEMICAL REACTION ENGINEERING HANDBOOK OF SOLVED PROBLEMS Stancey M. Wacas | Gordon and Breach Publishers eChemical Reaction Engineering Handbook of Solved Problems Stanley M. Walas University of Kansas, Lawrence Gordon and Breach Publishers ‘Australia + Austria * Belgium * China + France + Germany India + Japan * Luxembourg + Malaysia * ‘Netherlands * Russia * Singapore + Switzerland + Thailand * United Kingdom + United StatesCONTENTS Preface x List of Sources of Some Problems xi List of Symbols will CHAPTER 1. MATHEMATICAL AND NUMERICAL METHODS, seeienieennnennse L ‘THEORY 1 12 13 14 1s 16 7 18 Sonware.. sn Plotting and curvefitting.. Regression of tabular date Roots of numerical equations .. Integration and differentiation Ordinary differential equations... ‘Numerical solution of ODEs Partial differential equations Tables . PROBLEMS P'1.00.00 2 3 4 5. CHAPTER 2. REACTION RA’ Index of Reactions in Problem Section P2.02.XX .. Regression . Roots Integration and differentiation. Analytical solution of ordinary ditferential equations Numerical solution of ondinary differential equations. AND OPERATING MOD§S..... Index of Mechanisms in Problem Section P2.03.XX onan ee sone 33 THEORY 21 22 23 24 25 26 27 Rate of reaction... Concentration, mols, partial pressure, mol fraction Reaction time ou a Constants of the rate equation. Multipie reactions and stoichiometric balances Reactor operating modes Heterogeneous reactions, Rates of diffusion... Tebles ..vi CONTENTS, PROBLEMS 2.00.00 1. Stoichiometric balances 2. Integrated rate equations 3. Complex reaction mechanisms . 4. Numerical integrations . CHAPTER 3. TREATMENT OF EXPERIMENTAL DATA... ‘THEORY 3.1 Kinds of laboratory reactors . 3.2. Chemical composition... 3.3. Power law rate equations... ss 3.4 Rate equations for multiple mechanisms B.S Pressute $208 ve nsne 3.6 Other properties related to composition . 3.7. Temperature variation 3.8 Homogeneous catalysis. 3.9. CSTR data. Liquid or gas phase 3.10 Plug flow reactors. Laminar flow Figures PROBLEMS P3.00.00 1. Units g 5 2 Pressure changes Variables related to composition .. Half time and initial rate data .... ‘Temperature variation, Activation energy Homogeneous catalysis . Enzyme and solid catalysis Flow reactor data 10. CSTR data 11. Complex reactions .. Senawaen CHAPTER 4. IDEAL REACTORS ....... THEORY 4.1 Equilibrium constants .. 42. Temperature change and heat of reaction .. 4.3 Batch reactors ven 44 Continuous sitred tank reactors (CSTR) 4.5. Tubular and packed flow reactors 4.6 Recycle and separation modes. 4.7 Temperature changes 4.8 Laminar and power law flows ..... 4.9. Unsteady conditions with accumulation terms 4.10 Multiple steady states 4.11 Optima ... 4.12 Economic balance .. Figures.CONTENTS vii PROBLEMS P4.00.00 1, Equilibrium constants ..... 2. Temperature change and heat of reaction. 3. Batch reactors... 4. Continuous sitrred tank reactors (CSTR) 5. Tubular and packed flow reactors... 6 1, 8 98 283 Recycle and seperation modes... ‘Temperature changes sm Laminar and power law flows... Unsteady conditions with accumulation terms. 10, Multiple steady states 11. Optima 12. Economic balances... 370 383, 410 AIT 444 454 an CHAPTERS. REACTOR FFFICIENCY 1 489 THEORY $1 Introduction ... ve 1 89 5.2. Tracers, os nn 490) 53 Reactor efficiency 1 490 5.4 Tracer response vn 490 5.3. Tracer equations... 494 5.6 Characterization of curves 496 3.7 Chemical conversion... 498 5.8. The dispersion model nan nnn . 500 Figures and Tables... nnn a 503 PROBLEMS P5.00.00 L. Tracer response functions... 509 2) Correlations: Gamma, Gauss et. 331 3. Tracer response to combined elements ... 546 4, Conversion with known flow pattems. Laminar flow . 537 5. Segregated flow, part I. 568 6. Segregated flow, part II 584 7. Maximum mixed flow 602 8. Dispersion model 607 ‘CHAPTER 6. REACTIONS WITH SOLID CATALYSTS. fesse severe 3D THEORY 6.1 Catalytic processes. 6.2 Power law equations 63. Langmuir-Hinshelwood processes 64 Physical properties of granular catalysts. 65 Adsorption equations 66 Extensions of the Langmuir equation. os 6.7 Rate when adsorptive equilibrium is maintained .. 68 Rate when chemical equilibrium is maintained 69 Find the constants of a rate equation .... 6.10 Interpretation of data wnsnnnes 6.11 Severs! controlling steps... 6.12 With diffusional resistanceviii Figures and Tables «soso PROBLEMS P6.00.00 CHAPTER 7. REACTIONS WITH POROUS SOLID CATALYSTS... Physical properties of catalysts nr Adsorption «ers Reaction mechanisms... Finding rate equations Using rate equations, Diffusional resistance. THEORY 7A 72 13 14 15 16 17 18 PROBLEMS P7.00.00 Particles and pores ..... Diffusion and diffusivity Equations of diffusion and reaction ...00 Diffusion and reaction on nonpermeable catalysts. Diffusion and reaction in pores. Effectiveness... External and internal diffusion... . Variable temperature... Deactivation of catalysts . Particles and pores Diffusion Concentration profiles and effectiveness Conversion and reactor sizing . With external diffusion . Effects of temperature and deactivation CHAPTERS. MULTIPLE PHASE REACTIONS... 798 ‘THEORY 8.1 Axial and radial gradients in packed beds seven T9B 8.2 Gas-liquid reactions ....... 83 a4 as Liguid-liquid reactions... Gas-liquid-solid reactions... Biochemical reactors... Figures and Tables PROBLEMS P8.00.00 1 2. Gas-liquid reactions 3. Gascliquid-solid reactions... 4. Biochemical reactions ~ Index of Substances Index of Subjects secs Packed bedsPREFACE ‘This book isa collection of solved problems in elementary chemical reaction kinetics from an engineer 's point of view. Brief statements of definitions and theory begin each chapter, but detailed derivations of major formulas largely are left as problems to be solved. Some of the problems are original to the extent that “originality” is possible in an area that has been worked over for so many years. Those taken from the literature and textbooks often are modified and provided with solutions when they are not in the original, which is usually the case. The List of Sources of Some Problems may be consulted for additional problems, although solutions usually are not provided in these references. Standard textbooks also should be consulted for systematic parallel or fuller treatment of some of the theory covered by this collection, For the most part, the problems are quite short, ‘The object has been to present a large variety of problems and exercises, including some replication for purposes of drill. Accordingly, comprehensive design-type problems largely have been avoided—those requiring detailed knowledge and data of other areas of engineering such as mass transfer ‘or fluid dynamics or economics. The topics included are identified by chapter headings and subheadings. Briefly, they cover rate equations, analysis of rate data, sizes and performance of ideal reactors, residence time distributions and non-ideal models, solid catalyzed reactions, behavior of porous catalysts, and reactions involving mutliple phases. Solutions are presented in the form of equations, tables, and graphs—most often the last. Serious numerical results ‘generally have to be obtained with computersor powerful calculators. The introductory chapter describes the numerical procedures that are sequired. Inexpensive software bas been used here for integration, differentiation, nonlinear equations, simultaneous equations, systems of differential equations, data regression, curve fitting, and graphing. Students, other beginners in chemical engineering kinetics, and possibly experienced engineers who may wish to review their musty knowledge should be able to profit from the opportunites of “learning by doing” provided by this collection. Reactors are of course the basic equipment in any chemical plant, The large variety of substances that have been used in the research cited in the problems emphasize this point. Also cited are the many different kinds of equipment, analytical techniques, and methods of data analysis that have been used. The Indexes of Substances and Subjects are the keys to this information. Inspiration for the material in this book was provided by several generations of students; { bope that the current generation may find it of value. The word processor ChiWriter of Horstmann Software, Inc. was used. I appreciate the interest shown by Dr. Reza Shams and Professor Bala Subramaniam during the often tedious course of preparation of the manuscript. My parents Stanislaus and Apolonia and my wife Suzy Belle were with me in spiritSOURCES OF SOME PROBLEMS Aris, R, Introduction to the Analysis of Chemical Reactors, Prentice-Hall, Englewood Cliffs, NJ, 1965. Aris, R, Elementary Chemical Reactor Analysis, Prentice-Hall, Englewood Cliffs, NJ, 1969. Bares, J, Collection of Problems in Physical Chemisiry, Addison-Wesley, Reading, MA, 1962: Batalin, GT, Collection of Examples and Problems in Physical Chemistry, Kiev University Publishers, Russia, 1960. But, JB, Reaction Kinetics and Reactor Design, Prentice-Hall, Englewood Cliffs, NJ,1980. Capellos, C, BHI Bielski, Kinetic Systems: Mathematical Description of Chemical Kinetics in Solution, Wiley, New York, NY, 1972. Carberry, 15, Chemical and Catalytic Reaction Engineering, McGraw ill, New York, NY, 1976, Chen, NH, Process Reactor Design, Allyn & Bacon, 1983. Cooper, AR, GV Jeffieys, Chemical Kinetics and Reactor Design, Prentice-Hall, Englewood Cliffs, NJ, 1971 Espenson, JH, Chemical Kinetics and Reaction Mechanisms, McGraw-Hill, New York, NY, 1981. Fogler, HS, Elements of Chemical Reaction Engineering, Prentice-Hall, Englewood Cliffs, NJ, 1992. Froment, GF, KB Bischoff, Chemical Reactor Analysis and Design, Wiley, New York, NY, 1990. Fromherz, H, Physico Chemical Calculations in Science and Industry, Butterworths, Newton, MA, 1964 Brost, AA, KG Pearson, Kinetics and Mechanism, Wiley, New York, NY, 1961. Griffiths, PIF, JDR Thomas, Cafculations in Advanced Physical Chemistry, Edward Arnold, London, UK, 1983. Guggenheim, EA, JE Prue, Physicochemical Calculations, tnterscience, New York, NY, 1955. Hill, CG, An Introduction to Chemical Engineering Kinetics and Reactor Design, Wiley, New York, NY, 1977 Holland, CD, RG Anthony, Fundamentals of Chemical Reaction Engineering, Prentice-Hall, Englewood Cliffs, NJ, 1989, Levenspiel, 0, Chemical Reaction Engineering, Wiley, New York, NY, 1972. Pannetier, G, P Souchay, Chemical Kinetics, Elsevier, New York, NY, 1967, Pratt, GL, Gas Kinetics, Wiley, New York, NY, 1969, Sillen, LG, PW Lange, CO Gabrielson, Problems in Physical Chemistry, Prentice-Hall, Englewood Cliffs, NJ, 1952. Smith, IM, Chemical Engineering Kinetics, McGraw-Hill, New York, NY, 1981. Swinboume, ES, Analysis of Kinetic Data, Nelson, Chicago, TL, 1971. Walas, SM, Reaction Kinetics for Chemical Engineers, McGraw-Hill, New York, NY, 1959; Butterworths, Newton, MA, reprint 1989. Walas, SM, Modeling with Differential Equations in Chemical Engineering, Butterworth-Heinemann, Newton, MA, 1991, Westerterp, KR, WPM van Swaaij, AACM Beenackers, Chemical Reactor Design and Operation, Wiley, New York, NY, 1984. Wolfenden, JH, RE Richards, EE Richards, Numerical Problems in Advanced Physical Chemistry, Oxford, New York, NY, 1964.EO. E(t) FO. Kiko 2 names of substances, or their concentrations fee radical, as CH; concentration of substance A initial mean concentration in vessel, p. 506, 508 hheat capacity ‘Continuous Stirred Tank Reactor dispersion coefficient, p. $00, 617, 629 effective diffusivity, p, 721 Knudsen diffusivity, p. 721 residence time distribution, p. $07, 508 ‘normalized residence time distribution, p. 508 = CJC, of n/0,,, fraction of A remaining unconverted Age Function of tracer, p, 506, 508 Gibbs energy change, p. 249 Hatta number, p. 828, 829 heat of reaction chemical equilibrium constant, p. 248 specific rate of reaction, p. 35, 103 Jeagth of path in reactor parameter of Erlang or Gamma distribution, or number of stages in a CSTR battery, p. 497 number of mols of A present ‘umber of mols flowing per unit time, the prime (’) may be omitted when context is clear total number of molsxiv PB Pe PFR u(t) v ro 5H) subscript designating initial or inlet conditions, as in Cy, ayy V'gs --- partial pressure of substance A Peclet number for dispersion, p. 617 Plug Flow Reactor heat transfer rate radial position rate of reaction of A per unit volume, p. 34 radius of cylindrical vessel Reynolds number, p. 627, 717 Schmidt number, p. 627, 717 time mean residence time, p. 506, 508 = Ui, reduced time ‘Tubular Flow Reactor linear velocity unit step input, p. 492 volume of reactor contents volumetric flow rate volume of reactor axial position in a reactor =1- “CC 0F 1 ty ty, fraction of A converted = x/L, normalized axial position = VIR, normalized radial position, p. 410 skewness of distribution, p. $07, $08 unit impulse input, Dirac function, p. 492 fraction void space in a packed bed = vi, reduced time effectiveness of porous catalyst, p. 724 intensity function, p. 492, 508 viscosity SYMBOLSSYMBOLS ~ wp, kinematic viscosity total pressure density =1R, normalized radial position in a pore, p. 723 variance, p. 507, 508 normalized variance, p. 507, 508 = vi, reduced time tortuosity, p. 722 ‘Thiele modulus, p. 723 modified Thiele modulus, p. 731 vMN THEORY Software 1 Plotting and curvefitting 2 Regression of tabular data 2 Roots of nunerical equations 3 i. Single equations 2. Simultaneous Linear equations 3. Simultaneous nonlinear equations 1.5. Integration and differentiation 4 6. Ordinary differential equations § 2, Formulation Integration The second order OPE The Laplace transform method fumerical solution of ODEs 7 POLYMATH program CONSTANTINIDES program A. Second order equations with two-point boundary conditions 1.3. Partial differential equations, 9 fables 10 Boke s PROBLEMS Regression 15 Roots 18 Integration and differentiation 22 Analytical solution of ordinary differential eau Nuserical solution of ordinary differential equations tions The problens of this collection require numerical or graphical or sometimes analytical methods of solution. There is a large number of books and software on these topics. An outline with examples of these methods is the ail of this chapter. It is expected that the sludent wil! nave access to some equivalents of the software used here for the solved problems and listed subsequently. Some of the work can be done with a programmable calculator, but pot as easily as on a PC 4.1. SOFTHARE Of the following list, the first six items are the principal ones used here. All but TableCurve are currently availeble at reduced prices to students, but most of the required curvefitting also can be done with POLYMATH or AXUH. The last three items do analytical as well as numerical work 1. POLYMATH. AIChE Cache Corp, P Q Box 7939, Austin TX 78719-7939 Polynomial and cubie spline curvefitting, multiple linear regression, Simultaneous ODEs, simultaneous linear and nonlinear algebrate equations watrix qardpulations, integration and differentiation of tabular data by way of curve fit of the data. 2. CONSTANTINIDES, Applied Munerical Methods with Personal Computers, McCraw-Hill, 1987. Nonlinear regression, partial dirferential equations, matrix manipulations, and a mere Flexible program for similtaneous ODE: 3. CHAPRA & CANALE, Numerical Methods for Engineers, McGraw-Hill, 1988 Explains the methods but the diskette is limited. It does heve the trapezoidal 1rule for data in tabular or equation form. 4. SEQS simultaneous equation solver. CET, PO Box 2029, Norman OK 73070 Twenty simultaneous equations can be solved. The program seems to be superior to the one in POLYMATH S. AXUM. Trimétrix Inc, 444 NE Ravenna Blvd, Seattle WA 98115. High quality graphics and data analysis, including nonlinear regression. 6. TableCurve. Jandel Scientific, 65 Koch Road, Corte Madera CA 94925 Automatically fits 3000 different xy relations with statistical criteria 7. MathCad Numerical Supplement. MathSoft 201 Broadway, Cambridge MASS 02139 8. Maple V. Brooks/Cole Publishing Company, Pacific Grove CA 93950. 9. Mathematica. Wolfram Research, 100 Trade Center Drive, Champaign ILLINOIS 61820-9910. 1.2. PLOTTING AND CURVE FITTING Graphical representation and corresponding equations of tabular data are of value for interpolation, for revealing behavior patterns, and other purposes. The most complete software for this purpose is TableCurve. More limited but adequate for the present book are POLYMATH and MathCad. All spreadsheet software, for instance QuattroPro, can make plots of all kinds. In this book the most used software for making plots of tabular data and equations is AMUM which is also capable of fitting polynomials and noniinear equations to tabular data. All of these commercial packages have tutorials and user friendly instructions 1.3. REGRESSION OF TABULAR DATA Regression 1s a process of representing tabular data, say (C,t), in equation form. The purpose may be For interpolation of tnlermediate values of C or t To obtain an equation, C = f(t), that can be handled ‘readily in a computer progran ..To facilitate repeated differentiation or integration of the data The form of the equation is specified in advance, and the best correspnding values of any constants are found by least squares. The goodness of fit of several assumed equations are compared by statistical criteria such as the correlation coefficient or the F-test. When the number of sets of data equals the number of unknown constants in the equation, the constants are found by simultaneous solution. Otherwise a least squares regression is used. Linearity refers to the unknown constants. The following are linear in this sense, y = atbxtcx® and In y = atb In x + /x* but not b b) Ve za+ 2 = +P y= a+ 325 and y = exp(ar2) x although the last can be linearized as > Inysae2toks ny=a+2+c inx There are four main classes of data regression. ‘ 2 ; i 1. Polynomial, y = a + a,x + apx” + Linear regression is a special case. 2. Multilinear, y = ag + a,x + aX * ..., where %, xg, --. are independent variables or functions. 3. Nonlinear, say of two variables, x and y, 2Ye = £04: ag, aye Bare.) and the derivatives OE OE as ° Bag Jay ~ Ba, of the Least squares condition, Ely, — FOK389) a age... ))? > Minimum are not linear in the unknown constants a,. 4. Periodic data, using the Fast Fourier Transform. These topics are explained in specialist books and briefly by CHAPRA & CANALE. Polynomial and multilinear regression programs are in POLYMATH and AXUM, nonlinear in CONSTANTINIDES and AXUM. No periodic data are regressed in the present collection, Examples: Polynomlal regression is applied In problem P1.03.02. Several examples of POLYMATH multilinear regression are in sections P3.06, P3.08 and P3.10. A non-linear regression is worked out in P1.02.07 1.4. ROOTS OF NUMERICAL EQUATIONS Methods for finding roots of numerical nonlinear equations first involve making estimates and subsequently improving them by some systematic procedure ideal problems for implementation on computers. Many scientific calculators also have built-in capability for finding roots of single equations, for instance the HP-1SC or HP-32SII. 1.4.1 SINGLE EQUATIONS The Newton-Raphson method is based on the truncated Taylor expansion If xp is an estimate for f(x) = 0, an improved value 1s X = Xo ~ KF(%Q)/E? (xq) where f' (x) = df/dx and k is a positive fraction that is selected arbitrarily to speed convergence; k = 1 often is acceptable. When the derivative is awkward to find analytically, a finite difference equivalent can be used, for instance, ogy = £(1:0001K)-£ 6) £00 = “9 O00TK Then, 0. 0001x9f (x9) * = Xo ~ K FUT GOOI KS =F) The factor 1.0001 is arbitrary and can be changed to improve convergence or accuracy Wegstein method. This does not require a derivative and usually converges more rapidly than the Newton-Raphson. The equation is put in the form x = £(x) When xp is the estimated value of the root and x, is £(%), an Improved value Xof ()-£%q)® x of Ox? % © EGR )-aE OG) XytF OGIO, ‘The process is repeated with the improved estimate as a start Polynomials, a a,x azx* +a,x’ +... = 0. Procedures for finding all real and complex roots are on the diskettes of CONSTANTINIDES and Al-Khafaji & Tooley (Computerized Numerical Analysis, 1986). For instance the roots ofx® = 3x8 -ax4 ~9x + 10x? + 2x + 3 = 0 are x = -0.1438 4 0.1610j, -1.000 + 1.4145, 4.288, 1.000 1.4.2. SIMULTANEOUS LINEAR EQUATIONS These are solved by matrix manipulations. Programs are in POLYMATH, CONSTANTINIDES AND CHAPRA & CANALE. When the number of equations is not large, a manual procedure can be used to eliminate one variable at a time by reduction of the leading coefficients to unity and appropriate additions and subtractions of the equations 1.4.3, SIMULTANEOUS NONLINEAR EQUATIONS ‘The Newton-Raphson method for multiple equations also starts with truncated Taylor expansions. For the system f(x,y.2) = 0, g(x.y,z) = 0, blx,y,z) = 0 the corrections to initial estimates xg, yo, Zp are 2, b and ¢ found from the linear system fy + af, + bf, + xf, = 0 Bo + ag, + bey + cg, = 0 ho + ahy # bhy + ch, = 0 where the functions and all the derivatives, for instance f, = af/@x, are evaluated at (%9,¥o.%)). Programs are on the diskettes of POLYMATH and SEQS The speed of convergence and even the possibility of convergence depend on how close the estimates are to the correct values. It is of course possible that there may not be a solution in the range of Interest, or there may be several solutions INTEGRATION & DIFFERENTIATION Only a comparatively few forms of integrals are encountered in reaction kinetics, Some of the more complex ones are reducible with partial fractions. Table 1.1 of indefinite integrals and partial fractions supplies most needs When integrating between numerical limits it may be more convenient to proceed directly with a numerical integration rather than through an analytical integration, particularly when the coefficients and integration limits are long numbers, for example, the integral S88 —___*_____ ax = 1.2811, 50 trapezoidal steps 2.1-3. 78x+5. 86 1.2815, 200 trapezoidal steps by CHAPRA & CANALE which takes a very simple input. Such a result may well be more reliable than the laborious evaluation of the analytical integral by way of item 11 of Table 1.1 Softwares for numerical integration of equations include the calculator HP-32SI1, POLYMATH, CONSTANTINIDES AND CHAPRA & CANALE. The last of these also can handle tabular data with variable spacing. POLYMATH fits a polynomial to the tabular data and then integrates. A comparison is made in problem P1,03,.03 of the integration of an equation by the trapezoidal and Runge-Kutta rules. One hundred intervals with the trapezoidal rule takes little time and the result is usually accurate enough, so it 1s often convenient to standardize on this number For manual integration of tabular data, the trapezoidal or Simpson's rules usually are adequate. Between two points the trapezoidal rule is SI? yax = 0.50%5-%) (44a)and between n points spaced equally with Ax = x,"x%,; as interval, Yorn ax 5 + vityets-4¥nen) fie my vox Simpson's rule for three equally spaced points ts X17Xo iyet4y,t¥2) $2 ydx = * Differentiation. The main application of numerical differentiation in this book is to find a rate, dC/dt, from tabular data (C, t). In view of the availability of computer routines for fitting of polynomials and other equations to tabular data, this is the way to go, differentiating the curve fit equation analytically. POLYMATH can provide direct numerical values of derivatives and integrals from the curvefit result Numerical differentiation may be quite sensitive to the correlating equation. In problem P1,03.01, the results with four different curvefits do not agree well although the curvefits themselves are statistically satisfactory. In problem P1,0302, however, the agreement between the higher polynomial fits ls more nearly acceptable 1.6. ORDINARY DIFFERENTIAL EQUATIONS Differential equations arise in reaction kinetics through application of two main fundamental rate laws, which are 1. The rate of reaction 1s proportional to the concentrations of the participants. Law of mass action 2. The rate of transfer of mass ( or heat) 1s proportional to the concentration gradient. Fick’s law (or Newton-Fourier law). 1.6.1. FORMULATION ‘AS a basis, a differential element of volume, d¥, = dxdydz, or time, dt, is ldentified. In cylindrical geometry, the element of volume may be a thin disk, Adz, if changes occur only in an axial direction, or a ring 2urdrdz, if changes occur both radially and axially To this element of space the conservation law is applied in the form Inputs + Sources = Outputs + Sinks + Accumulations where cach of these terms may be a quantity or a rate. Inputs and Outputs are accomplished by crossing the boundary of the reference volume. In case of mass transfer this occurs by bulk flow and diffusion. Sources and Sinks are accretions and depletions of a species without crossing the boundaries. In a mass and energy balance, sinks are the rate of reaction, raV,, or a rate of enthalpy change, ~AH,pdC. Accumulation is the time derivative of the content of the species within the reference volume, for example, (8C/at)d¥, or C, (87/2 )pav, Conversion of the differential balance to a differential equation follows after division throughout by the differentials of space and tine. Boundary and initial conditions are specified to complete the physical description of the problem, With ordinary differential equations the number of such conditions is the same as the order of the equation. With partial differential equations, the safest rule to follow is that the problem be completely defined in a physical sense. For example, the condition of every entering and/or leaving stream must be defined, the initial state of the vessel must be known (or a final state if the initial is to be found), symmetry conditions (such as radial symmetry) must be recognized if they exist in the particular problem, and conditions at the boundary such as rate of heat transfer or rate of reaction or rate of diffusion must be formulatedmathematically. A detailed application of the conservation principle to the derivation of a second order equation is in problem P5.08.01. 1.6.2. INTEGRATION Differential equations of the first order arise with application of the law of mass action under either steady or unsteady conditions, and second order with Fick's or Newton-Fourier laws. A particular problen may be represented by one equation or severa) that must be solved simultaneously Solutions of the commonest first order equations are listed in Table 1.2. Variables separable and first order linear are most often encountered. Exercises dealing with first order equations are in problem P1.05.05 Sometimes an equation out of this classification can be altered to fit by change of variable. The equations with separable variables are solved with a table of integrals or by numerical means. Higher order linear equations with constant coefficients are solvable with the aid of Laplace Transforms. Some complex equations may be solvable by series expansions or in terms of higher functions, for Instance the Bessel equation encountered in problem P7.02.07, or the equations of problem P2.02.17. In most cases a numerical solution is possible. ‘Some problems with diffusion or dispersion give rise to the second order linear equation with constant coefficients, 2 SY s oky B+ uty = F(t) ate When £(t) = 0, the equation is called homogeneous. The general solution is the sum of the solution of the homogeneous equation and a complementary function which can be found by several means. The form of the homogeneous solution depends on the value of the discriminant, D = k*-1, as tabulated. minant Solution Positive ¥ = Cyexp(yt)+Czexp (At) Zero y = (Cy+Cat}exp(-kwt) Negative ye exp(-kut )[Cyeos (utd 1-1 *)sCosin(wtl 1 2 y = C exp(-kwt cos (wt! i-k® -¢) y = C exp(-kut )sin(wtl1-K® +9) where A,,Az = w(-kHB), ¢ = [c2c3, g = arctan(Cy/Cy) The complete solution of the non-homogeneous equation can be found directly in some cases by Laplace Transform, as the problems of section P1.04 show. Several examples of second order equations are in problem section PS.08 The Laplace Transform of a function f(t) is defined as Lif(t)) = f(s) = F = $8 £(texp(-st) at Several notations are in use, as indicated. Tables 1.3 and 1.4 summarize various operations and provide some pairs of functions and their transforms.Transformation replaces a differential equation with independent variable, t, to an algebraic equation in variable, s. The latter relation can be solved algebraically for the transform f(s). Then f(t) is found by inversion with Table 1.4. Problems P1.04.01 ff are examples. Cases of multiple reactions are treated this way in problems P2.02.08 and P2.02. 10. Step and impulse inputs. These discontinuous functions are used particularly in Chapter §. Their definitions and transforms are Step: H(t-a) = 0, tsa 1, tea Ltit(t-a)) = 2 exp(-as) Impulse: 8(t-a) =0, tea llesa L{3(t~a)} = expl-as) The inverse of a transform with exp(-as) as one of the factors is L{£(s)exp{-as)} = f(t-a) B(t-a) f(t-a), tea 0, tza Example. For the equation with a step input, SEs se = W(t-ad at f(s) = Sep s(s"4u*) and the solution is f(t) = SU - costw(t-a)) H(t~a) La = costuit-anl, tea a o, tsa With an impulse input, “oe 8(tra) at = exp (sas) f(s) = a situ s(t) = 2 sinfu(t-a)) m(t-a) 3 sintw(t-a)l, t= a 0. 0: For numerical processing, a first order ODE is arranged explicitly for the derivative,. aye y == fy) A procedure based on the truncated Taylor series is named after Fuler. With increment h = Ax, successive values of y are Yar = th £Oq,yy) A substantial ‘Improvement employs the following Lteration, eS yl o.sml eG yy) fC qs ¥r where the superscript denotes a trial number at a particular value of i. This is called the Modified Euler Method Both POLYMATH and CONSTANTINIDES use this method and also a fourth order Runge-Kutta method. Other methods are available in other software, but these two are adequate for the present book Higher order ODEs are reduced to a set of first order equations for solution by these softwares. Thus the third order equation, 3 2, ay = toay, &, SH dx dx’ becomes the set dy . dy" " se Sev, Bev, = fGayy ay") The independent variable is x and the dependent variables are y, y’, y" and y' Integration Is started with known values of the dependent variables at one value of the independent variable, except when the "shooting method" Is needed. Auxiliary algebraic equations can be entered to the program along with the differential equations and the boundary conditions 1.7.1. POLYMATH PROGRAM A variable name may have any combination of up to ten lower case letters and numbers. A typical equation entry is ax xy 0. 48x Ge Oraey 7 04% BOIL) = 0-0. Atte ~ xy 24 oo dly)/dtt) = -2% dz _ O1xy ous fe" ome d(z)/d(t) = 0.1% © = xty/(0.2+y) with intial values t = 0, %) = 0.1, Yo = 10, 2 Note the parentheses in the derivatives. There is no choice of the number of integration intervals; it is supposedly adjusted to obtain a good precision. The output can be a graph or a table with 20 divisions of the independent variable. The scale of the ordinate is selected automatically to fit the range of the abscissa. 1.7.2. CONSTANTINIDES PROGRAM The independent variable is always designated x and the dependent variables y(1), y(2), .... The derivative is designated dy() Sar = Fb yd, yl2)...., CO), C2),...) 6)where the Cli) are constants that are entered during the course of the solution and can be changed to obtain a range of solutions. In this nomenclature the equations of the POLYMATH example becone, xty(2) GO) = Biay ~ O-etyID) = © - O.atxty(a) =. 0.2442) 5g, ot) D2eyi2zy ~ 6 3) = OT KY(2) og gag GS) = “Gzeyrzy = OF oe = xty(2) O.ay(2i with initial values x = 0, y(1}g = 0.1, y(2)y = 10, y(3)p = 0 This program permits any number of intervals with a printout at each interval, and the ranges on the axes of the graph can be controlled, 1.7.3. SECOND ORDER EQUATIONS WITH THO-POINT BOUNDARY CONDITIONS Second order equations or a pair of first order equations require two conditions. When these are at the same value of x, say yo and (dy/dx)y at Xo, a numerical integration can be started. When one condition is yp at xo and the other is (dy/dx), at x, the shooting method can be applied. This consists of several steps 1, Assume a value of (dy/dx)g at xp 2. Do the integration from x) to * That result will provide both y, and (ay/ax),, 3. The correct integration will be attained when the specified and calculated values of (dy/d), agree. This procedure also 1s described in Section 5.8.2. Numerical examples are problems P1.05.02 and P5.08.23 , as well as P5.08.02, PS.08.03, PS.08.11 and PS. 08,12 1.8, PARTIAL DIFFERENTIAL EQUATIONS Common situations in reactors are when the conditions can vary with time and position as independent variables. Partial derivatives of dependent variables such as concentration and temperature with respect to each of the independent variables then are involved. Such an equation, for unsteady state dispersion in a cylindrical reactor, was derived in problem 5.08.01, namely we, #48 at © oy? ry or oy BE gem u SE ke! In this book PDEs appear primarily in Section 8.1 and problem section P8.01 Some simpler methods of solution are nentioned there: Separation of variables application of finite differences and method of lines. Analytical solutions can be made of some idealized cases, usually in terms of infinite series, but the main emphasis in this area is on numerical procedures. Beyond the brief statements in Chapter 8, this material is outside the range of this book Further examples are treated by WALAS (Modeling with Differential Equations in Chemica! Engineer ing, 1991)Table 1.1. Integrals and Partial Fractions 1. fier bres Say Ge te ax) 2. In (ex +b). 3, ~ itn (ax +). 4a aerey thine b), 5. 6. 5 dx * Swern eto 8. ¢__ ze ot Fb) Ox Fa * pal ax r 1 9. fe bt > 4 00 Suepueye je panby Vege OE jo. fii ~ 3. Siticye* rare 400 xdx Lime 3 Fore sg Or thet Z 1 A 8 c 2. pant hard "eee t eee tere here A= 1 B= 1 c= 1 whee A Gea" 0 ES OCT I 4 2 © > 3. wyaete xte ¥t6 uae’ ¥ed where d= “GE aay ae 34, t f CHD eee)” Jomo Va 1GTable 1.2. Solutions of Ordinary Differential Equations of the First Order 1. Variables separable, The differentia! equation hxlgstyi de + fabelgaty) dy = 0 hes the solution Aid aly) Led iy 4 f Se ay J Ao} os 2. Homogeneous equation, The equation dyldx = flyix} has the solution ov inx= f +6, wherev® 1” 3, The linear equation dyldx + filxly = galx} has the solution yeer|frinvreree], wneess [sie 4, Totel or exact differentia! equation. The equation f(x, y) dx + file, vl by = 0 Is exact when af, fay ~ af,/ax. The solution is Jove fla-2 Jaafar where y is constant when integrating with respect to x, and x is constant when integrating with respect to y. may be possible 10 find an integrating factor 4 that will make aluhHay = aluhMax. 5, Explicitly solvable for one of the variables'in Fx, y.p) = (2) Solvabie for p. Flu yale (y~ Mi yie~ fUX yi) 0, One incegral is abtained for each factor ayia ~ file.) (b) Solvable for y. Fle, y,p) = ly ~ flx. pilly ~ fle, pi] --- = 0. Etimin ste y from each factor by differentiation: dy ah aap pa Wh tee dx ax” op ax The solution will be Glx, p, C)= 0, It will be possible to eliminate the parameter p between the integral and the original differential equation, The final results will be 9, (x, y, C) = 0. Solvable for x. Fix, ¥.p) = Ix ~ fly, pillx = fale, pil + 0. Eliminate x from each factor by differentiation: tc 1M hee dy p sy apdy The solution will be Gly.p, Ch= 0. 1 will be possible to eliminate the paremeter p Between the integral and the original ditferential equation. The finad result will be glx, y, C) = 0. 6, Simuttaneous linear differential equations with constant coef: ficients. Take the pair Baar Baath) and Me asx + Byxs tb hlth a a Apply the Laplace transform to each with L{dx/at) = sf, ~ xj. Solve the resulting pair of linear algebraic equations for x = gy{s) and 2 = galsi; then invert to x, = y{0) and xs = hylel with the aid of a table of transforms. aLaplace Transform Operations Aa Fls}= Tish sa [lernoa 2 teri 0140 Sern 13 2 fhe PAs Nt amie sri) D 8m) 8. fit A= 0.060, ees Bena trey > [anes Sr # fnase- ne Fale testoen hore «ts srbasl = s 0, etl Fix, 8) = #0, 0) Prins! 2 efins)_ ao) ae rn) aay A ve nse tem ena ines 1S Sree oem nashTable 1.4, Laplace Transform Pairs Ae) a, ost Ble) nit ienpulee at Foedie) unit siep starting at =0 tH romp tonation ahr n= positive integer fait , 3 s. Hea) unitstep starting at? = @ 6. HO=HUt~ 2) rectangular pulse 2. e"" —exponentiat decay 1 = postive integer {stay p . 1 sista) yo, — ae ale # a a Ste Sts + alls + 6 2 — lew oits+o 3 —p (so ayer) te SE Bs ast Bi 1 e om & 8 i a a isralistole+) = Bm alle— ai oe 5) a 16 sta fa~ale , fan sie™ | te cle isFoltsroRs +a © alie~ ah" (e-dys Hl ta ello— v7 = sino 18. cost —s 48. sintot tg}, @ = arctan 20, sinhot + 8) 2 aie tot tg): pm arctan FE . 1 intut — a); db arctan® a . tera o%) 24 + aoe 1 Me Fy Beast wl as, S42 GrateTable 1.4 (continued) 26. 22. 2a, 28, 29, 30, 31 22, 3 34 38, 36. wrarre 1 e+ ero SIS + 2fens +o) SF a FO te Gralisra +57 od s(e+ elles a +B sist ois + a + BA Flere} 1 sis aye Bist sis + ais +b} sie + a) 64) sinlbe-s gy = arctan eM sin(or= gh é= arctan Fie sists Vim Fe ahs > arco y infbt+ oy = arctan " siniot— 6) Vicar +o? aE cle= a +O” Vea pVig wale 6 veesnveisun 2 $= arctan Hsinkbe + ah fe aretan 2 — arctan £~ arctan 2 Fleder Jeera Flo oo ato~ ate" 0, 294 ao peas BEF OO or 25° ela 8) Bia $84 Mat = BF aya + aa + b¥loy = 20)" 2 snot + 6 warctant; cheats ot 14PROBLEMS, CHAPTER 1 Vapor pressure data of toluene, in °C and Torr, are T -26.7 4.4 6.4 18.4 31.8 40.3 51.9 69.5 89.5 110.6 pot 5 10 20 40 60 100 200 400. 760 The Antoine equation is fitted to the data in the original and linearized forms, »’ T2732" The two TableCurve plots show that the constants are a = 18.62 and b = -4570, exactly the same in the two cases. The modified Antoine equation, however, B THD cannot be linearized. Although this form Is not in the TableCurve repertory, the following relation can be used, 2 atx, B = b ae p = expla + x7g7q-g) and In p= a inpoa- Trbx xD where A= c/b, D = ivb, B = D(A-a) 41 Ean 15, wesigalgsoomsewe form! sem 0 rot" 00) 0 ot 20 100 ° 3s 1000/{T#273.2) rey P1.01.02. POLYNOMIAL REGRESSION A quadratic equation will be fitted to N sets of data,(x,,y,), by least squares y = a9 + ax + agx® Ely, ~(agtayetagx?))* » Minimum On setting 8 | Of aE Ga, Bay Gay the resulting “normal equations” are zy = EX; 2 agN + ayEx, + ag&xp = 2 3 agEXy + ayExy + agExy 15gE, ajExp ta,Bx} = Edy, The various sums are tabulated below so the normal equations become llag + 6.0la, + 4.6545a, = 5.905 6.Olay + 4.6545a, + 4.1150, = 2.1899 4.6945ag + 4.1150a, + 3.9161a, = 1.3357 and the correlation becones y = 0,998 - 1.018x +0.225x" x [0.05 O11 O15 031 046 052 0.70 0.74 082 098 117 ¥, | 0.956 0.890 0.832 0.717 0.571 0.539 0.378 0.370 0.306 0.242 0.104 Dx = 6.01 N= Dx = 46545 LY = 5.905 Dd = 4150 Dxy = 2.1839 Y xf = 3.9161 Day = 13357 P1.01.03. MULTILINEAR REGRESSION The data of the first three columns of the table are to be fitted to the equation ¥ = ay + ayy + agxy The least squares criterion is Ely, - Cagtayxytayxg)]? 2 Minimum Applying 8 oz Jag Ba; makes the normal equations aN + xy + ax, = BY, AoE + EEL + aE ve = Bay On substituting the various summations from the table, the equations are a9 + 16.5a, + Mag = 54 16.5a9 + 76.25a, + 48a, = 243.5 lay + 48a, + Sda, = 100 The solution is y = 5 + Ox, -3x.. ae ee 500 0 0 0 0 0 6 3 4 8 5 3 ew ee ee a a gS ok 8 BF 3 8 % How 8 Bose 16s #7825 5k B25 100 1.01.04. NONLINEAR REGRESSION The normal equations will be written for the least squares regression of the nonlinear equation for N sets of data, by.y,), 16b eat2 Yr 88 sre The least squares criterion is by )2 Ely, “Cat g)1? > Minimum &_ 8 _ 8g 3a ~ Bb > Bc ~ Be _ -a-? = & = atzty,-a-2r1 = 0 an + pe t= 5, a mre 7 er wa Pye 1 - 5 7 UEC -agead > gagh) = 0 1 1 ye EA ab ake + PEG ey)” = Ege (2) =e Fe = 2B 1 yz i Ms atl, )° + bE(—_— —s 3) ee re Ge i Equations 1, 2, and 3 are nonlinear in a, b and c. In principle they could be solved simultaneously, but an improved technique is explained in problem P1.01.05. Take the case of a function of one variable and two constants, yy = fOys a, b) Estimates of the values of the constants are made. For the j-th iteration they Will be called ay and b, and corrected values will be aya = ay # Aa, by = dy + Ab a Represent the function by the truncated Taylor series, af (x4) af (x,) Fay = FOq), + AG Ds dat (GE, ob =f + fyna + f,Ab (2 The least squares criterion is Ely, “FOG yaql? = Ely — (fda tyOb)]? » Minimum The function and the derivatives are evaluated at the trial values a, and by of the constants. On placing o_o da ab the normal equations become ~f ,ha-f,Ab) (-f,)1 -£,ha-f,Ab) (-f,)] 0 or babte + AbUff, = Lyf) fy (3) qTbakf,f, + AbEf, = Ely~f)f, @ where 8 by) af (x) oy fe = as (s) Solve for da and Ab from (3) and (4), substitute into (1) and repeat the procedure. Continue until values of 4a and Ab are near enough to zero £2 £64)), fa Data of the first two columns of the table are to be fitted to the equation . b y = £(x) = expla) Trial values of the constants are a, = 18.6, by = -4.57 The derivatives are af f, = Fy = explatb/x,) = Of L fy = 3p = ) exp(a+ b/x;) Corresponding values of the function and the derivatives are tabulated. The various summations are Efe = 0.61(10°), Beg = 4.26(10°), Eff, = 1.61(10%), E(y-f)f, = $720, E(y-f)f, = 15624 Eqs (3) and (4) of problem P1.01.05 become 0.614 + 1,614b = $720(10°°) (3) 1.61da + 4.26db = 15624(10°°) @ Accordingly fa = -0.1084, Ab = 0.04498 and corrected trial values of the constants are a = 18,6-0.1084 = 18.492, b = ~4.57+0.045 = ~4.525 ROOTS OF A SINGLE EQUATION The equation is y = -1 + 0.7% expl0.5(1-x)*] + 1.2(1-x) exp(.5x*) = 0 or 2 ) 1.2(1-x) exp: 0.7 exp{.S(1-x)*} The derivative is x =x +1)40.7 exp(0.5(1-x)?] - 1.2 exp(0.5x7)} 18The plot shows that the roots are approximately -0.47 and +0.65. Hi ai 1 oO 1 2 3 4 5 6 1.02.02 Programs are written in QUICKBASIC for the Newton-Raphson method with analytical or numerical derivatives and the Wegstein method. The particular equation jowever, ssumed -1 and +1. rial ~0.7687857 0.76534 ~0.4971118]9. 66673 ~0.4721097|0. 65458 ~0.4706308]0.65442 -0, 4706259|0, 65442 -0. 4706259 P1.02.01 EN-R SOLUTION OF Y=F(X)=0 WITH ANALYTICAL DERIVATIVE, SHORT X INPUT X PRINT X 19 GosUB 30 HEYYL XoX-H PRINT X BE ABS(H/X)<~.0001 THEN 29 Goro Iv END SR FOR Y AND YL Yon ToXAEXP(Se{ =X) 241.24 1 -X)MEXP (502) YI (K2AKE Io HEXPC SH{I-XP2)~ 1.2 EXP(50X2)) RETURN 20 30 NCR SOLUTION OF YFOQ=0 WITH NUMERICAL DERIVATIVE SHORT X INPUT X PRINT X 10 Gosup 30° yey Xr 1.00014% Gosun 30 ~0, 495743] 0.95931 -0.479811/0.73556 -0, 470626 |0. 66884 0.65492, 0.65442 is entered following line 30. 20 30 10 20 to test the Newton-Raphson and Wegstein methods, starting values were The successive evaluations are tabulated. Wegstein is a little faster for the negative root but a little slower for the positive one. PROGRAMS FOR ROOTS OF SINGLE EQUATIONS The one used here is from problem yey, 001+ X¥1/(¥2-¥1) X=X/1.0001-# PRINT X_ IF ABS(H/X)<=.0001 THEN 20 Goro 10 END USRFOR YF) YD) LAs XSEXP {| WEGSTEIN SOL'N OF X=F00 SHORT X PUT xt PRINT XL XeX! x2ex ‘GosuB30 xvi Gosus30 Xe (RIeVINX 2YKIFYI-20) IF ABS(X-YI/(X+Y1))S=.0001 THEN 20 PRINT X Xinx Goro 10 END ESR FOR Yi=X=F00) Yim(1=1.24(1- KEXP S0X2Y,T/EXPL Se (=x)°2) RETURN P1.02.03. MULTIPLE LINEAR EQUATIONS ‘A set of linear equations can be solved by a variety of procedures. In principle the method of determinants is applicable to any number of equations but for large systems other methods require much less numerical effort. The method of Gauss illustrated here eliminates one variable at a time, ends up with a single variable and finds all the roots by a reverse procedure. In the example, each of the four equations are divided by the leading coefficient, 2.0, of the first equation. By appropriate additions and 19subtractions the variable x, is eliminated from the second, third and fourth equations. Similarly x, 1s eliminated from the third and fourth equations, and so on. The second group of equations is the result. By a reverse procedure, all variables are evaluated by the third group of equations. 2.0%, 10x, 0.12, +1.0:,=2.7, 0.48, 4 05e,-$4.05,—85x, 221.9, a 03e-— 1.02, 4 10%, -+5.22,——39, Ly, $0.2¢)42.52,—1.02, 09.9. 2, 4$0.8x,-0.05:, +055, 35, 1 Fe#1S.AOe— 29.002, 71.20, (2) 1.12296, = 4.72286, 1.11998x, = 1.11588. =~ 1.00000, y= 4.72298 — 1.72298 =3.00000, @) 2,=71.20—13.40-3-4 29,0 =2.00000, #1 1.35-- 05-24 0.05-5440.5m1.00000, P1.02.04. SOLUTION AFTER LINEARIZATION For the rate equation r= xctcB data are Ca 0.7 0.9 1.6 Linearize the equation and substitute data ln 0.4567 = Ink + @ In 0.7 + 6 In 0.2 in 1.0707 = Ink + @ 1n 0.9 +8 In 0.3 ln 2.5917 = Ink +@ In 1.6 + 8 In 0.2 The solution by determinants is r= 3.scz cp Data of the first three columns of the table are to be used to find the constants of the rate equation r= kchcd In the linearized form, Inr=Ink+p Inc, +q Inc, or in the simplified notation, you+ep + Bq POLYMATH multilinear regression could be used to find the constants w, p and q but the problen will be solved directly. The least squares condition is lw + ap + Byq - y)* » Minimum Apply a= _ ah _ ah _ oy” Op © Bq to obtain the normal equations Nw + pEay + azB, = Ey, mo 20WEa, + pay + q¥o,By = Lay, (2) WEB, + pEayBy + EB; = EBs (3) ‘The various summations are evaluated from the data of the table and substituted into (1), (2) and (3). The following groups of equations are for successive eliminations of the variables w, p and q. The coefficients are listed. From the last line, q = -1.2160/0.8625 = -1.4098, Then p = 1.0815+0.7388(- 1.4098) = 0.03994. Finally, w= Ink = 3,492, and k = 32.85 so the rate equation is r= 92.8809 c,h? Values from this equation are listed in the last column of the table. The agreement is only fair. The pair of equations sinx+y=2 and expx+y?=3 are plotted to estimate the solution. SEQS is used to obtain accurate values of the roots. x 7 Converged Values 3 2 WwW Does not converge -4 1 3.42267, 1.72261 45 1 ~ 3.42267, 1.72261 2 “5 1 ~9.69606, 1.73203 y -5 W7 6.01118, 1.73134 “6 1 ~ 6.01119, 1.73134 + —10 i ~8.69606, 1.73203 Which roots are found apparently denends en the prior esti: 0 mated values. =10 -5 * 0 21 woP1.02.07. THO NONLINEAR EQUATIONS In Newton’s method for a set of nonlinear equations, each equation is expanded in a truncated Taylor series. The result is a set of linear equations in corrections to previous estimates. Repetition of the process ultimately may converge to correct roots provided initial estimates are sufficiently close Suppose the equations are F(x,y) = 0, Glx,y) = 0 mm and estimates of the roots are x, and y,. The successive approximations then are computed by the following formulas. tegen [Fen HF yl am) eat TE WG (sn 4056 94) [~The | og ay EG Flee wale, ap Ines YF Fd] Clery U2) G0, gn) 2* Te a" where apn] Ete In) Fy len Ye gon a|Fe lene He) Fem In) "1G bus Yn) Gyn ta” PVG vs) Glen 90) and the Jacobian Fee, y) Pyle 4) Gite, uy) Gylx, 9) Example 1. Find the real roots of the system F (x, y= 28 —y'—1 0, Ge, yxy —y—4=0. Solution, Find graphically the approximate. values x,=1.2 and Je, y= leo Computing the Jacobian at the point (1.2; 1.7), we have From formulas (2) we get Lact [One 3.40 *—e7310| 0.1956 9.40 8.64 —0.434 = 17 —era75/ 4/91 0.1986 |~ 1-70-9980 = Continuing this process with the obtained values x, and y, we get &_ = 1.2343, 6615 and so forth. Joey) J(L% 17, x 1,2+0.0349 = 1.2349, 6610. P1.03.01. DI NTIATION OF FITTED EQUATIONS Four different equations are fitted by TableCurve to the data of the table. They all have correlation coefficients > 0.995. The derivatives are evaluated at selected points, and mostly do not agree closely. Presumably tne derivatives from the equation with four constants are the best. Vig = 2(atbxtex™ eax?) (b+2ex+3dx”) ¥3, = béZex Yar = explatbxtex?) (b+2cx) 22Yao > ee WONmasan~ % eceeeekece vente a-cencoe ge 8 e2ke Catalytic oxidation of carbon monoxide is studied in problem P3.07.06. The change in pressure is given as a function of the time in the first two columns of the table. Polynomials of several degrees are fitted to the data and the derivatives, -dP/dt, are found at selected points by POLYMATH. Values derived fron degrees 3, 4 and 5 agree fairly well. aP/at, 0.7555 |0.7789|0.7722|0.7710 0.4539 |0.3864]0. 3854) 0.3865 -0,1494]0.0889]0.0511]0.0570 23sam (uble Satine P1,03.02, TRAPEZOIDAL AND RUNGE-KUTTA INTEGRATION The trapezoidal program of CMAPRA & CANALE and the Runge-Kutta routine of CONTANTINIDES are compared for the integral ys Sy aes x J e-22erx020 with several intervals as tabulated. The Runge-Kutta is superior Intervals RK 2 1.6488 10 1.6498 50 1.6498 100 1000 1.6498 1.6498 P1.03.04. ANALYTICAL AND NUMERICAL INTEGRATION The integral to be evaluated is p22? 1 Yo SCs Gales) bas. o1ao.sy The integrand is transformed into partial fractions by item 13 of Table 1.1. 20.2 ( _ 0.2892 , 0.1538 _ 0.02339 | 0.1587 Jus (" san2 * ees "55.0 * Saas)? & = 0.009326, by analytic evaluation 0.009377, by trapezoidal rule with 100 intervals With the aid of the computer, the numerical evaluation is much less laborious. y 24P0491. A ANALYTICAL SOLUTION OF FIRST ORDER EQUATIONS Separable Variables (ol x?y' cosy + yon xaex (b) 2y' scos2yet, yo Pa, xe (1 Oy =sinyst, po bn xe (d) (18 xy’ feos? 2ye0, yd, xo-= le} e” = ey’ +1, y being bounded when x» += (0) be + tly’ =y— Wy bsing bounded when x (al y= 2sln# yl. y being bounded when x» Oo) ty a sinayet, yo la, xa te Answers to ya aren) 56 t yoauma(eh) on V3! (©) y= 2arctan(s = + arctan x) 4 22 (a) y=} arctan| an 2 (el yeo yet (el y= =m (h) y= arceot La Sp ae B. Homogeneous (a) 2xy dx + b+ yh dy = 0 to) (+ VP = xyl dy —y de (cl t+ yd Yaymo (2) xy = y= xsin\yix) = 0 (eh (2073 Ph des by? = 216 (8) Px + WV =a ~ xy dy 0 (9) Leos hax — (EsinY + cost) dy «0 2 My OR Answers (a) 3x77 4 Pac, Ol ysce"V" y>ox y. (e) Acetaniyii) ~§ fools? + y" (9) y= 2rArctan ox el xi + log xy 0, x #0, #0. (0 0x2 VAR, oF equivalently, ty + Vy aay 7 >a {g) ysiniyixl =e. 25, (3) ¥ cosx-y sin x™ 2% Yo (6) xy = 2y =2%c0s x My ~ytanx= costs, een (0) ying y= 3° Int {h) @e= Aly © 2y Ai) y+ y008%= €08x; Yleeo 1 Answers (a) pax a2, Wb) ye (ore, (0) yaiC+xie™, (a) p= x*Hleos x) (eh ys OF + x4sin x. (1 y= (sin xiticos*x} (a) y= (C +20) Inx (n) xem cy = v2, a Simultaneous wo toh & a tel ta 2 fo) & 3 ws Answers (a) Ts tte (0) fo) @ He Seahy ee ae pe ee taette zm CSE H (ey FD (oy eal + 05 le) xm etbey varie te, beat” (9 xm ae! Slsineteosts yet 1 tee"!P1.04.02. LT SOLUTION WITH INITIAL VALUES UNKNOWN ‘Transforms of the first two derivatives are it) nsr-m, (EB ete-a- ‘The initial values, yo and ys, can be made part of the integration constants The equation is y* + 3y' + 2y = dt, and its transform is 29~sy0~ 5+ 9107~ vol 2V= 4 Isolating the tanstarm, pe [4 egten tea ys Pr emaiera (tO +8) lavert with the data of Table 1.4 Yabo 0% 4 2-34 (207 em Myo +(e"! ois, (4+ Ayo + ysle™" = 1 yo vile" + 20-3 — Cie" + Coe + 20-3 This solution alsa is found readily by the method of undeter- mined coefficients ‘When the conditions are y{1) = 1 and y{2) = 2, the integra. tion constants are found from = 0.86700, + 0.13530; + 2-3 2 0.1989C, + 0.01830, + 4-3 Cy 4 yo + Y= 8.5287 Ce= HU) yy + y6) = 8.4071 ‘The initist conditions are found from these equations as Yo= 2879, y= 10.2061 P.04.03, LT SOLUTION WITH CONDITIONS AT TWO POINTS The equation is aya? +0.25y=0, with conditions 10) = 0, yln) = 0.5, The transform is S9~ ayo yo + 0287= p--tiy, fo with yo = 0 F028" * Investing, y= 2ybsin 0.8 Since Yin} = 0.5 = 26 sin(x/2) = 2¥6, y= 0.26, and the solution y= 0Ssinast 26P].04.04. LT SOLUTION WITH SQUARE PULSE INPUT (cos 1)=(1=c05 1ult-3) Ng The transform ie SY sI07 yb WY With the initial conditions yo = ye 0, pe -- 1 TOF er wa) Lo-cor nutes) / yf The second term corresponds to @ delayed response. The in- eA verse ie ° 3 v0 15 1 ya dott cose - G1 cos ule 3) Te two contibutions of the response and the net response are piloted for w= 1 and 9~5. Pi.04.05. IMPULSE AND STEP INPUTS The solutions of second order equations with impulse or step inputs are to be found y" +y = 6(t-a), with y'() =0 am 2" +z = H(t-a), with 2(0) = z'(0) = 0 (2) The transforms are ye exp(-as) set z a> exp(-as) s(s*41) The inverses are found from Table 1.4, y(t) = sin(t-a) u(t-a) sin(t-a), tea Oo, tsa z(t) = 1 - cos(t-a) ult-a) 1 - cos(t~a), tea Oo, tsa The plots with the two inputs are shown for a = 1. Fonction 1.04.06. USE OF THE CONVOLUTION THEOREM The convolution theorem, item 8 of Table 1.3, is of value when the transform is a product of two factors whose inverses are known individually. Take the case of the equation, y" + By’ + 2y = £(t) = exp(-3t), with y(o) = y'(0) = 0 The transform is (s%* 3s + 2) ¥ = F(s) 333 or yls) = £(s) ED £(s)g(s) where 271 a) © ERT g(t) = exp(-t) - exp(-2t) Also g(t-8) = exp[-(t-9)] ~ exp[-2(t-9)} Since f(8)} = exp(-38), application of the convolution theorem gives y(t) = Sif (o)g(t-o)ds = SSexp(-30) {exp{- (1-0) J-expl-2(t-2) 14a = 0.5exp(-t) -exp(-2t) + 0.Sexp(-3t) This can be checked by finding the inverse of 1 s+1) (s+2) (s+3) with item 29 of Table 1.4. y(s) = P1.05.01. POLYMATH AND CONSTANTINIDES Three simultaneous ODEs are to be solved. 8 2 ay, 8% = styzy, MH = aete, at tity, ae S(y-z), at Btt+z with to = 0, ty = 1, Yo= 1, 29 = Wo = The POLYMATH input is ay) a(z) a = 5*(y-z), 2 acey = t™2+y. Sey = S*Grz) " d(t) Note the parentheses around the variables in the derivative. The CONSTANTINIDES input is G(1) = x@y(1), G(2) = S*(y(1)-y(2)), G(3) = S4xty(2) Note that the independent variable is always designated x in this program. The two graphs agree. = Sttez 5-887 poLynarll Kev: sat rey ge 4 CONSTANTINIOES Wa 3.58! 2.88 1 5.89, 408 828 6M 868 BE t 281.05.02. SHOOTING METHOD FOR EQUATIONS WITH ‘The higher oller ODEs are reduced to systems of first-order equations and solved by the Runge-Kutta method. The missing condition at the intial point is estimated vatil the condition at the other and is satisfied. After twa trials, linear interpolation is applied; after three o: more, Lagrange interpolation is applied. {a) Fluid enters an immersed cooling coil 10m long at 200° and is required to leave at 40". The cooling medium is at 20% The heat balance is nos a00, wn no wich Is equi lent to the pair of equations & 1 = o.0n7 ~ 20) ‘The table end the graph show that the exk point condition is satisfied when 70) « ~46.515. {b) The equation yaxys (2 02Kyy" with yt} = 2; 3} =0 Is equivalent to the system a Was Bavy st —o2xye gree i ‘The value y'{0) = ~1.493 makes the solution satisfy the con: ition {3 = 0, The xy plat for that condition ig the midaile one. {c) The third-order equation yom yh= ae xty, with WO) =0; yl) = 15 yi)» =10 js solved as the system The curves and the tabulation show that y(Z] = ~10 is satisfied with the assumption ¥"(0) = ~3923. {d) The equation of part (b} is solved for the terminal con. dion, yi3) + 2/13) = 0. The results of several trials are vn yea yi) + 2918) Graphs of ylx] and y'{x] are shown for the coreect value, y'(1) = 1.8708. 29 TWO-POINT BOUNDARY CONDITIONS O39) 209 mS pes GijeePL.0S.03. DIRECT AND LAPLACE TRANSFORM SOLUTIONS (a) A pait of consecutive ceactions, Reactions: a8, Rate equations: Pe — tang at 08 6 kyo, ~ kane at ‘Material balance: Pao t Poet Aco My +8 + Me The solution of the first rate equation is direct 14 ge Substitution into the other rate equation results in @lineac differ. tential equation of the first order: 108 6 bang = karage Tht Hate kat of which the solution is ate, Ae = age + Ieo ks letters Also, Ina 90 Meg ~ age = age ateeggnbi hy Ay =i ) (0) Solstion of part (2) by Leplace transformation toy fate ts” tt silky 8} The inverse transforms are found in Table 1.4. and give the same results as part (a). 30P1.05,04. LAPLACE TRANSFORM AND NUMERICAL SOLUTIONS A set of reversible-consecutive reactions, A $! B 3 = “kA + kge k,A ~Ckgtky)B & a ~ Laplace transformations are made and rearranged to (stk, JA = KgB = Ap wh +(s#kgtg)B = By ~KgBtst= Co linear equations D= 8 + (kytk tky)s + kykz 5 = fo8t kathy) AoreaBo These are solved for the transforms as = _ Bostky (Ap*Bp) Be = _ keBeCy cH 3 Formulas 24a and 27a of Table 1.4 can be used for ‘transforms to obtain A, B and C as functions of t. A numerical solution is found, alternately, by 42 c, has the rate a) (2) (3) (a) () (6) mM inversion of these application of the CONSTANTINIDES program for these values of the constants: k, = 1, k, = 9.5, ky = 0,3, Ay = 1, By = Cy = 0. 1 ” 2 2 c 16 5 4 13 8 2 A a “gaa s 31CHAPTER 2 REACTION RATES AND OPERATING MODES THEORY A. Rate of reaction 34 2. Concentration, mols, partial pressure, mol fraction 35 3. Reaction time 36 4. Constants of the rate equation 36 1. Linear regression of the rate data 2. From the integrated equations 3. Plots of the data 5. Multiple reactions and stoichiometric balances 37 1, Multiple reactions 2. Stoichiometric balances 6. Reactor operating modes 39 1. The stirred vessel material balance 1. A filling operation 2. An emptying operation 3. A batch operation 4, Steady state operation (CSTR) 2. The stirred vessel heat balance 40 3. Tubular flow reactor 41 4. Packed bed catalytic reactor 41 7. Heterogeneous reactions. Rates of diffusion 41 Tables 43 PROBLEMS 1, Stoichionetric balances 50 2. Integrated rate equations 54 3. Complex reaction mechanisms 68 4 Numerical integrations. 86 1. qA 9 Products at constant V or constant P 2 AeB 3 A+BSC+D 4. A+ Be C+D, in terms of equilibrium conversion 5. aA + bBo cC + dD, at constant P 6. A+ B+ Co Products 7. A933, Bac 8. ASBSCSD 9. Hydrogenation of cottonseed oi} 10. A@BeC 11. Ae Bec 12. 2Ae BHC 13. A 9B, A+B9C 14.4 +B9C,B+C 4D 1S. A+BeCH+E, A+CHD+E 16. A+B 2C, A+C > D, Numerical 17. AB, 2B eC; 2A= Bs C; 2A9 2B, 2B C. Analytical INDEX OF MECHANISMS IN SECTION 3 1. Diffusion and n-th order reaction 2. Enzyme kinetics, Michaelis-Menten equation 333. Enzyme kinetics with reversible decomposition 4, Cell growth rate. Monod equation 5. Solid catalyzed reaction. Langmuir-Hinshelwood mechanism 6. Chain polymerization 7. Rice-Herzfeld mechanisms of thermal decompositions 8. A+3B > C+D by a three step process 9. ABCD from the components by a three step process 10. A+2B » C+2D by a two step sequence 11. Acetaldehyde thermal decomposition 12. Pyrolysis of ethyl nitrate. Data from a CSTR 13. Decomposition of ethane 14. Nitrogen peroxide decomposition 15. Hydrogen and bromine reaction 16. Phosgene from CO and Cl, 17. Photochemical oxidation of phosgene 18. Decomposition of ozone catalyzed by chlorine 19. Ozone decomposition 20. Decomposition of diethyl ether 21. Chlorination of n-heptane 22. Decomposition of nitrous oxide 23. Phosphorous acid 24, Acetone decomposition 25, Thermal cracking of propane 26. A kinetic reforming model This chapter deals with rate equations of chemical reactions carried out under batch or flow conditions. The applications are to identifying mechanisms of reactions, to sizing equipment, and to evaluating its performance. Tables 2.1 to 2.6 are an overview of the substance of this chapter. The participant A is identified by subscript a. Thus the concentration Js Cy, the number of mols is n,, the fractional conversion is x,, the partial pressure is p,, the rate of decomposition is r,. The capital letter A also is used on occasion instead of C,. The flow rate in terms of mols is ny but the prime (’) is left off when the meaning is clear, The volumetric flow rate 1s V', reactor volume is ¥, or simply V of batch reactors, the total pressure is om 2.1. RATE OF REACTION The term “rate of reaction" means the rate of decomposition per unit volume, , mols/(unit time)(unit volume) (2.1) > = Pao Xa _ 2 FP Ge! Ma = aol I-x,) (2.2) where x, is the fractional conversion of substance A. A rate of formation will have the opposite sign. The negative sign is required for the rate of decomposition to be a positive number. When the volume is constant, ac, - we only at constant volume (2.3) Law of mass action. The effect of concentrations on the rate is isolated as 34ry = KE(C, Ge.) (2.4) where the specific rate, k, 1s independent of concentrations but does depend on temperature, catalysts and other factors. The law of mass action states that the rate is proportional to the concentrations. For the reaction aA+ B+ cC +... 9 IL + m+... (2.5) the rate equation is 14M, Payp(PeyaPeyr r Vae RGGI. (2.6) = k.CRCICE..., at constant volume (2.7) The exponents p, q, T, ... are empirical, but they are identical with the stoichiometric coefficients a, b, c, ... when the stoichiometric equation truly represents the mechanism of reaction. The first group of exponents identify the order of the reaction, the second group the molecuiarity. Effect of temperature. The Arrhenius equation relates the specific rate to the absolute temperature, k = kgexp(-E/RT) (2.8) = exp(A-B/T) (2.9) ink =a-% (2.10) E is called the energy of activation and kg the preexponential factor. From experimental data, the constants are found with the linearized plot, Eq 2.10. 2.2. CONCENTRATION, MOLS, PARTIAL PRESSURE, MOL FRACTION Any property of a reacting system that changes regularly as the reaction proceeds can be formulated as a rate equation which should be convertible to the fundamental form, Eq 2.6. Examples are rate of change of electrical conductivity or of pH, or of optical rotation. The commonest other variables are partia) pressure p, and mol fraction N,. The relations between these units are, n Pa (2.11) ny = VC, = aN = % where subscript t denotes total and m the total pressure. For ideal gases, La vy ry, ny = TEC, = oy = ae = FM (2.12) Other volune explicit equations of state are sometimes necessary, such as the compressibility factor equation, V = 2RT/P, or the truncated virial equation, v = Btisp). the quantities z and B are not constants so some kind of averaging may be required. More accurate equations of state are even more difficult to use but are not often justified for kinetic work. Designate 8, as the increase {n the number of mols per mol decrease of substance A according to stoichiometric Eq 2.5, by ateror? (2.43) The total number of mols present is De = Myo*SA(NGO-Ma) = Nyt Xe = NegtSpXy T° (2.14) It then follows that -o Se _ 5 Ste (2.15) at vat ~ Peat . 35At constant volume, any ac, oy apy aN, any a Yacma "ha * Mae (2.18) At constant pressure” dn, dc, dn, ny (dC, /dt) 1. AT), ar 1), BufaCy at 7 rae “aE = qaRTE Cc, (2.17) dn. n, (dp,/at) ze Sp (2.18) any ny (aN, /at) ae Ta (2.19) An equation like Eq 2.7 can be written in terms of partial pressures and mol fraction as Fy = KeC'= kPa = Kye (2.20) The relation between the specific rates is k= (Rte, = Ey %y (2.21) Typical units of a first order reaction in terms of different variables are: Variable Rate equation ‘Typical units of k Concentration r= KC sect Partial pressure r = kp nols/(Liter) (sec) (atm) Mol fraction r= kN mols/ (liter) (sec) 2.3. REACTION TIME Flow reactors usually operate more nearly at constant pressure, thus at variable volume with gases. An apparent residence time is defined as the ratio of the reactor volume to the inlet volumetric rate, Papp = VeZVo (2.22) The true residence time is found by integration of the rate equation, t =f dv,/v' =f dn/rv’ (2.23) Both the reaction rate, r, and the volumetric flow rate, V’, must be known in terms of the number of mols, n, of the reference component. The apparent residence time is popularly used to indicate the loading of a reactor. A related concept is that of space velocity which 1s the ratio of a flow rate at STP (usually 60 F, 1 atm) to the size of the reactor. The most common versions in typical units are, GHSV (gas hourly space velocity) = (volumes of feed as gas at STP/hr}/(volume of the reactor or its content of catalyst) = SCFH gas feed/cuft LHSV (liquid hourly space velocity) = (Volume of liquid feed at 60 F/hr)/cuf t= SCFH liquid feed/cuft. WHSV (weight hourly space velocity) -= (1b of feed/hr)/(1b of catalyst) 2.4 CONSTANTS OF THE RATE EQUATION The problem is to find the constants of rate equations such as aC on =- Hake (2.24) 36or pe — Ek exp(a-p/t) cm (2.28) or ra = kCRCR. (2.26) Experimental data that are most easily obtained are of (C, t), (p.t), (r,t) or (C,T,t). Values of the rate are obtainable directly from measurements on a continuous stirred tank reactor (CSTR), or they may be obtained from (C,t) data by curve fitting and then differentiating. Several methods are conmonly used to find the constants. (4) Linear regression of the rate data. Take logarithns of Eq 2.25 Inr = ink +*A~-B/T +n In€ (2.27) The linear variables are In r, 1/T and In C. The term (In k + A) Is a single constant. A multilinear regression program can be used to find the constants, or only three sets of data can be used and the constants found by simultaneous solution of three linear equations. For a linearized Eq 2.26 the linear variables are the logarithms of r, C,, Cp,....The logarithmic form of Eq 2.24 has only two constants so the data can be plotted and the constants read off from the slope and intercept of the best straight line. ii). From the integrated equations. The integral of Eq 2.24 is - c Le (2.28) cot ot Tee wed yo)" 1), when n #1 (2.29) A value of n is assumed and values of k are calculated from the data. The correct value of n has been chosen when the values of k are nearly constant Integrals of some common rate equations are summarized in Table 2.2, Others are developed in problem Section 2 of this chapter. An(C/Cy) = k(t=to), when n = 1 (2.30) azey* = (1c) + ktn-1)(t-tg), when n #1 (2.31) A value of n is assumed and values of the left hand side are plotted against (t-to). The correct value of n has been found when the data are collinear. The correct value of k is found from the slope of the best straight line Before an expression such as Eq 2.26 can be integrated, the RHS must be expressed in terms of the single variable C,. From the stoichiometric Eq 2.5, Bao-Ma _ Peo~Py _ MoT | Bao"Pe a > ny _ Ayonx Co Ry - (2.32) Rygubx/a ~v Rggrex/a (2.33) . Vv Also, 37Cro = BC yo-Cy) Ce = Cop ~ ElCyo-Cy) (2.34) Thus the rate equation becomes ree bok 2 1 Pe Vat Vodt Nyo~* p Myo-b¥/A, 4 Neg-Cx/a. = kOY ae eae (2.35) In terms of concentrations, Ta =~ ae = kCRCECE. = KOZ (Cyo~B(CyonCy) 39 [Ceo ElCaomCa) > +: (2.36) 2.5.1, Multiple reactions. When a substance participates in several reactions at the same time, its net rate of decomposition is the algebraic sum of its rates in the individual reactions. The rates of the individual steps are identified with subscripts: (dC/dt),, (dC/dt)2,.... Take this group of reactions: c 1 A+B> 2 A+CSD+E 3 3 where itis not necessary true that 2 Yy 4. Ateonstant volume = 4) a 1 nf CHtse= DaPesNGre= Ge ° vere 0 LRT balan a CCompated integrals for some values of and Bargin Tobie 2-2 5, Idea! gases at censtont pressure aM net ing rk 6, Temparature ofect onthe specie eo oxplE/AT = xa 6/7) igebraie sur of the take the theee Fa tae Fant as = Cla” Oly + Cae Clo hCala Fe EyCaa + Ea FEC Fema ‘The number of independent rato equations is the sama a the umber of independant stoichiomettie relations. In the present ‘example, reactions 1 and 2 ore a cevarsible action and are not indapendent. Accordingly, C and Cy, for example, can be eliminated from the equations for r, and f, which then bacome an Integrable. system, 43TABLE 2.1 Ccontinued? 8, Mass tronserroslstance: Cus= interacial concentration of rexctant A Sense, coeter=i(e,-Z) om , =n “The relation between 1, and C must be establishes (numerically it ‘eed be) trom the second tine Belore the integration con be competed solid catalyzed rections. These wvotve simultaneous diffusion, adsorption and surface reaction. See Chapter o. 10. A continuous sted tank reactor batery (CSTR Matecalbatances: Mom nb ra Mayer yr forthe jth stage For 8 fist order tesetion, with 4 = KC, Su, CTF RUIN FEED FED 1 TRY" {or tants in series with he same temperatures ond residence times y= Ml Vi, where Vs the volumetric How rata 11, Plug tow reactor (PFA ng Sb sex Sha sczet Hoy VIMO v oy, 12, Motarie! snd eneray balances for batch, CSTR and PFR are in Tables 2.3, 2.4 and 2.5 13, Notation A.BR,S ace panticipants in the reaction; the leitersslso are used to represent concenvations G.= Al, 0F nf/V, concenteation = mols of componeat jin the reactor 1} = molal flow rate of component | % = volume of reactor Vie volumetric low rate y= swoichiometric coefficient Gm rate of reaction of substance # {molffonittimeliunit volums}] if m eenpirial exponents in # rate equation 44TABLE 2.2. Some Isothermal Rate Equations and their Integrals 1 A+ products: Ae ae A Mbo epl-Ktty, Get 1 ere. aed 5 THCq-AD ASTER tos 2. A¥B- producte: FAB=HIA+ By A) AdA+ BoA) Be Het) 3. Reversible reaction A by A~ fg Ba ~ AD + DA ily Be) byAg~ be Tht RIAq bat Bah (eee +s 4, Reversible reaction, second order, A+ 8 & AB ~ KAS = KALA + By — Ah = kale + Ry — Allg # So Al aA + BA y oak hy Br bylBy~ Aa) + kel2Ay # Ro + Se) UA Ralls + 5) oir Zara + B aca p ere Ly [(2adokBoa\(204e 090) 2 ell Neearaza)) 9° Kt okt Bt q)\2oAw pf 5, The reaction v/A+ 8-2 v/R t vl* w Qt ° © Solve £9 (6}10 ind T= f1C,}; combine Eqs. (1) and (2) and integrate os @ 4g CP ersar semen yature and time a8 a function of composition are ehawn fortwo values of UA/Y, or a paniculat ease represented by at walsoo = Ty Fa [sooo srs AEE r= exp(te-s000/7) T3860 Cont on : i i os 46TABLE 2.4. Material and Energy Balances of a CSIR ‘The sketch identifies the nomenclature Mian residence tine few eo ‘Temperature dependence kseaple'— 270 a Rate equation pea kOT = det = 15 x= (Coe CNG © Matai batece: 6 Enthalpy balance Deity E notes O— Atma ni) © (Ler n eh = thant | AG er © For the rection #4 +B (A +55, 8G, = Gye 5Cpu — Cpu Ga oy \When the heat eapaciies are equal and constant, the heaCbalance is GoW (T= Te OAH ICo~ 6) 100) qs (2) and (5) combine to 500 Fes and Eq. (10) becomes, "= 2{0.9|7—350)—25x1,, Meal/nr “The tomperature ane the rate of heat input @" are tabulated as functions ‘ofthe residence time for conversions of 30 aad 85%| TABLE 2.5. Material and Energy Balances of a Plug Flow Reactor CPFRD The balances are made over 8 different Fate equation: volume d¥, of the reactor Dianeter, 0 ayant o = a enestea' vin o Enthspy balan: ath thet [86.67 @ co=uin nas, Merny sui =n, = hay o 60+ AH, dni Sm dh =D ny oT @ BE AH AUT = TD a7, Fd o z a Ta [At constant Ty, Ea, (7} may be integrated numerically to yield the emperatere a¢ 2 function of the number of mols T= oto @ ‘Then the resctor volume is found by integration ° Adiabate process: ao=0 to The balance around ane end of he reaetor is Trobe Ehaloia=oid= Lo = Soa [Ger on in tren tempaature aT entapis Ha 0 ora Sa f Guat wa, Aciabaeproznts with AC, =0 and with constant heat capaci Mea ray btlaltio= aw . Tiny “Ti exprsson i ubeiute instead of Ea (8) 10 fing he volume wth at 4BTSBLE 2.6. Material ana Energy Balances of facked Bed Reactors Difusivity and thermal conductivity are taken appreciable only in the redial direction ‘Mataral balance equation: Be) dene 0 Enecgy balance equation: aT_k (27,197) she, Be ae (Sate ac, "9 a ithe net —_—__ x10, 7) = x0 * 3) 10, = Te rR ‘a z za ithe center: § 5 « roa, fo 6 0 > Alte walt % 2» & @ aru Zelir-n ” When the temperature T° of the host 1ransfer medium is not constant, snother enthalpy balance must be formelated to relate T” with the process temperature. ‘A.vumerical solution uf these equations msy bs obtained in terms of Fite diferonce equivalents, taking m radial increments and ‘ones. With the following equivalents for the derivatives, the solution ray be caried out by direct aeration: ®) a 0) a Expressions for the x-dervatives are of the same form: ‘res eate of cbaction, a function of sand T G= mass flow rate, mazs/timel(superficial cross section} um linear velocity itsivity ice thormal conductivity 49PROBLEMS, CHAPTER 2 P2.01.01. STOICHIOMETRIC BALANCES The reactions are 3A # 2B and 8 + 2C 4D, two reactions involving fou components. Express C and D in terms of A and B and formulate a pair of solvable ODEs. Consider the reactions to proceed consecutively, and identify intermediate concentrations of those substances that participate in more thay one reaction, in this case substance B. Eliminate the intermediate concentration B, from these two equations 2 By = BytS(Ag-A) CorC = Be -S = B+D-Do C= Cor $lAgrA)-2(By-B) a 2 D = Dg +5 (Ag~A}+ (Bo-B) (2) The differential equations are | dA 3. 2 ae 7 KA +KB (3) aB 2. 2. Se = KA gB?-KkBC™ = kyAP kg BK BECg-G(AgA)~2 (By-B)]? w A and B are found as functions of t by integration. Then C and D are found algebra. “The reactions are AaB Awe B+2C3D They are assumed to proceed consecutively. Accordingly the relations betwee the conversions are omy = B,-By a Ay-Ay = Cy-Co (2) B,-B = 0.5(C,-C) = D-Dy (3) Only D needs to be found algebraically. Eliminate A, making AorA = By-By + Cy-Co @ From (3), B, = B+ (D-) cy = C+ (2(D°Dg) Substitute into (4) and solve. so(Ag-A) + (By-B) + (Cy-C) p=n+ereree (5) The differential equations are GA ~OytkglA g = kyA-k BC" SE = ak spc After integration for A, B and C, D = f(t) is found with (5). P2.01.03. PAIR OF SECOND ORDER EQUATIONS The reactions are AtB = CHE Atl + DHE The relations between the changes in concentration are wm (2) D-Dy Combine these relations so as to eliminate the concentrations with subscript 1 and to find C, D and E in terms of A and B. = CotBy-B (AgrA) -2(By-B) (3) =(By-B)-(Dy-D) ~ (By-B) = (Ag~A}#2 (By-B) = = (A-A)+ (BoB) (4) =(AgrA) (5) Eys (3), (4) and (5) are the desired stoichiometric relations. The rate equations for A and B are, aA at ae at = -K,AB - kAC = -A(k,Btk, [Co~ (Ag“A) #2 (Bo-B) ]} (6) K,AB 7 P2,01.04. THE REACTIONS 2A » B, 2B + € The relations between the changes in concentration are = By-By @ = Cy @ Combining, A B, = Bot < B + 2(C-Co) "A. Bo-B Cy = * +> a) The differential equations are SL= k,A-k, After integration, C is found from (3). THREE REACTIONS, FIVE COMPONENTS The reactions are 2A > BIC, AXC > D, AWD FE D and E are to be found in terms of A, B and C. The stoichiometric balances are = C,Co mM D,-Dy (2) AjrA = D,-D = E-Eg (3) Eliminating A, and Aj, Ap-A = 2(By-B) - (Dg-D) - 2(Eo-E) (4) Also, AgrA = 2(Cy-Co) +Cy~C+E-Ey C#(Ag-A)#(Eq-E) #2Cy ge ee = Co“ (BoB) Rearranging, Co-C = (Ag-A)43(By~B)+(Eg-E) (5) and EgrE = ~(Ag~A)-3(Bg-B) + (CC) (6) Then, Dg-D = ~(Ag~A)~2( (By-B)-2 ( (EE) «) = (Ag"A) #4 (BoB) -2(Cy-C) mM The differential equations are dA 2, HSE = iAP agAC HAD = ALKA #kaCtkg[ (Ag~A) +4 (By-B)-2(Co-C) +Do] } dB_ Kia ~ae a ac Ly Kt Ge 7 Alp A + RC) After these three equations have been integrated, D and E are found from Eqs (6) and (7). 2.01.06. THE SHIFT REACTION Carbon monoxide is shifted to the dioxide for ease of removal by the reactions CO+3H, @ CHy+H{O, A+9B 4 C+D COFH;O # Hy+COp, AMD § BYE Components C, D and E are to be expressed in terms of A and B. The stoichiometric relations are 52AoAy = CCy = Di-Dy a@ A,-A = D,-D = B-B, = E-Ey (2) Eliminating Ay, (Ag-A) = =(Cy-C) - (EgE) (3) Solving for By, B, = B+3(Cp-C) = B4(E-E) which becomes, (By-B) = ~3(Cg-C) + (EgrE) @ Combining (3) and (4), (CoC) = tpn) = 408,-8) (s) Substituting into (3), (Eq-E) = = (Ap-A)~(Co-C)4 3 1 = -FlAg-A)+G(Bo-B) (6) Solving for Dy, Dy = DotC-Cy D+E-Ey from which Do-D = (Cy-C)=(Eg-E} = FA ADF (8-8) 7) Items (5), (6) and (7) are the required stoichiometric relations. The differential equations of the two reversible reactions are GA AB? ,CD-KgAD+K BE TK AB“+K,CD+K3AD-K,BE Substitute for C, D and E before integrating. REACTIONS. For the reactions, A+2B ® C and A+2C » D+2E, only A and B are present initially. Find the minimum number of differential equations that will give the composition of the mixture as a function of time, Let x = amount of A converted by the first reaction y = amount of A converted by the seccnd reaction A + 2B oe C Agr By-2x x A +20 9 D+ 2E Agx-y x-2y yay The final values are A= boox-y B = Bo-2x C= x-2y Dey E = 2y Elimination of x and y results in 933(Bp-B)-4(Ag-A) ss te qa 2fAg~A)~(By-B) = z (2) E= 2D (3) The differential equations are . dA _ 2 ~98 = kyaB™ + aac’ 2, Ke 2, = ACK:B'+ Z13(ByB)-4(Ay~A) 173 aB “in = 2ky. AB? After these have been integrated, the other compositions are found from (1) (2) and (3). 2.02.01. REACTION, gA » Products, AT CONSTANT ¥ OR CONSTANT P ‘At constant volume. the rate equation 1s sc ae and the integral is = kct . 1 egia k(toty) = giyt€ c Ca¥ (q-t)kCH? (t= tg)? exp[-k(t-tg)] q 1 At constant pressure qa = vB + vc + (vytygt.. I-a 3, = Wetter a q The total mols and the ideal gas volume are Dy = Neg + Sy (qo) v= BE and the rate equation, [ngot8g(ngg-n) The variables are separable, ot pao [Megt8qlMag-,)] K (toto) (He? = se? 0 < dn, ‘a ng When q = 2 for instance, sak(t=to) (/RT) = (myotSango) 2.02.02. FIRST ORDER REVERSIBLE, A » B The reaction, A $B, has the equilibrium constant Ke = ky/kp = By/hy = (AotBomhe)/Ay The rate equation is _ da a = kAHK,B = (cytkg)A ~ ke(Ag*By) = k, LO H/KIA = (AgtBo) Kel The integral is (k, +g) Aka (Ag*By) (kytkg) (tty) = In When By = 0, Ky = (Ao-Ag)/Ae, ko = KyAe/(AorAy) wk io a and the integral is PZ.02.03 SECOND ORDER REVERSIBLE. A+B « C+D The reaction 1s A+B $ C+D and the stoichiometric balances are = By-B = C-Cy = D-Dy wm The equilibrium constant is C.D, _ (AgtCy-Ag) (Ag*Do~AQ) Re lBo=ho*Aa) @ Ka/ky, = x, The rate equation is ~ As k,AB - &C0 KyA(By-AgtA) ~ ka (Ag*Co-A) (Ag*Do~A) k = ZIKEACBy-AgtA)~(Ag#CoMA) (Ag*Dg~AI fe“ LIA7# IK, (Bp-Ag) #2AgtCytDgA —(Ap#Cg) (Ag*Dg) (3) = (ky7kp)A*+ fk, (By-Ag) +2AgtCo#Dg Ak (Ag#Cg) (Ag*Dg) (4) Special case with Ag = By and Cy = Dy = 0. = SA = (hee, )A“ +2 AoAMKaAG (3) In terms of x = Ag-A = Bo-B = C-Co = D-Do (6) BE ey (hyn) (By) “Keg (Co) (Dy) ) 55k, = ZLK,(Ag“x) (By-¥) = (Cot) (Dgtx) } (3) L(K-1)x* EC gtDg#K, (Ag*By) 1X +KgAgBy-CoDg} 9) Bx ty) (10) The coefficients a, @ and y are defined by comparison of Eqs (9) and 10. The) discriminants are Ia? ~Aoy qa) Tan -B* (a2) There are three cases: When q°>0, the integrals of several cases are in, 4 q the tabulation. When q°0, grlarctan22%"B) ~ arctan(f/q’)] a3) and when q 0, 1 +i 14) D The graph shows the effect of K, on fractional conversion x when the rate equation is ax 142; 22, Ge ARAGL C30)? -x77K 1 as) Revenstaiz Sscono-onven Reactions tq Cat = 8 = 9)(2am ~ 0 +g) KV = q'" Garp +0)(am B= 9) a= VF action ae React & « e 7 : | c+D Bip Me — 2) ~ (na + 2) + 2)) -1 | KV tnet ne KV nay — nang k zs w=c [Mow - 3k (m0 +3)] K 2iknas + F Kina — Ving _ k . 2 2 ne tae « case+p [icine 29 = (ne43)(o0-43)] | aa | ame ee | eat ne AtB=C 37 lr — 2)'me ~ 2) — Vina +2) K Kova +10) +9 Katie ~ Vr A+BeCHD tna — nae = 2) ~ (na #2 a) | Kt | Kerem) ene tae | Karta — a 56x = fractional conversion 18 P2.02.04. A+B $C +D, IN TERMS OF EQUILIBRIUM CONVERSION Solutions of three of the cases in the Table of problem P2.02.03 are rewritten in terms of the conversion, x, = Ag-A,. Substitute for K, in terms of x, G)A+BeC+#D, with & =D 2 Bee ky Llp)? - “OE Xe S06 eer)? = 2x2 + Agx?] x eer = 4x2 (7A)? AoKet% (Agr 2%Q) pees ae @ (il) A@ BHC, with By =C)=0 ct AoXe = = [Ag - SS x] Xe SL OxeAg)x® =o + Axe) a= Bday = x2(x,-2hy)* x Aoket (Age) a8 = 20s) IP Agtexd (ii) A+ Be C, with C= 0 (2 2 (Agr%,) Be dx ae = Ki (Ag-x)) x] k, = ted (Ag-xx,) Application of the standard integral gives the desired result STax J Taeby(perq) = bp-ag ™ axsb’ (P~ag#0) (3) P2.02.05. aA + bB > cC + dD, at Constant Pressure The change in the total mols per mol decrease of A is Me = Megt SalMgo-Ma) = MyotSaXq ven U- (ngot6 x4) EE The rate equation is ax, k a bl yb BE aero He) Cao BHe) a > (Byars, (Baga) (mao b4e/8) ‘RT atb-1 (myo .%a) Standard integrals cover the cases with a = 1 and b 1or 2. a 1 lee Sermerm ~ aaa EE) 0 r= of, 072, Si - wig lobe le tal Eta @—9 Pele ta = clog Jo 21 Soriere SFR T=aeTS +7 @aeFD og [22 ~ pil 2: 2 Sortie ier + Sap let al + CS lo le + 582.06. THIRD ORDER, A*B+C = Products Four cases of irreversible thiord order reactions are considered. (i) When the reaction is A¥B+C + Products SE = kla-x) (b-x) (o-") The integral is evaluated after application of the partial fraction rule, 1 4 ee GtOG+)G+) eta etd ave’ 1 1 1 where 4 = ea Pe @-he~ sy" ene oe 3” The integral is a (41) When a = b and dx/dt = k(a-x)?(c-x), the integral is guoted in problem P2.02,05, (a-x) (c-%) Te kt = (2) tera) Yaxo (ili) When the reaction is 2A+B # Products and dxdt = k(a-2x)*(b-x) the integral is given in problem P2.02.05, (a-2x) (b-Xo) xt = 4 raracte- i) + ee (2b-a) oreo HX (iv) When the reaction is 3A # Products and dx/at = k(a-x)? the integral is =i kt = 5 - 1 (a-x)®— (a-xy)* = CONSECUTIVE REACTIONS, A> B, BC The pair of differential equations are solved either directly or with Laplace transform, with a table of inverses. (a) A pair of consecutive reactions, Reactions: 59Material balance: Pay fag + Mea = M4 0M The solution of the first rate equation is direct ‘Substitution into the other rate equation results ina linear ciffer~ ‘ontial equation of the first order: 28s bang = kinase at ‘of which the solution is faa get ght Hig EAs grb — ooh ee 00 ky Also, fe = Pag * Reg Hes ey Hag * og #9" we — Moge™ mh geht, (0) Solution of part {a) by Laplace transformation, Sha Stig = M59 hyile coe ee noo + hive Poo, Katag ts kets litle sd P2.02.08. CONSECUTIVE REACTIONS. 4 = B = C + D. LAPLACE TRANSFORM The consecutive first order reactions have the rate equations da ae 7 KA a 2 = kyA-k2B (2) ac de > KaBrksC @) Component D can be found by material balance after the three differenti; equations have been integrated. D = Ag+BgtCy#Do-A-B-C ) The Laplace transforms are SA - Ag = -K,A or (s#ky)A = Ap (5) sB ~ By = k,A -k2B or kA — (s+k2)B = By (6) sf ~ Co = 2B -k,C or kB - (s+kg)E = Cy ca The ‘determinant of the coefficients is (sty) 0 ° k, 7fStK,) |= s¥k,) (stky) (s#k5) fg) ° ky = (stk) 60Accordingly the individual transforms are Ao 0 ° K |B -(stk,) 0 | = a (9) Co ky (tks) (stk) A oO 1) mo - fe Kiko (10) a 1 Bo srk, * (sek, )(stKa) Oy -Cstk3) (stk) 0p ky (-(stkg) Bo ° ke Co kik kB ¢ - ako © an (stk, ) (stk, )(s*k,) (s¥k,) (sty) "stk, Inversion with a table of Laplace transforms gives the results, A= Ay exp(-kyt) az) Kit Be ogy lexp(yt) ~ expt-kgt)] — Bo exp (kt) (13) _ exp(-k,t) exp (-kt) C= Kikoto Ge Meg) * Eg ikrk) KkaBo = pe texp(-kgt) - exp(-k3t)) ~ Cy exp(-kgt) a4) ake Finally D is found with Eq (4) 2.09. HYDROGENATION OF COTTONSEED OIL. ‘or the hydrogenation of cottonseed oil, the main reactions are postulated by Eldib & Albright (Ind Eng Chem 49 825, 1987) as aisle nd (8) “Noe vnaic wine’ fp Semseetat ALA Tsooteic acid (C) On the assumption of all first order reactions, integrate the equations for A, B and C Gh = = Chey) a SB yA ~(cgeky)B 2) ac GE kegh MgB “ket (3) élThe first equation has separable variables, the other two turn out to be linear. A = Agexpl-(k, tka) t] (a) Substitute into Eq (2). SB es Ccgtkg)B = kyAgexpl (ky +k) t] B expl (kgtky)t] = kyA S expl (kytkg-ky-ka)t]at # I B= By when t = 0 {exp[=(k,#ka)t] - expl=(kgtk,Jt] } + Boexpl=(katky)t] (5) Substitute into Eq (3), ac Kakaho SE + KsC = Kohgexpl-(ky#ka)t] + expl-(ky+ky) t] 3 onl (ki ke Ky Ao Pk a(Bo- amc) OPI Cake) #] (6) 7) Ky Ao Kpkk =k B = KglBo - (3) The integrating factor of Eq (6) is exp(kst) and the solution is C explkyt) = J{ a exol-(ky+k,)t] + Bexpl=(kytk,-kg)t] dat + 1 = % (ky +k ~—# = (cH + = ag rignkOMP (Ketek) tay agen Okstkeke JE] + Evaluate the integration constant I, taking C = Cy when t = 0. Then multiply by exp(-kst). C= St fexp(-kgt) -expl=(ky +k, )t1} 1*Ka7Ks +B fexp(-ket) -expl-(kytky)t]} kk aks 5 atky For the final results substitute the values of « and ® from (7) and (8) Component D can be found by solving the equation ap at after substitution for B and C, or by stoichiometric balance with the result; for A, B and C. = kB + oC 2.02.10. REVERSIBLE AND CONSECUTIVE REACTIONS For the reversible first order reaction followed by a first reaction Agesc 3 The rate equations are aB ae = “XiA + kB a) 62SB = ya = (ky )B (2) C = AgtBgtCo~A-B @ Transforming (1) and (2), SA - Ay = -k\A +K2B or (stk, )A - kB = Ag SB - By = kA -(k+k,)B or -kyA + (s#kz+k3)B = Bo The determinant of the coefficients is stk, -ky 2 Be TO cateeieg| 7 S84 Ratha )s“kyks = (948) (88a) where 6, and By are the roots of the quadratic. Solving for the transforms, 1 (s “ke __ Botha kets) +k Bo Re BR |By s+ka+k,| ~ (548, ) (s*83) ‘stk, Ao] _ Bostky (Bo~Ag) -ky Bo] © (s*B,)(s*82) When By = 0 the inverses are, Bin [kgtkg-By) expl-B,t) - (kgtks-Bg) exp(-B2t)] K1Ao fy (PCB yt -exP(-Bot)] p2.02.11. A @ Be C, CONSECUTIVE REVERSIBLE, These consecutive reversible first order reactions, AGB 3 C, have the rate equations dA get KA + kB aB Fe = KiA Ocgthg)B ~k3C dt _ _ ae k3B The transforms are, SA -Ay = -K,A + koB or (s#k,)A = kB = Ap SB - By = kA -kpB - kG or -k,A +(s+ka)B +k,C = By sC - Cy = kgB - ky or mk + (stk,)E = Cy The determinant of the coefficients is (stk, -k, 0 B= | -k, (stk,) ky 0 ky (s#k,) 0 (stk,) (stky) (stk,) - kyka(stkg) + kG(stky) (s#B,) (S482) (etBy) " 63where the B,; are roots of the cubic equation. Solving for the individual transforns, a an By (s#k,) ky Cy -Ky (s¥ky) pie Ao (tka) (stg) “kak sCotkpBo (a4 g) *kahg (Sky) +k GAg (S+Kg) : Rofo S*Ea) atolsthet 2+ + s? + as + a, ~ {s+B,) (S48) (S+B3) Formulas for B and € ave similar in form, a ratio of a quadratic and a factored cubic. Formulas for the inverses are given, but since no simplification appears possible, the final answers will not be written down tates waa ni Wale Weed at wrartoed | Gane eae Lp wood — ot Bae tea Walle dA 2 Sh = aka A Ao T#2k,Agt) 3B 2 GB + kB = KA 2 =e (142k Agt)® The integrating factor of this first order linear equation is exp(kzt) so the solution is, KAS exp (kat) (142k Agt)? An analytical integration is possible after expansion of the exponential in a B exp(kgt) = f power series, namely explx) % xn The indefinite integral that applies is forex 407 8s _[eractiyniem firotect tye] ~a@rEED wos rT fenacreen feces). Gia) oa oresFor practical purposes, however, a numerical solution may be easier 2.02.13. THE REACTIONS, A + B AND A*B + C The rate equations are aa GA eo “kA ~kgAB = ~A(Ky #428) (os) GP = yA -k,AB = AGe, KB) 2) C= Cy +0.5(Ag-A) +0.5(Bo-B) (3) Eliminate the variable t between (1) and (2). op KKB pk a” ~ Kk; 7 Bek k = ky/kp Integrating, B 2k neck ) A= Ag-BytB -2k 1nBok Substituting into (2), OB (K,-1 -B,+B ~ Bok Ge = (ki7kP) (Ag-BytB ~2k In) (s) Although the variables are separable, the integral cannot be found analytically, but B= f(t), numerically. Then substitute into Rq (4) to obtain A as a function of t, and finally find C with Eq (3) Alternately the numerical solution of Eqs (1) and (2) can be found directly by software ODE, without going through Eq (5) 2.02.14. PAIR OF SECOND ORDER REACTIONS, A+B + C AND BC 4 D. The rate equations are, dA LL oA AB mM dB Ge 7 TK:AB -k,8C (2) ac Ge = AB -k,8C (a) D = Dy #{Ap-A) #{Cg-C) (4) The variable t is eliminated to give 4B _ + ko . a gat tatty () Co ke 4 Se teak (6) where k = ko/k, and y = C/A (7) Equations (5) and (6) are first order homogeneous types. Differentiating (7), aC = Ady + yaa ac a Agy da > Y * Aaa The integral of (8) is =-ttky (a) 65cn ay yy (k-1)C7A = Covkg URL) y= KT PTT CSAS which could be rearranged as C/A = £,(A) (ao) and substituted into (5). Then the variables will be separable with thi| integral, B In(A/Ag) = J ) +h (148, (Al}4A = £2(A) a ° Substitution into (1) and integration gives Hy (toty) = ata a2) from which A= £5(t) a3) Some further juggling will yield B, C and D also as functions of t, but fe most values of k = K,/k, none of the required integrations can be don analytically. The alternative solution Is numerical integration of the differential equations from the beginning. P2.02.15. SIMULTANEOUS REACTIONS, A+B = C#E AND AC > D+E The solution proceeds by first eliminating the varlable t from the tw) rate equations. ‘The reactions are A+ 8+ C + Eand A+ G-r D+ €, with Cy Do = 0, The stoichiometric balances are Aon A= C#20 co By B= C+D 2 A= Ay~ 2B0~ 8) +6 (9) The rate equations are 08 mH k\AB a Eo AB bAC 6) “a Dividing out de and rearranging, ‘The integrating factor for this first-order linear equation is, re exp {(~S)on= a ‘and the solution is or fismaaeere= Rearranging, ob " 66Substitute (6) into (3} and that result into (4), which becomes as Bo nao ot al after eyo ‘The variables are sepacablo, but for most values of ra numerical integcation will 6e called for. 2.02.16. SIMULTANEOUS REACTIONS A+B » C AND A+C > D The specific rates are k, = 0.3 and k, = 0.1. Initial concentrations are Ag = 0.9, By = 0.3, Cy = Dp = 0. The stoichiometric balances are C = 3(By-B)=(Ag-A) = ASB D = (AgcA)-(Bg°B) = 0,648-A The rate equations are ~ GA = ka + k,AC = 0.388 + 0,15A(A-38) dB - = kab = 0.948 The process of eliminating the variable t from the rate equations, as in problem P2,02.14, does not lead to an analytically solvable problem, but a nunerical solution is developed by ODE and is plotted. P2.02.17. SECOND ORDER SEQUENCES. ANALYTICAL SOLUTIONS Several cases are solved in terms of higher transcendental functions by Chien (JACS 76 2256, 1948). These are (a) A» B and 2B » C; (b} 2A 4B» C; (c) 2A 4B and 2B + C. Only case (a) 1s reported here, with By = 0. The rate equations are aa oA = aa a dB 2 Be ka Hk, (2) C = Cy 40.5 (Ag+By-A-B) (3) Substitute the integral of (1) into (2), GB = kyhoexp(-k,t)~ 8 a 67This is a Riccati equation. On applying the transformation _ 1 du 8- rag (5) the result is a linear second order equation, ~kykpAgexp(-k,t) u = 0 (6) 2 dt A change of the independent variable according to t = exp(-k,t) ua) leads to a Bessel equation, dg, wu . . ae Gy) “Ku = 0, K = Ky kao (3) whose solution may be written wD u = ayJo(atKe) + agy Hy (21K) @) where a, and a are integration constants and Jy and Hy!) are Besse) function: of the first and third kinds of zero order, in the notation of Jahnke & Enik (1943 or 1966), and = {-1 After return fron the variable u to the variable B and application of the condition By = 9, the solution becomes o 8 ae 35) ~ BH (9) 0) | AE oa + aK?) o y= 2HKt, B= 53, (a) HE ay 01. DIFFUSION AND n-th OF REACTION The rate of diffusion is proportional to the difference 4 concentrations between the bulk of the fluid and at the interface. I[n tl steady state, the rates of diffusion and reaction are equal p= k(C-C,) = k,C} = ky(C-r/k,)” For integral values of n < 4, theoretically this polynomial always can ¥ solved for r in terms of C, although some questions may arise about the proy choice from among multiple solutions. When n = 1, kiko ky 42k Kika A quadratic equation for r also results when the surface rate equation is simple L-H type, as 68c ka (C-r/k,) Bm (EE) = ECCS) = GEIR P2.03.02. ENZYME KINETICS. MICHAELIS-MENTEN EQUATION The enzyme E and the reactant or substrate S are assumed to combine to form a complex ES that subsequently dissociates into product P and uncombined enzyme (Michaelis & Menten, Biochem Zeit 49 333, 1913) 1 S+E SES ESSe+P If equilibrium always exists, (3)(E) _ (5) UE (ES) | (es) ~ TES) ~ where (Ep) is the total of the free and combined enzyme and kK, is a disseciation constant. Solving for (ES), (&) (9) (S) (ES) = TRS) 7 KS The rate of formation of the product is ae _ KalE9)(S) ae 7 KAlES) = sy Several different linearized arrangements of this equation are in use for determination of the constants fron rate data. In the simplified notation, ac, HC ie four modes are, () ky¢ o) = Xq In(C/Cg) +0-Cy Integrated equation k aoi-2beh Lineweaver-Burk 1 1 Hanes , rei ie aw §=e- Fad P2.03.03. ENZYME KINETICS WITH REVERSIBLE DECOMPOSITION The postulated mechanism is S+edESSE+P where E is the concentration of the enzyme, S is that of the nutrient and P that of the product. The concentration of ES is assumed to attain constancy ales) at The material balance on the enzyme is (Ep) = (E) + (ES) Accordingly, = k,(E)(S) - (katk,) (ES) - k,(E)(P) » 0 69k, (Eq) (S) +k, (Ep) (P) kegtky*ky (S) +k (P- The net rate of formation of the product 1s (Es) p= GE) = kg (ES) ~ kq(E)(P) After substitution for (ES), kjk, (Eq) (S)-K%, (Ep) (P) gtk (5) 4k, (PY P2.03.04. CELL GROWTH RATE. MONOD EQUATION | The growth rate of cells {s taken proportional to the cell) concentration, x, and to an empirical form of the dependence on the) cencentration , p, of the nutrient. That empirical form was assumed by Monod (1942) to be the same as in the Michaelis-Menten model for enzyme kinetics. This makes the rate of cell growth, dx _ KP at = keep a) An additional assumption is that the change in cell concentration is proportional to the change in nutrient concentration, that 1s, dx es (2) Solving this for p and substituting into Eq (1), P= PolX-Xq)/ky (3) K1k5 (ksPo-m%yt® ae = Kies (KsPo-Xo w E> Eksp ee Integrating, . = B 1 aka(tote) = SU staeeny * axl (ar) were = EB anctaexy * ase (s) & = KaP9-Ko B = KgkstksPo%o The pioneers are Langmuir (JACS 40 2361, 1918) and Hinshelwood (Kinetics of Chemical Change, 1940). For a gas phase reaction, A + B » Products, catalyzed by a solid, the postulated mechanism consists of the following steps: 1, The reactants are first adsorbed on the surface where they subsequently react and the products are desorbed. 2. The rate of adsorption of A is proportional te its partial pressure and to the fraction, 8, of uncovered surface. 3. The rate of desorption of A is proportional to the fraction, 9, of the surface covered by A. 4. Adsorptive equilibrium is maintained 5. The rate of reaction between adsorbed species is proportional to their amounts on the surface. 8, = fraction of surface covered by A ®, = fraction of surface covered by B 708, = fraction of uncovered surface = 1-8,-0, The net rates of adsorption are Ty = KaPa®yka%, 9 0 Ty = KyPpy-k yo, 2 0 Substitute for 8 and rearrange to (cgPa7k-g)9_ + KyPa®p = KPa KpPpa + (kePp7 Ky) = KyPp The last two equations are solved for the surface coverages as, KPa re on k,/k, TK Pa*KiPp KyPa%v KyPo THK yPatKyPp 1 — T+K,PaKPp The rate of surface reaction is KyPydy, Ky = Ky/Ky K’PaPp (19K ,pstkePe) From measured rate data, the constants may be found with the linearized KO,0, = KK,KyPaPyOe = fora, y = Jbypy/7 = (14K,pytkyp,) Ae” 2.03.06. CHAIN POLYMERIZATION The process of chain growth of a polymer postulates a three step mechanism: 1. An initiator, I, generates a free radical R” 2. The free radical reacts repeatedly with monomer by a process called propagation. 3. The free radical eventually disappears by some reaction called termination. The stoichiometric equations are Initiation, x 19! aR ke Ro + M5? RM Propagation, . ke RMD + M3? RMS Teraination, k, BM, + RM 3° RoMay, OF RMatRMa The rates of formation of the free radicals R’ and M’ reach steady states. dR* a7 2k,(1) -k2(R") (M) oO GE = keg (R")(M) ~2k, (4)? = 0 1These equations are solved for R’ and M’ and substituted into the propagation equation. The rate of polymerization becomes aM . =e eye ye, p> Gem ROOD = GC") Thus the process of chain polymerization is first order with respect to the monomer and half order with respect to the content of initiator. Thermal decompositions of gaseous organic compounds are found to involve free radicals (Rice & Herzfeld, JACS 56 284, 1934). The process consists of an initiation step that forms free radicals, then propagation steps, and finally termination steps that destroy the free radicals. Three different kinds of termination steps will be examined The first step is the decomposition of t dissociation of a carbon-carbon bond = molecule into two radicals by « Ma’ Ri] +R}, Uinitiation) a The radical Rj, is not involved in the propagation but Rj participates in the following chain, 6 Rj + M3°R3 + RyH (propagation) (2) x RZ 3° Rp + (propagation) (3) In reaction (2), Rj abstracts a hydrogen from M and forms the radical R3. In reaction (3), R3 dissoclates at a carbon-carbon bond and regenerates the radical Rj. The sequence continues until one of the following termination steps occurs: ge R; + R) 4° Product (4a) Kan R, +R 5° Product (4b) R} +R; 3° Product (4e) (a) Termination mechanism (4a). Kinetics of 3.2 order The free radicals Rj and Rj are assumed to reach steady states, a(R) Ser = KOM) kg (MD (RED + Kg(RQ) ~ Hag) = 0 From which R, = [k7u, IM The rate of disappearance of M is _ al) “at x, KOM) + kp(R, JO) = (MD 1+ 22(R3)) 1 After substitution for Rj, 72ke Sikes The specific rates of the initiation and termination steps are small so unity in the bracket is negligible and the rate becomes _ aM) Be “at amy) = kefky 7k 4, (M) (p) Termination mechanism (4b). First order reaction. The steady state hypothesis is applied to the two free radicals = ky (M)-k2(M) (Rj )+k3 (RZ) = 0 Kp (M1) (Ry )-k3(R3)~kyy (RZ)? = 0 from which Ry = [ky7ey HF ky ky 0.8 Ri ie tag a Kan (My The rate of disappearance of M becomes, Kg Kikeo ka “Geo = G0 142089) = k, 00 [2+ + Neglecting 2 in the bracket, ay) ~ GE = balks ane? {c) Termination step (4c). Kinetics of first order The steady state equations for the free radicals are (Ry) mae = Ka (MO~K2 (Rj) (6) Hg (RZ) Kye (Ri (RZ) = 0 a(R )(M) ~ k9(R3)-kge (R; (RZ) = 0 By addition, K, 00) 2kye(Ri) Substitution into the previous equation gives 2 2kq (Ri)? = ky (RE) ~ kgky/Kg, = 0 Neglecting the middle term since both k, end Rj are small, The nate of reaction becones,gy Kp Koka ~ SSE OO OERD) = KONO ba which is of the first order. Consider the reaction, At3B » C*D, for which the postulated mechanisin 1s x ASB @! X+D ka « X4B e? Y4D Ky « eB ocd X and Y are unstable intermediates whose net rates of production are zero, Find the equation for the reaction of A da ~ Ge 7 KAAB ~ kpxD a = as + etd thay -kyID = 0 k,AB + k,YD 4 4 (2) KD 48 XB +K,YD *ksYB = 0 Kx Rpg ° Combining (2) and (3), (kD + K,B)X = k,AB +k! Olgas KsAB (ay K,BD &,D+K,B Substitute into Eq (1) and rearrange into the desired result... k2D+ksB ~ 3 Ky kgkgAB a (5) 2 “HegkgBD kg D' “The overall reaction, A+B+C+D + ABCD, is assumed to proceed by three second order reversible processes, * AsB ge! AB a) ka x ABH @° ABC (2) Ka x ° (3) ABC+D @° ABCD ke 4where AB and ABC represent intermediate products whose net rates of formation are zero. Derive the equation for the rate of formation of ABCD. For the intermediates, a(AB) _ SCAB) = (A) (B) -Ka(AB) -kg(AB)(C) +e,(ABC) = 0 a AOABE) 45(AB) (C) -Kq(ABC) ~Kg(ABC)(D) *Kg(ABCD) = 0 (14) The value of (AB) from (i) is substituted into (11) which is then solved for (ABC) as yk (A) (B) (C) + [kgkgegkg(C) ] (ABCD) (asc) = Kak tak (D) +k (CID) on For the net product, ACABED) ieg(ABC) (D) kg (ABCD) Gy) Substitution of (iii) into (iv) gives the desired result, aCABCD) _ Kikks(A)(B)(C)(D) ~ kak,k, (ABCD) a Kak ytkaks (D) thks (C(D w™ 2.03.10, REACTION A + 2B + C + 2D, WITH A TWO STEP SEQUENCE The reaction, A+2B 3 C+2D, proceeds according to the mechanism x A+Bel X+D a ka ks X+Be C+D @) Ky for which ax at = k,AB -kjXD and K,AB4K,CD Tepe @ Substitution of (3) into ga. - ~ Gh = kab - xD @ gives the desired result, (5) if reaction (2) is not reversible, 2 ky kg AB -4 > (6) 2.03.11, ACETALDEHYDE THERMAL DECOMPOSITION For the thermal decomposition of acetaldehyde, a chain reaction propagated by free radicals is postulated: x CHACHO 3* CH3 + CHO: Initiation a 758CH, + CH,CHO 5? cH, + cH,CO Propagation (2) CH,CO 2 ck; + CO Propagation (3) ack; 5* Cig Termination «@ Apply the steady state hypothesis to the free radicals CH; and CH;CO’, CH; . “ae. = Ky (CH,CHO) ~ ke, (CHyCHO) (CH3) + Kg(CHjCO”) -2k4(CH3)? = 0 (5) 4(CH,CO" ) . on Ge = Ke(CH CHO) (CH3) - ky(CR{CO") = 0 (6) from which ky (CHJCHO) = 2k,(CH3)7 m The rate of reaction of acetaldehyde becomes (CH,CKO) ~—FE = Ki (CHCHO) + kp (CH CHO) (CH) Kk. = ky (CHCHO) + | (cHycHo)®* (8) 4 The first term of (8) is the initiation rate and is presumably small comparison with propagation. Accordingly, d(CHCHO) we - SP = k (cH CHO) 9) Also, aUCH,) GE = Ke(CH3) (CHACHO) = kel ky72Ky (HCHO)? ao) 2.03.12. PYROLYSIS OF ETHYL NITRATE, DATA FROM A CSTR A chain reaction was proposed for the pyrolysis of ethyl nitrate Houser & Lee ( J Phys Chem 71 3422, 1967): CoflgNO, St CyHi,0" + NO, Initiation a Calis” 5? chy +cH,0 Propagation (2) CHS + CAHZONO, S°CHWO, +CgHO Propagation @) 2CH,0" 54 CHACHO + CghgOH Termination (a) The rate of reaction, mols/(ksec)(m?), was measured in a CSIR in terms of concentration, mols/m?, with the results, C 0.0975 0.07590 0.0713 0.2714 0.2436 ro 13.4 12.2 12.1 23.0 20.9 Find a rate equation consistent with the proposed mechanism and check it against the data. Rewrite the reactions in simplified notation A = CoHgONO, B= C,H 76c = CH For the free radicals, ae 2 BB ee arkBrk ACHE = 0 SE = kB-kgtc = 0 From which B= fare IX x, |k c= Ref alka fe For the ethyl nitrate, aa 1 GE 7 HA HAC = AC I Kallace Both k, and ky are small in comparison with k, so the second term dominates. Accordingly, - ga at The log-log plot of the data has the equation In r, = 3.754 + 0.4858 ln A or 15 Eqn 4 ye(orby) 2=0998050771 ry = 42.69 ao f068 on 57558172 which confirms the half order closely + Aes Inra P2.03.13. DECOMPOSITION OF ETHANE The postulated mechanism for the cracking of ethane involves three free x radicals, H, CHy and C,Hs, with the reactions,CjH, + 2CHy k. Clly + CH, 9” CHy + Colts « Coll 2° CoHyt H kg Hot Cy 3° Hy + Cally x H+ Cy, 3° CoH 7The steady state equations for the free radicals are 4 (CH) at = 2k, (CoH) kp (CH) (CoHg) = 0 @ ) = key (CHg) (Cyllg) “Kg (Coty) kg (H) (Calg “Kg (HD (Cols) = 0 (2) a(H) _ Nae 7 KalCally) ky (H) (Calg) “Kg (HD (CoH) = 0 (3) Addition of (1), (2) and (3) followed by rearrangement gives, (C,H) OD = RCH « Insertion of this into (3) gives, Kyks (Cols)? - kykg (Cyl) (Calis) - kyky(Czt,)® = 0 (5) Since k, and ks are both small, the middle term can be ignored, so that (Cats) (6) This makes the rate of production of ethylene, kkk, a (CoHy) 7 which is a first order reaction. d(C) a = kg (Cas) = 2.03.14. NITROGEN PENTOXIDE DECOMPOSITION For the decomposition of N,0; this mechanism is postulated, x NOs @' NO, + NOg Initiation 2 « No, + NO, 5? No +0, + NO, Propagation . NO + NO, 34 2NO, Yermination Assume that NO and NO, attain steady states an GINO) — 5(NOg) (NOg) ~ K4(NO) (Ng) = 0 (WO) = Cey/eg) (NO) aw (NO) Ferm = Ki (NgO5)=Kea(NOg) (NO) (NO) (103)-Kg (NO) (NO3) = 0 ky (305) (803) = ea TONOT (2) For the decomposition of the pentoxide, (N05) FEO = ky (Me0g) - Kp(NO,) (NOS) kik, 2kiky = Ws) Uy} = - 52 (H,05) (3) STUNT a2 ka42k, * 2s Also, it turns out that 78a(NO,) _ 3kyKy (0s) at Krk 2.03.15. HYDROGEN AND BROMINE REACTION ‘A proposed mechanism is the following: ke Br, 3° 2Br Initiation A Br +H, 3° HBr + H Propagation ke H+ Bry S° HBr + Br Propagation x, H+ HBr 9" H+ Br Inhibition x Br + Br 9° Bry Termination The rate of formation of HBr is HB SOIBP © ey ((Br) (Hy) Hee (H) (Brg) ky (H) (HBr) a For the free radicals (H) and (Br), d(H) _ SO = Kp(Br) (Ha) +k, (H) (Brg)-k, (HBr) = 0 (2) = 2k, (Brg)-k, (Br) (Hy) te, (H) (Bra )+kg ((H) (HBr )=2k, (Br)? = 0 @) Addition of (2) and (3) gives (Br) = (k7e)° (Brg) (4) Substitution of (4) into (2) results in ky lka/kg)? Ft) K, (Br, 34k, (HBr) Final substitutions of (4) and (5) into (1) gives Bodenstein's formula ap (s) adiBr) _ 2kp(k,/k_)°°S(Ba) (Bra)? 5 dt” —I+Tk(HBr)7k,(Brg)T © 2k yk Oye)?" (ity) (Br) * K, (Brg) +k, (HBr m One postulated m Cl, @ 2c1 cl + CO COCl hanism consists of these reactions. Po COC] + Cl, =" COCl, + C1 The first two reactions are taken to be at equilibriun. cu? | rz) {COC1) Tooy(cn) 2 19From which the intermediates are (oocn) = K?%k, (co) (c1,)°* (cr) = KP (cig)? * The rate of formation of phosgene by the third reaction becomes d(COC1,) Fe = Ka(COCLI (Chg) = Ky lk” “Ke (C0) (C1,)*"* (b) An alternative mechanism is Cl, © 2C1 Cl'+ Cl, # Cl, Cl, + CO 4 COCl, + CL Assuming the first two reactions to be at equilibrium, (c1)*/(Cl) = K, | (C1g)/(C1) (Clg) = Ky From which (Clg) = Kq'5k,(c1,)'§ Then d(COCl2) a = (C1) (CO) = KRY KA (C0) (C1) '"* 2.03.17. PHOTOCHEMICAL OXIDATION OF PHOSGENE For the reaction 2COCL, + O, » 200, + 2C1z it was shown (Rollefson & Montgomery, JACS 55 142, 4025 rate equation is 1933) that a suitable a(Co,) kIp(COC13) . “at * THR Cig) Wz) © where Ip is the intensity of the incident radiation. The experimental rate equation is accounted for by the following mechanism: cocl, + hv 4 cocl+ c1 coci+ 0, 3 co, + C10 cocl, + Clo 3.co, + Cla + C1 coci+ Cl, 3 cori, + ch cl+ crm Sci,+M It was assumed that the radicals C10 and COC1 attain steady state. BECO) 16 (COCLg)-Kp(COCL) (0g)-ky(COCL)(C1,) = 0 k,Ig(COC1,) (COC) = GTO a (CIgT © HEI). — (04) (COCL) ~ky(COC1,)(C10} = 0 k2(0,}(COC1) (cio) = 2 Ky(COCIS) o The rate of formation of CO, is 804(C0,) gE = Kq(0g) (COC1) +k3(COC12) (C10) = 2k2(0,) (COCL) __ 2kyI9(9,) (COC1,) ( © “¥3 (02), (C14) 0 _ 27g) To(COC1g) > Tek 7kpICI 710, 6) Lines (1) and (5) are of the same form 2.03.18. DECOMPOSITION OF OZONE CATALYZED BY CHLORINE The catalytic decomposition of ozone by chlorine is believed to occur by the following chain reactions, Cl, + 03 4 Clo + C10, initiation a C10, + 05 3 clo, + 0, propagation (2) C10, + 0; 3 C10, + 2 05 propagation (3) 10; + C10, $ Clz + 3 0, termination () The chain carriers C10, and C10, are assumed to attain steady states. The rate of disappearance of ozone is (05) . ~ SHBe = ky (C1g) (Og) ~ ky (C2OQ) (03) + ky (CLO) (0) (5) For the chain carriers, a(Cl0,) ae = Ky (Cg) (g)-Ke(C10,) (03)#k (C105) (02) = 0 (6) (C103) 2 Aye = Ky(C10,) (Og) (C105) (03) Ky (C105) = 0 (ca) Addition of (6) and (7) followed by rearrangement gives, (€105) = fiq7kg (C1,)'77(03)'* «a) Substitution into (7) then gives 12 Ka [ky Ky (cio) Elk (C2) (03) + (C2) 09) Final substitution of (8) and (9) into (5) gives, (05) k y -oe. aft (Cig)*/7(05)°7 * 2k, (CL) (05) (10) Since the chains are long compared with the initiation step, the second term of (10) can be dropped and the rate becomes (03) et . 32 = k(Cl,)*77 (05) a) 2.03.19. OZONE DECOMPOSITION The reaction, 20, » 3 03, is believed to have the following mechanism, 0,+4$0,+0+M eo) 2 3 0+0,320, @) 81where M is any molecule. Find the rate of decomposition of the ozone, with either of the two assumptions of parts (a) and (b) (a) Assume that (0) attains steady state 810). =, (05) (49-Kg(01(04) (H ~K9(0) (04) = 0 (3) K, (05) (H) (©) = Sor aETET @ The ozone rate becones, 4(0) Fee = -F(O4) (8) #9 (02) (0) (HK (0) (03) ky (03) (4) iy-kg¢ 1(05)4) + Gere yay sry tOyp lkaCOa) Ik (04)] _ -2. ky (05) s = ey) Flaw ) (b) Assume that reaction (1) is in equilibrium. Then, K,(03)(M) _ K, (05) © = “ow ~ To. 6) The ozone rate becomes, alo. gk, (03) . gE = Ka (03) (0) = SF ae a When the second part of the denominator of Eq (5) is relatively small, (5) ang (7) will be of the same form 2.03.20. DECOMPOSITION OF DIETHYL ETHE! Thermal decomposition of diethyl cther is postulated by Hinshelwood (Kinetics of Chemical Change, 1941) to proceed by the chain mechanism, CoHgOCgHg 4 CH, + CH,OCH, CHg + CaH,0CH, 3 CH, + CHOC RH, CH,OC,H, 3 CH, + CHACHO CH, + CH,OC,H, 4 end of chain CHOC He 3 CHOC Hg In the steady state the derivatives of the free radicals B and C are zero. aB Ge = KA -kQAB 4k gC -k,BC = 0 a ac GET KA + KaAB - KC ~ BC (2) On combining (1) and (2), Kaks ‘ mk, (a) For the rate of deconposition of A, B 82aa kk. ~ SET KA + koAB = (ey + kp =e (5) Since k, ls small in comparison with kz and k, and of the same order of magnitude as ky, the first term in parentheses of (5) can be neglected with the final result, A(C HOC HS) | kyk, (CaHg0C Hs) (6) at Ke 2.03.21, CHLORINATION OF n=HEPTANE The reaction between chlorine and n-heptane involves the free radicals Cl and CH. as Follow: a,s20 Cl + Cris 3 CH, + HCL Cys + Clo 3 CyMysCl + CL CH,s 4 end of chain Find the rate of the reaction, Cl + Cys 2 CpHysCl + BCA The free radicals attain steady states. HEL 2 Hy (Chy)Kg(CyHyg (CL) + Ky(CHhg)(Clg) = 0) d(C His) “ors Kg (CyHyg) (CL) Kg (C7Hys) (Cly)-kg(CpHys) = 0 (2) Fron (1) and (2), 2k (CoHys) = ee (ci) (3) and the rate of chlorination becones, a(cl,) = yeh = kr (Cla) +9 (C7thg) (Cla) «@ 2k = (LU + Fi) s) 3.2: COMPOSITION OF NITROUS OXIDE. The decomposition of nitrous oxide is believed to proceed with the intermediate generation of atomic oxygen according to the reactions 4 NO $N, +0 n,0 +0 3N, + 02 The atomic oxygen attains a steady state. 4(0) at from which = ky (NZ0) ~ kQ (Nz) (0) - k3(N,0)(0) = 0 _ 0803 () = Sark, ON 83For the nitrous oxide, d(N30) = ae = ky, (N20) — k2(NQ)(O) +kg(N20) (0) = y [3 (NO) “Kp (Nz) (NO) = k, (N20) + ae TN) #k3 (NZ 2 kyky(NZ0)* * KIN.) +k, (QO) P2.03.23. PHOSPHOROUS ACID In the presence of an oxidant (Y), hypophosphorous acid (A) is transformed into phosphorous acid (B). The kinetics of the reaction has these features: (1) at low concentration of oxidant, ry = k(¥)(A) (2) at high concentration of oxidant, r, = k(H")(A) To explain this behavior, it is postulated that with hydrogen as catalyst, H,PO, is transformed into an active form, X. This intermediate form then reacts with the oxidant to give H,P0;. Show that this scheme explains the observed kinetics. (Levenspiel, 1972) HPO, (A) + HT $x + HT x + ¥ 3 H,PO, (B) The concentration of the intermediate attains steady state. 300 = ky (A) 08) =k, 00 (HY) -k 300 (4) = 0 Ky (A) (HO) -_S a , (HT) +3 (Y) The rate of formation of phosphorous acid becomes (HPO) Kk (A) (HY) (Y) ry = Ge = OO) = ES (2 ka (H") +k, (Y) At low concentrations of the oxidant Y, the second term of the denominator of (2) becomes negligible and ry = K(Y)(A) = k(oxidant) (hypophosphorous acid) At high concentrations of the oxidant, the first term in the denominator becomes negligible and ry = kOH)(A) = k (hydrogen ion} (hypophosphorous acid) both in accordance with observations. 2.03.24. ACETONE DECOMPOSITION The following mmechanism has been proposed for the decomposition of acetone by Rice & Herzfeld: cH,cocH, 4 cH} + cHco” 1 2 ow cH,co’ 3 cH + co ‘ 3 , CH + CHCOCH, 3 CH,COCH, + CH, 84cH,cocu; 4 cH + cH,Co CHS + CHCOCH, 3 C,B.COCH, Let A = CH,COCH,, B = CH, C = CH,CO’, F = CH,COCH}. Assume that the concentrations of the free radicals B, C and F reach steady state. The rate equations are ae at ac at oF at Adding these equations, 2k,A - 2kgBF = 0 KA 1 F kB (4) Fron (3) alone, “tt (6) Kytks)B From (4) and (5), KegkgB® ~ KikgB ~ kk, = 0 (6) Since both k, and kg are small, neglect the middle term of (6) and solve for Kiky B= lee 7 Substitute into da _ ACCHACOCHS) . Kyky SE ge =O tHBIA = Cet] EA = cy fke + Ligegka’eg) A> [i kgky/ke (CHyCOCH,) on egain neglecting a relatively small term. Thus the decomposition of acetone is a first order process a) a K,A + k,C - kjAB +k,F - kgBF = kA ~ k,C = 0 (2) = KgAB - K,F - X,BF = 0 (3) F a 2.03.25. THERMAL CRACKING OF PROPANE The thermal cracking of propane is practiced industrially for the primary purpose of making ethylene and propylene, but other reactions also occur. A scheme worked out by Sundaram & Froment (Chem Eng Sci 32 601, 1977) consists of the nine reactions of the table. Equilibrium constants were deduced from thermodynamic data and the other constants by nonlinear regression from the extensive data on this topic in the literature and laboratory. Resction Rate Rate equation 1 GH, ——> GH + CH, n= hiCols 2 CHs === GHe +H, no h(Com ~ SepSu 3 Gilly + CaHe HE FM = bsCosn Conn +4 ICH, ——> 30H, r= Cen, 853 2C\H, ——> 0.5, +30H, 6 CB === GH + CH, 7 CyHg + Ce ——+ Cally + CHy 8 GH, == GH +H, 9 GHe + GH, ——+ Cally 2.03.26. A KINETIC REFORMING MODEL The purpose of catalytic reforming of gasoline 1s to improve its octane rating, largely by increasing its aromatic content. The reactions involve a large number of participants. In the development of the Mobil Kinetic Reforming Model (Ramage et al, in Wei (Editor), Advances in Chemical Engineering 13 193-260, 1987), some 300 individual species were identified These were lumped Into a much smaller number of pseudo components identified by carbon number and chemical nature. The lumps vary with the age of the catalyst. The table shows the 13 lumps adopted for the “start of kinetic cycle". The kinetic characteristics of these lumps are proprietary data. KINPTR Stant-or-Cvctt Kiweric Lunes (06%) Carbon Sixearbon-ring Five-carbonsting number naphihenes (Ny) raphtheaes (N53) Paraffins (P) Aromatics (A) Cav Cyr cyelohexanes (I) Cae eyelopentanes (2) Cy. parafins (3) Cy. aromatics (4) Cy Methyleydobesane (5) Cyclopentanes (6) Heplanes (7) Tolvene (8) Ce Cyctohexane (9) Micthyleyclopentane (10) Hexanes (11) Benzene (12) Ce 2.04, 01. ALKYLATION OF ISOPROPYLBENZENE Isopropylbenzene (A) is alkylated with propylene (P) using HF catalyst. The mono (B), di (C), tri (D) and tetra (E) derivatives are formed. Relative specific rates are given by Rodiguin & Rodiguina (Consecutive Chemical Reactions, 1964) for the case of a large excess of propylene which makes the reactions pseudo first order. The relative specific rates used here are k, = 1.0, ky = 0.5, ky = 0.3 and ky 0.2. The system of linear differential equations can be solved by Laplace transform but the result is quite cumbersome. The nonlinear system with limited propylene is not solvable analytically. Here, both linear and nonlinear systems are solved numerically with Constantinides ODE software. The nonlinear set is solved with Py = 4A = 400, just enough to convert Ay = 100 to the tetra derivative. The differential equations are Ty = KAP (ky A-k,B)P (cgB-k3C)P (cgC-k DP X,DP 100 0 = Cy = Dy = Ey = 0 P+ 400 -B ~ 2C - 3D ~ 4E The tables shown how the equations are entered into the program. For the linear case, P is incorporated in the specific rates as constants. Re 86‘The solutions of both cases are obtained equally readily by the program. The graphs show behaviors to be similar. The true time behaviors are not known because only relative values of the specific rates have been used. Linear equations, g(t) = -y() (2) = y(t) - 0.5*y(2) g(3) = 0.5"y(2)-0.3y*y(3) (4) = 0.3*y[3)-0.2%yf4) a(S) = 0.2%y(4) Wonlinear equations, g(t )=-y(1)* (400-y(2)-2*y(3)-34y (4)-44y(5)) g(2)=y(1)-0.5*y(2)}*(400-y(2)-24y(3)~3*y(4)-a*y(5)) g(3)=(0. Sty (2)-0. 3*y(3) )* (400-y(2)-24y(3)~3Fy (4)-4*y(5)) g(4)=(0,3*y(3)-0.2%y(4))* (400~y(2)-2*y(3)-3¥y (4) -4"y(5)) g(5)=0.2*y(4)* (400-y(2)-24y (3)-3¥y(4)-4*y(5)) 180 Nonlinear 8 +02 .84 88GB Time Time 2.04.02. DIFFUSION AND SOLID CATALYSIS. ‘A reaction, Ap # Products, has the rate equation 1.50, r= 1.28(C-C,) = (1+0.3{Cy40. 10,)? where C, is the interfacial concentration. This is a case of diffusion to the surface followed by reaction with dissociation on the surface. Fliminating C., 1.8(C-0.8r) (140. 1C-0.8F 49.1(c-0.8r) 12 The available software for numerical integration of first order ODEs is applicable only when dC/dt {s available explicitly. Here a "root solver" is used to find the relation between C and r. Then the relation to t is obtained by integration with the trapezoidal rule, = soo SC tele 87The work is tabulated. 0 o.114 0.232 0.355 0.484 0.619 0.760 0.910 1,069 1.233 1.422 1.621 1.840 2.084 2.360 1.1189, 1.1601 4.2054 1.2566 1.3141 1.3795 1.4541 1.5406 1.6412 1.7603 1.9033 2.0777 2.2952 2.5747 2.9864! 3..4650]2. 680 4,2391/3.065 5.5218 /3.553 8.0710] 4.233 15.70 |5.422 EMOAUOUH OHNE AHO C9 99000C OM EAE HEED 2.04.03. FILLING A BATCH REACTOR A vessel is being filled with a ceacting solution. The material balance is derived as Eq 2.44 of Section 2.6.1. In the present application it is ac _ 2c dt t Although this ODE 1s quite innocent looking, it must be solved numerically. The graphs are of solutions with k = 1 and k = 5. ~ cz a Concentration: P2.04.04. A HEATED STIRRED REACTOR Heat and material balances of a batch reactor are derived in Section 2.6.2. In the present instance, the differential heat balance is Heat of reaction + Heat tranfer = Sensible heat gain or 9000 dx + UA(T-S00)dt = 450 dT @ The rate equation is 83ax. oe? = Ore) (2) and the specific rate is k = exp(18 - 11000/T) (3) Substitute dx from Eq (2) into Eq (1) and rearrange, aT _ 9000 k (1-x)* + UA(T-s00) at 350 o substitute for k in terms of T and solve ODEs (2) and (4) simultaneously. The graphs show solutions with UA = -5, 0 and +5. ‘ 302.3 aes, j0.046 2 ease z eae i i i 55 i wa | see 2 ze oa ae ae ee P2.08.05. MAXIMUM MIXEDNESS A reaction of order 1.5 is conducted under such flow conditions that its residence time distribution is like that of a three stage CSTR. Under maximum nixedness conditions the rate equation is af _ 5 pts . a2 At) 13.502 A(t.) = ———*_, 143t, +4. 5t2 Mo) = 3 2 £45 - 3(1-£,) =0 fq = 0.650 The equation is to be integrated, The endpoint of the integration Is f = fee at t, > 0. The starting point is £, = 0.650 and any value of t, above 2 or so The graph shows the result to be insensitive above this value of t,. The exit value is f, +/Cq = 0.330 89FC/C, + n 2.04.06. DEACTIVATING CATALYST. The activity of a cracking catalyst declines with time on stream. A case of gas oil cracking has the rate equation, ac 8 8.5C de (a6. 54) (140,020) with inlet concentration Cg = 0.2. Find C as a functlon of t with (a) deactivating catalyst; (b) with stable catalyst of the initial specific rate. The variables of the differential equation are separable, but to find © as a function of t requires a numerical quadrature and application of “root solver" many times. A direct solution by ODE program is simpler. eactivating 2.04.07, PROCESS WITH A POROUS CATALYST. ‘A process with a porous catalyst has the rate equation ac L - GE = 070C 1.8 The Thiele modulus is ¢ = sale ana the effectiveness is 9 = 2:0387+0.31734+0.000437¢" 140,41729+0. 13997 POLYMATH ODE is used for the integration in preference to Constantinides ODE because it allows printout of algebraic as well as differential variables. In the tabulation, x= C, £ = ¢ and e = 7. 901.88 x £ € 2, ae 16.971 3. T3aL Lisas 15,867 1458 1.48 1.5291 14.839 5.1545 13383 13.881 51646 Ant (2.998 8.1751 1.0 i262 12156 #1363 #8995 11,381 8.1998 5.7889 18,859 #2184 ne 8.6925, 5.9858 #2283 Hef) 9.3508 2068 EST 87751 DSC ua Lae ie 6an tae hae t REACTION WITH DISPERSION. The dispersion model of a reaction has the equation ae of sf ——= Pel — + 1 az? a2 Caso. al)? Pe=5 ae ~ azo at z= 0, 1 = (f -f'/Pelg, fo = unknown In order to use an ODE program, the second order equation is transformed into a pair of first order ones. af Ef af! Lope y _7.5E ett caso. aff? The shooting procedure is applied to solving this boundary value problem: (i) Start at z = 1 where f) = 0 (ii) Assume a trial value of f; (iii) Integrate backwards to z there 1s satisfied, (f-£'/5). 21 The tabulation shows three trials. The graph is of the final trial. (E-£" 5], Q, and check if the boundary condition +. 0.40 |0.8268 0,419|0.8615 -0.6971]1.0002 check | -0.7339] 4.0645 gt2.04.09. PRIOR ELIMINATION OF For the pair of reactions a+Bda2c, acd these conditions are given: ky = 0.1, ky = 0.05 Ao = 0.9, By = 0.3, Co = Dy = 0 The concentration profiles are to be found. The material balances are, C = 3(By-B) -(Ag-A) = A-SB am D = (Ag~A)~(Bg-B} = 0.6+B-A (2) The rate equations are, | # = -K,AB - k,AC = -k, AB -k,A(A-3B) = 0.05A(B~A) (3) | aB _ yap e | Se = KsAB = 0.148 4) aC. 0.05 | SE = A(0.2B-0.08¢) (s) | ap SE = 0-05aC (6) | Method A procedure that requires solving only one differential equation at a time applies when t is first eliminated between Eqs (3) and (4). _ dé KA ky-3kz O.5A =x, = O:5A _ 9, 7 a kB 7 Bp OS m This is a linear equation whose integrating factor is 1/{B and whose solution | is a= Bry O58 ey ope BC - ID (a) iB 48 | Substitute this result into Eq (4). aa 1.5) Ao Se = 0.1 Sip + 2 - fap 9) | Bo The variables are separable, but analytical integration 1s not possible. A | mumerical Integration will provide the solution B= 4(t) This can be substituted into Eq (3), but analytical integrations of the differential equations stop at this point Method (b). Numerical Integration of the four equations, (3) to (6) is accomplished with ODE, either Constantinides or POLYMATH. Alternately, the material balances (1) and (2) and only the two differential equations (3) and (4) can be solved together. This procedure is better carried out with POLYMATK ODE 92Concentration a 20 48 | 68 86 4e0 2.04.10. THE SEQUENCE A The rate equa aa SRA, SB = igh ~ KB = K,Agexp (kt) ~ These were integrated analytically in problem P2.02.17. Here they are done nunerically with program ODE. The second equation is rewritten as d(B/Ap) a The plots are for several combinations of the constants k, and kjAg. The intermediate participant, B, reaches the peak values that are typical of many sequential reactions. = kyexp(-kyt) - kgAg(B/Ag)® 2 1 3 3 -°\wa, 13 wa, 7 7 6 BA 6 VA 5 2 ‘ho 3 Kaho 4 1 4 1 3 2 3 2 “2 1 3 “a 3 e 3 et 2 2 4 s “9° x @, 3a 4 5 93CHAPTER 3 TREATMENT OF EXPERIMENTAL DATA THEORY Kinds of laboratory reactors 94 Chemical composition 95 Power law rate equations 95 one The integrated form of r = kC™ Method using the differential equation, -dC/dt = kc™ Half time data CSTR data Integrated form of -dc,/dt = xcac® The differential form of -dc,vat = Kc&o® The reversible rate equation 4, Rate equations depending on multiple mechanisms 97 1. Solid catalysis and enzyme catalysis 2. Multiple reactions 3. Mixtures of hydrocarbons 5. Pressure data 99 6. Other properties related to composition 100 7. Temperature variation 100 8. Homogeneous catalysis 101 9. CSIR data. Liquid or gas phase 101 10. Plug flow reactors. Laminar flow 102 Figures 102 SOW PON PROBLEMS Units 103 Data of chemical composition 106 Pressure changes 145 Variables related to composition 164 Half life and initial rate data 177 Temperature variation. Activation energy 187 Homogeneous catalysis 202 Enzyme and solid catalysis 210 . Flow reactor data 222 10. CSTR data 234 11. Complex reactions 238 wOrAngone Data of the behavior of chemical reactions are obtained from laboratory units designed for or adapted to the purpose, or from pilot plant or commercial units. The larger units have the advantages of more instrumentation and controls but have less flexibility. Fundamentally what is determined is the time dependence of composition or pressure, or some measurement that can be related to these properties, and of the temperature. 3 KINDS OF LABORATORY REACTORS Various kinds of laboratory reactors differ in some important respects, sone definitely better than others. The criteria include: 1. Equipment cost 2. Ease of operation 3. Ease of data analysis. 4. 5. Accuracy Versatility 946. Temperature uniformity and control 7. Suitability for mixed phases In terms of cost and versatility the batch reactor is the unit of choice. One disadvantage is the need for frequent sampling or monitoring of the performance, although instrumentation can be provided at moderate cost nowadays. The residence time can be varied over a wide range and many different reactions can be handied at different times. The quality of mixing and heat transfer may not be easy to relate to those in an eventual commercial unit. CSTRs and other devices that require flow control are more expensive and troublesome to operate. Particularly in the steady state condition, however, their great merits are isothermicity and the fact that their mathematical representation is algebraic, not involving differential equations, thus making data analysis easier. Tubular flow units, like the CSTR, usually are operated at steady state. It is not always easy to measure the temperature profile accurately. In some high temperature operations, the coil is immersed in a fluidized sand bed or lead bath so there is fairly good temperature control. Sometimes it is felt desirable to do the laboratory work in a tubular unit if the commercial unit js to be of that type, but rate data from any kind of equipment are adaptable to the design of PFR. Reactions between phases -- gas-liquid, liquid-liquid or fluld-solid — is carried out in CSTR-like devices. With granular solids such as catalysts or immobilized enzymes, the preferred laboratory equipment nowadays is a rotating basket or fixed basket through which the fluid is recirculated continuously, with net input and output to the chamber. Laboratory operation of equipment with a fixed bed of granules is not. highly satisfactory because of difficulty of temperature control and measurement in both radial and axial directions. A short packed bed with extensive recycle, however, can achieve substantially isothermal behavior and neasurable differential conversion. Reactions between liquids and gases of low solubility is conducted in stirred vessels. The liquid 1s charged first and the gas is fed continuously at the rate of solution or reaction, sometimes with internal recirculation in larger units. Miscible liquid reactions may be conducted similarly in order to moderate undesirable temperature play. 3.2. CHEMICAL COMPOSITION Most analyses of kinetic data have the object of identifying the constants of a rate equation based on the law of mass action and possibly sone mass transfer relation.. The law of mass action is expressed in terms of concentrations of the participants, so ultimately the chemical composition must be known as a function of time. In the laboratory the chemical composition is determined by some instrument that is suitably calibrated to provide the needed information. Titration, refractive index, density, chromatography, spectrometry, polarimetry, conductimetry, absorbance, magnetic resonance -- all of these are used at one time or another to measure chemical conposition. In some cases, the calibration to chemical composition is linear with the reading. 3.3 POWER LAW RATE EQUATIONS Three of the more frequently occurring examples of power law rate equations are 95ct (3.1) ” aE ra = Kc&ch (3.2) ra = k,08C8 - kgctc8 =k, (cc - ched x.) (3.3) By stoichiometric balances all concentrations can be expressed in terms of C. For the evaluation of the constants from measurements of data of (C,, t), the three equations require somewhat different techniques. Some of the methods are summarized on the graphs of Figure 3.1. THE INTEGRATED FORM OF r = kc 1) asl (3.4) i zn (Cyc) past (3.5) By one procedure, values of a are chosen until one is found that makes all calculated values of k substantially the same, or that makes a plot of t against 1/0" or against In C a linear one (see Figure 3.1}. kc* 3.3.2. METHOD USING THE DIFFERENTIAL EQUATION, -dC/dt The data of (C, t) are fitted by a polynomial or other algebraic equation and differentiated to obtain the derivative. The constants then are found from a linear plot of In r= Ink + @ In C. Figure 3.1 shows this plot also. The time by which half the reactant has been converted is called the half time, ty,2. The equation ts particularly simple: kty2 = in2 wel ae (3.6) ot (e-1)C5) When several sets of (Co, t/2) are known, values of a are tried until one Is found that makes all k values substantially the same. Alternatively, the constants may be found from a linearized plot, at In tye = In Geayg + (1a) In Cy (3.7) Such a plot appears in Figure 3.1 3.3.4. CSTR DATA The steady state material balance of a CSTR with uniform volumetric flow rate is (3.8) (3.9) 96or in linearized form, Inr,=Ink+@inc, +B InG (3.10) The constants can be found by multilinear regression or by solving sets of three suitably spaced data. When only one exponent is involved, a linear plot is made, as in Figure 3.1. 3.3.5. INTEGRATED FORM OF -dC,at = xc®c® By stoichiometry the equation is converted, for example, into ac, ~ FE = KC Cor Cyotea® Gn) After values of « and @ are assumed, this equation can be integrated either analytically or numerically over the time ranges of the data. If the values of the k's are substantially constant, the correct choices of a and B had been nade. It is usual in this method to try omly integral or half integral values of the exponents, starting with the assumption that the rate equation conforms to the stoichiometry, xc? 3.9.6. THE DIFFERENTIAL FORM OF -dC,/dt When the rate data come fron a CSTR, the analysis was indicated in section 3.3.4. Other data of (C,, t) can be fitted by an algebraic equation and differentiated to obtain the derivative. Then the analysis is continued by Equation 3.10 3.3.7. THE REVERSIBLE RATE EQUATION The reversible rate equation, Equation 3.3, is easier to handle when the equilibrium constant is known. Then ry = k,(08C8 - Bch Ke) (3.12) Method (2). The burden of finding the five or six constants can be placed on a computer program of nonlinear regression, At the start, that ptocedure requires estimates of all the parameters. Those may be suggested by the stolchionetry of the reaction and by trial. Method (b). The equation may be integrated following trial values of the exponents. The correct choices were made when the specific rate k, is substantially the same for all tines Method (c). A portion of the problem can be solved with Initial rate data. Thus, Tq = kyC%oCBy (3.13) with subsequent rate the data, the equation to be analyzed becomes y = tr = K,C%C8) = ~K,c%c8 (3.14) vbich is handled asin Section 3.3.5 or 3.3.6. Problem P3.11.13 deals with a reversible reaction in this way 3.4. RATE EQUATIONS DEPENDING ON MULTIPLE MECHANISMS. Some examples of processes whose rate equations depend on rates of subsidiary processes appear in Section P2.3. In such cases, specific rates and exponents may appear in all sorts of places. Non linear regression Is in principle always applicable, but that procedure sometimes is harassed by convergence problems and does not always appeal to engineers who do not like black boxes. A fairly general technique is to arrange the differential equation or its integral into a form that can be handled by linear plotting or 97multilinear regression. As a last resort, a number of equations at selected data points equal to the number of constants can be set up and solved simultaneously, although the solution of sets of nonlinear equations also presents problems. Particular equations, of course, may suggest particular solutions. 3.4.1. SOLID CATALYSIS AND ENZYME CATALYSIS The mechanism of solid catalysis involves processes of diffusion, formation of loose combinations with the solid and reactions of those combinations. Reactions with enzymes also involve intermediate, temporary combinations with the enzymes. The rate equations that may proposed in particular cases depends on what are believed to be controlling mechanisms. | Many such eqautions are considered in Chapter 6. Here only one of the simpler forms will be examined for evaluation of the parameters, namely, dp, ky (P,Py"PePa/Ke) n= - Gee i (3.15) (CitkapatkpPptkcePetkaPa) The data are of the rate and all the corresponding partial pressures. The rate may have been obtained in a CSTR or by differentiation of (p,, t) data correlated by an algebraic equation. The obvious linearization when the equilibrium constant is known is PaPp~PePa/Ke. PaPo PePalte 12 _ (tepytkypetkepetkapa)/Jig (3.16) The constants are found by multilinear regression or by solving an appropriate _ number of linear eqautions. The constants of the simpler equatlon, ys 2 k, Pe (3.17) (+k,p) are found by linear plotting of pr = 1/fky + (ko/Jkp)p (3.18) MULTIPLE REACTIONS There are two main kinds of multiple reactions: (a) Those involving short lived intermediates such as free radicals known to exist or invented to account for a particular form of rate equation that is tested against data. Several examples are cited in Section P2.3. Catalysts also are believed to form transient compounds. (b) Those involving known species engaged in a variety of simultaneous and consecutive processes. Some examples are cited in Section P3.3. So many kinds of rate equations can arise that the only general solution method is nonlinear regression, although simpler techniques may apply in particular cases. Reliance must be placed on ingenuity. For the case of problem P3,03.08, the equation is 3.4 3 k, AB - a - a 5 (3.19) K,B*+k,BD+k .D' If the exponents are accepted the k’s can be found after linearization, but there is no simple approach to verifying the exponents. MIXTURES OF HYDROCARBONS. Industrial hydrocarbon reactions are a complex between a variety of 98feed compositions and a variety of products. Compounds that have been formed go on to form other compounds, and so on. Dozens of reactions may need to be taken account of. Sometimes the approximation of a network of first order and pseudo first order reactions is made, for which the mathematical foundation has been largely laid. As a ‘different example, a model for the cracking of propane is cited in problem P2.03.25 that consists of nine first and second order reactions. When a very large number of reactants occurs, as in the treatment of petroleum fractions with a virtually continuous spectrum of boiling points, the problem is made more tractable by lumping the composition. The lumps are nade up of pseudo components with limited boiling ranges and of partcular chemical types such as aromatics, paraffins, naphthenes, olefins and so on. In a model for catalytic reforming of gasoline, cited in problem 2.03.26, some 300 chemical species are identified, broken up in one case into 13 lumps characterized by carbon number and hydrocarbon class. The kinetic characteristics of such lumps are proprietary information. 3.5, PRESSURE DATA ‘A common way of following the progress of a gas phase reaction with a change in the number of mols is to monitor the time variation of the total pressure, m. From this information and the stoichiometry, the partial pressures of the participants can be deduced, and a rate equation developed in those terms. Usually it is adequate to assume ideal gas behavior, but nonideal behavior can be taken into account with extra effort. Problem P3.03.06 is an example of nonideality. In the simplest case, the rate of the reaction, A + Products, becomes ra = £(p,) or = kyp$ = k.C3 (3.20) Akey relation is that for the total number of mols which is determined by the stoichiometry of the reaction. This and other relations are Dio * Sa(Mao"Pa) (n/n, n,RT/n = n,/V = p,/RT so the rate equation becomes ra = KeCh = kpps = k,(RT)Sc% which relates the two specific rates as k, = k,(RT)* (3.21) Usually k, is the specific rate that is sought because the law of mass action is expressed in concentrations and is the basis of rate equations .1 RATE EQUATION IN TERMS OF TOTAL PRESSURE Since some adulteration of raw data occurs when they are transformed mathematically, by differentiation or taking logarithms or reciprocals or otherwise, it is better from a statistical point of view to change the rate equation to read in terms of total pressure, rather than to change the data to partial pressures or concentrations. Such a transformation is worked out for a reaction, aA + BB > cC + dD, with a typical rate equation, - dc,/at = Kctck. The familiar series of equations using the ideal gas law is: Pe = Mo * Sa(Mao-Na) wl Me Ly, FalMeo TM Mo Meo 1a) 99Then the rate equation,- dC,dt = kC%, becomes 1_ an k_ Pao Toh a SRT at ane Rte +) (3.22) 3.6. OTHER PROPERTIES RELATED TO COMPOSITION Some of the properties that are being used to follow the course of reaction are indicated by the data of the problems in Section P3.4. Such a property should depend strongly and uniquely on the quantity of a key participant, Reports of the experimental work usually need not provide the instrument reading, I, but only the calibrated value of the concentration or amount of the key. When the calibration is linear, such as a polarimeter reading or electrical conductivity, it may be convenient to develop a rate equation of the form r= klil® but this is transformable to an equation in terms of k,. 3.7. TEMPERATURE VARIATION One of the longest standing equations of chemical kinetics is that of Arrhenius for the effect of temperature on specific rate, Kk = kgexp(-E/RT) = exp(A-E/RT) (3.23) or ~,-Ed Ink =a ~ 5G) (3.24) where ko is the frequency factor, E is the energy of activation, T is the absolute temperature, and R is the gas constant, say 1.987 cal/(gmol)(K). The constants are readily evaluated from the straight line plot of this equation , as on Figure 3.1. Deviation from linearity may occur when the net reaction is a composite of subsidiary reactions with differently varying sensitivities to temperature, or when the mechanism of the reaction changes with temperature, One kind of composite process is that of a reaction occurring both homogeneously in the pores and on the surface of a granular catalyst. Activation energies of chemical processes usually amount to tens of kcal/gmol, but those of physical processes such as mass transfer have only a few hundred cal/gmol. Several of the examples of Section P3.06 have variable activation energies. A particular modified equation has theoretical justification for sone reactions, namely, k = koT"exp(-E/RT) (3.25) 100but normally it is needed only over very wide ranges of temperature Data are sometimes taken of the time dependence of temperature as well as composition. Then a reaction equation of the following type is applicable, - dC,/dt = exp(A-B/T) Ch (3.26) AMter linearization by taking logarithms, the three constants can be found by multilinear regression, 3.8. HOMOGENEOUS CATALYSIS. All catalytic reactions appear to involve the formation of intermediate compounds of the catalyst and the substance undergoing the reaction (the substrate, S), the sequence of reactions being S + Cat + ¥% + Product + Cat Many ions catalyze homogeneous reactions. The hydronium ion, H,0", and the hydroxyl ion, OH catalyze hydrolyses such as those of esters, ferrous ion catalyzes the decomposition of hydrogen peroxide, decomposition of nitramide is catalyzed by acetate ion. Many such effects are known. Some catalytic reactions proceed at a reduced rate in the absence of catalyst. For a reaction, A Products, the rate equation then will be r= (ky + kp(cat]%) (a8 (3.27) Some reactions will not proceed at all without catalyst, for instance some enzyme reactions, Then the rate equation is r = ktcat]*ial® (3.28) The exponent a in both cases is often unity. Enzymes also are homogeneous catalysts, although they are sometimes attached to solid surfaces without degradation. They possess a different form of rate equation, for which the development may be found in problem P2,03.02. Their behavior is especially sensitive to temperature and to substrate concentration. 3.9. CSTR DATA. LIQUID OR GAS PHASE. Data obtained in continuous stirred tank reactors have the nerits of isothermicity and of an algebraic relation between the variables rather than a differential one. At steady state in a CSTR the material balance on a reactant his VoCgg = V'Cy + TaVy (3.29) The rate may have any mathematical form, say, ry = KORE = KCB Cyp-CygtCa)™ (3.0) In most’ liquid phase reactions the volumetric flow rates are nearly the same in and out, so Cao = Ca + KICE(CypCygtCg)® (3.31) where € = V,/V’ is the mean residence time The three constants k, « and B are found by multilinear regression with data of (C,, t) of this arrangement of the material balance, Cao, 20 In = ink +e InC, +B In, (3.32) t For gas phase reaction with a change in the number of mols, the material balance is made in terms of molal flews, By ae 8 n+ kV GE GP) 101FE) = Imotd (myorm) EE v Substitute and rearrange into, Tyo"Pa V, (3.33) we y+8 Maya Mr Kp GG This is analyzed after linearization just as Eq 3.32. 3.10. PLUG FLOW REACTORS. LAMINAR FLOW. Experimental plug flow reactors may be small diameter tubes or packed beds with a larger ratio of diameter to length. The argument in favor of their employment is that they may simulate commercial units more closely. Rate data from pilot plant or commercial units also may need to be analyzed. A short packed bed may be operated with a high recycle ratio and will thus achieve substantially isothermal behavior and may have appreciable change in conversion between the net input and output streams. A PFR operates at substantially constant pressure. A typical material balance on a differential volume of reactor is ny wang = Mod = nav, = KGET Substitute V' = n,RT/w and rearrange into ox Pa a8 Paya Me 8 Pao fae = 7 aE RG PE) (3.33) When values of the derivative can be obtained from the experimental data, the constants are found by multilinear regression as usual, or by plotting when only one exponent is to be found The constants also can be found by trial after integration. Values of « and B are assumed, the integration is completed and values of k are calculated at different values of n,o/V,. If they are substantially constant the correct assumptions had been made. A special kind of tubular flow reactor has laminar flow, The specific rate of such a case is found and compared with plug flow in problem P3.09.15. 102vert we t ‘ r= ke, Stope = #(Q-1) tn Wye in Fe KC’, Slope = 1g 0), ink RANGE 800-3000 Mos Ga Os Oe 07 G8 a8 10 4d err ia TE = explA-e/Rr), Slope = -€/8 Problem 73.06.18. Varfable activation eneray. Figure 3.1. Linear Plots of Rate Equations, 102aPROBLEMS, CHAPTER 3 3.01.01. OF THE SPECIFIC RATE The units of the specific rate depend on the order of a power law rate equation and on the units of the rate of reaction which are basically, (nass)/(time) (volume). (a) A specific rate is k = 3.0(10°°) liter’*mol**sec! In other units, k = 3.0(1075) iiter? 1000 cc’* 60 sec _ , g _co'”* . Teco u/2 Pmin 7" ve, mol “sec Liter mol ““min ve v2 we mol ““sec liter 6.06(10°") molecule "26. co’? = 4,.95(10 %) ————____ i) molecule ““sec (>) In the rate equation, r = k,Cé, the rate is in lbmol/(hr)(£t*), Cy is in lbmol/ft") , k, = 0.004 and the temperature 1s 700 K. Changing the units, __cuft 28300 ce _lbmol hr Tbmol hr ~ cuft 453.5 gmol 66 min = 0.00816 cc/(gmol) (min) (c) In the rate equation, r = kjpy, the rate is in Ibmol/(hr)(cuft), p, is in atm, and k, = 0.004 cuft/(hr)(1bmol). The temperature is 700 K. Then 2 ky = ke/(RT) fe = 0.004 cuft 0.0283 > __bmol cary® = 0.004 Toor hr curt 453.5 gmol : -6. nm? atm 2 (82.05(107°)(700) SY = 7.57407) —mel __ brn? atm (a) A third order reaction in a perfect gas system has a specific rate k, = 300(cuft)*/(h)(Lbmol)* at 700 R. Find k, in the units h, atm, cuft and Tbnol. RT = 0.73(700) atm cuft/1bnol 3 ky = ke/(RT) (out t)? RT. 3 = 300 ——Ceuft)_ | 1 — br Cibnol)2(Rn® | 51? atn(euFe)7TEROTT = 2.250 reno} hr cuft atm 103(e) A first order reaction in an ideal gaseous system at 800 R has a specific rate, k = 0.14 lbmol/(350 cuft)(atm)(h}. Find the value in 1/sec. k= 0.14 ibmol 350(1.626) cuft atm h ** (35S curt) (atm) (hy Tomol 3600 sec = 63.2(10°°) /sec (£) A rate equation is r = 0.0031 C* gmol/(min) (22.41 liters) at 700 K, with C in the units gmol/(22.41 liters). Find the specific rate k, when the pressure is in atm and the rate 1s lbmol/(cuft)/(min) The ideal gas volume is 22.41 liters/gmol at 273.2 K and 1 atm. _ 700 | atm(22.41 liter) RT = 373.2 = 2.562 ‘enol K ky = k,/(RT)® 22.4 liters gnol = 0.0031 Seal min S62 atm (22.4 liters = aru0") gnol Ibmol__ 22.4 Liters min atm? (22.4 liters) 453.5 gnol 0.792 cuft = 1.316(107*) ibnol atm cuft min P3 1 2. TRUE CONTACT TIME OF FORMIC ACID REACTION The gas phase decomposition of formic acid, HCOOH = H,0 + CO is studied in a plug flow reactor. In one run the space velocity 1.29 (liters feed at STP)/(min)(liter of reactor volume) results im a conversion of 60% when starting with pure formic acid. The reactor operates at 150 C and 1 atn. The reaction rate is first order with k = 2.46/min, What is the actual residence time? 1.29 Meo = 35-4 Volumetric feed rate, Vg = 1.29(473.2)/273.2) = 1.549 liters/(1iter) (min) Apparent residence time, tapparent = 1/1.549 = 0.646 min a Material balance on the plug flow reactor, -dn, = dV, = k(n,/V" )aV, from which 0.0576 gnol/(1iter) (min) dn, _ n(2.5) Se = 0.373 min (2) 3.01.03. TRUE CONTACT TIME. POWER LAW AND L-H RATE EQUATIONS Find the true contact time in terms of the rate equation and the flowing Pa 1+k2Pa mol rate, m, when the rate equation is r, = kC$ or ry = ky( (a) Power law rate equation. ny is found by stoichiometric balance, and the flowing volumetric rate is 104nRT © Material balance on a plug flow reactor, -dn, = r,aV, ‘The contact time then is v, Op ao aS, i (2) Take the 3A go" reaction, 2A» 3B, for which ny = —“5—* and q = 2. The volumetric flow rate is (Snyo-n,)RT vee on and the equation for the contact time is RT pngp SMao7Pa jee Fn SF any (3) an: (b) With the L-H type rate equation, kj ¢ Pe kyngn/ng russ 7 V’ THEPa (1skgngn/ny)* Substitute into -dn, = rgdVp and rearrange into av, ny+kpnn, popecti si Me Vi Kent ! ny ny P3.01.04, SPACE VELOCITY IN BENZENE HYDROGENATION The hydrogenation of benzene to cyclohexane, Clg +3K, @ CgHyz, Is carried out at 500 psig and 400 F in the vapor phase over a nickel catalyst. The space velocity is WHSV = 2.0 lb benzene/(h)(cuft of reactor). A 200% excess of hydrogen is used. Benzene purity is 99% and that of hydrogen is 65 nol%, the balance being methane. Find the total feed rate in the units (a) Ibnol/(h) (cuft of reactor); (b) actual cuft/(h)(cuft of reactor) Benzene, 8 = % lbnol/(h)(cuft of reactor) iQ = 38 CH, = 3(65735)B inerts = B/99 ‘The total feed is 105Fe eae +3 + 3(65/35) + 1/99) = 0.1445 lbmol/(h) (cuft) 860, 14.7 + 0.1445(359) (755) (Se actual ofh 2.60 cafe of reactor 3.01.05. SPACE VELOCITY IN TOLUENE SYNTHESIS: The production of toluene from benzene and xylénes was studied by Johanson& Watson (National Petroleum News, 7 Aug 1946) in a standard 1-inch pipe reactor with a silica-alumina catalyst. At the reaction temperature of 932 F (773 K) the reactlon mixture was vapor phase, but the feeds were measured as liquids. The feed consisted of an equimolal mixture of reactants. The stated LHSV is {ml feed at 60 F/h)/(ml reactor}, The reactor contained 85 g catalyst packed in a volume of 135 ml. The densities of benzene and xylenes at 60 F are 0.879 and 0.870, respectively. Given the data of the first two columns of the table, find {a) (g catalyst )/(gmol feed/h); (b) (ml feed/h)/(ml reactor); (c) the actual contact time, sec. There is no change in the number of mols of mixture on reaction. 1 gmol CgHg = 78.1/0.879 = 88.85 m1 1 gmol CgHy = 106.2/0.870 = 122.07 ml 1 gmol mixture = 105,46 ml Feed rate is V, (LHSV) ng = EI = MSUIBD — 1 2eorcnusv), gnol feeavn We 85 66.40 nb ~ T2801(LHSV) ~ LASV These values are recorded in column 3 of the Table. vi _ MRT _ 92.05(773) (1.2801) (LHSV) _ 8842(LHSV) (b) ir “PVD * 714.7) (135) - P These values are in column 4 of the Table. Assuming the voidage to be 40%, the true residence time is pa We 04 bas ae fe) These are in the last colum of the table Wo/n! fa) 136.0/10.59 P3.02.01. PSEUDO FIRST ORDER The aqueous reaction, A # R +S, proceeds with the data of the first two columns of the Table and the initial conditions, Cgo = 0.1823 mol/liter, Crp = 0, Cyo = 5S Find the rate equation. From the data, the reaction appears to reach equilibrium. Assuming the rate equation corresponding to the stoichiometry, 106ry = gel = ke(CaHC.Cy/Ke) = kylC, - (0. 1863-C,) (55. 1863-C,)/K,} w At equilibrium, r, = 0, C,, 20.0494, K,"= 182.8. Integrating, ¢, dc, ka = ¢ SoC STO 1BeS-C, ISS. THEI-C,)7ISD.B @ The integration is performed numerically. The values are tabulated in column 3 and are perhaps nearly enough the same to confirm the assumed rate equation. If the water content is assumed constant at C, = 55, then C,, = 0.0494 and K, = 2.771. The integration is 1 Ca acy Lo" CC 186S-C, 172.771 3) These are tabulated in column 4 and are nearly the same as those of column 3. t Ki 3.02.02. BATCH REACTOR PROCESSES {a). Liquid A decomposes by first order kinetics, and in a batch reactor 50% of A is converted in 5 minutes. How much longer would it take to reach 75% conversion? k = £ In(o/c) = £ in 2 = 0.1986 at = gahgg in HER = 5 min (b). Repeat the previous problem if the reaction is second order C= C(t) § (2-1) = 0.2 = 15 (c), A 10 minute run shows that 75% of a liquid reactant is converted by a 0.5 order rate. What would be the conversion in a half hour? aC Lye = KC ax _ k we we ce (1x) = kt x) k= ¢ fi-(-)*7] = 0.101 ~ 0.25'7) = 0.08 107t = 20(1- (1-x)'7) When x = 0, t = 20, and x remains 0 when t = 30 min. (a). In a homogeneous isothermal liquid polymerization, 20% of the monomer disappears in 34 min for initial monomer concentration of 0.04 nmol/liter and when it 1s 0.8 mol/liter. Find the rate equation, Try the power law equation, ac _ ax cates ye ~ Get ect oor FE = cpt») Since the fractional conversion is independent of Cg the reaction is first order. al 1 2 _ k = — In Fy = gg In 1.25= 0.0656 (e).After 8 minutes in a batch reactor with Cg = 1 mol/Liter, conversion is 80%, and after 18 minutes it is 90%. Find the rate equation. Try the equation, = = kCS1-x)", whose integral is Sax a-x)* Substitute the data, at 38 Lb og = 0.1)" = 1 8 (o.2)** - 2 Therefore, a = 2, second order. (f). The decomposition rate of pure ethane is 7.7%/sec, but with 85.26 inerts present the decomposition rate falls to 2.9%/sec. Find the rate equation. The given data are of initial rates, (2%). = Kc™ 1% » ect 0.077 _ Soure yet Tapure 9-029 1 jan 1474 Cmpure whence @ = 1.51 (g). The first order reversible liquid reaction, A @ R, takes place inal batch reactor with C,o = 0-5 mol/liter, C.o = 0. After 8 minutes, conversion of A is 33.3% while equilibrium conversion | 66.7%. Find the rate equation. de = KC.SC, ~ 0.25) 1081 y, 1.8(0.5)-0.25 is T.5C,-0.25 8, C,/Cyo = 0.667, C, = 0.393 kt = When t =i = k = peray 17 ozs = 0.0578 Thus the rate equation is ac, ~ er = 0.0878 [C,-(0.5-C,)721 93.02.03. CHANGES OF VOLUME. These two reactions are first order, inconsistent with the stoichiometry. Find the specific rates. (a). The stoichiometric equation is A » 1.6 R. The pressure is 1.2 atm, ‘the temperature is 25 C. When starting with pure A, the volume of the mixture {ncreases 50% in 4 minutes. by = natn, B vom. =4 Yo Bao a/Ngg = 16 k = £ In (nyo/ny) = 0.25 In 6 = 0.448 (b}. For the first order reaction with stoichiometric eqaution, 2A » R, ‘the volume decreases by 20% in 3 minutes when starting with 20% A. Myo = 1, inert 0.2, Mao = 0.8 ny =n, + Ny + 0.5(nyo-n,) = 0.6 + 0.5n, n, = + = 0.6 + 0.5n, = 0.8 when t = 3 Yo Peo (0.8-0.6)/0.5 p " 14, Bao lt kegingeegin 04. THE RATE IS KNCWN NUMERICALLY ‘A gas phase reaction, 2A 9 B, occurs at 50 atm and 700 R. Originally 5 Ibmols of A were present. Wnen one-half of the A has disappeared, the rate of lisappearance of A is 0.34 lbnol/(h)(cuft). Find the specific rate. ny = Ny + 0.5(ngo-n,) = 0-5(ngotn,) = 0.5(542.5) = 3.75 at 50% conversion MRT _ 3.75 (0.73) (700) _ vee = SOY = 98.99 curt = 0,94(°3-22)? = 79.9 cuft/(h) (1bno01) The acid catalyzed conversion of gamma-hydroxy-butyric acid into its tone was studied In 0.2 N HC] solution at 25 C, The initial concentration the acid was 18.23 in arbitrary units. The lactone concentration was 109observed in the same units at different times, in minutes. The data are in the first two columns of the table CH,CHOHCH,COOH $ O(CH,),00 + H,0, Ae B+C Find the specific rates of the forward and reverse processes. Water is present is great excess so its concentration does not change appreciably as the reaction proceeds, and the magnitude is incorporated in the reverse constant ac, = P= Cy kgCy = Key (Cy - Cy/KQ) = Ky (CyoCyCy/Ke) at Fron the data, = 13.28 - Ke = Teraa-1a.2e ~ 2-683 and the rate equation becomes acy ~ SP = k(18.23-1.3730,) The specific rate is given by _1 dG, ol 1 ki = ¢ Jo, Teas1.3730, ~ Tavat ” 1-0 07SaC, The values are in column 3 of the table, and are nearly constant. The reverse coefficient is ky = ky/Ky = k,/2.683. ‘A first order gas phase reaction, A # SR, is first studied at constant pressure of 2 atm starting with pure A. After 15 minutes the volume increases by 75%. When the same reaction is carried out at constant volume and the initial pressure is 2 atm, how much time is needed for the pressure to reach 3 atm? The rate equation is dn, ge = kay kt = In (nyo/n,) At constant P, Vo" Fao Peo = 4.75 when t = 15. VoL Me, 3Mx072M 3 - 2n,/ngo Then Tg/Mgg = 0.625 110k = gg In(1/0.625) = 0.0313 i At constant V, rom lye Bog 7 37 24/0) In (1/0.75} = 19.2 min, when 1 9.02.07. EQUILIBRIUM AND INITIAL RATE DATA A reaction has the rate equation 2 _ ac 2 _(2.2-C) re - Gp =k IC . Initial concentration is Cy = 1.5, initial rate is rp = 1.076, and equilibrium concentration is C, = 0.6798. Find the constants. 2.2 ~ Coa _ (2.2-0.6798)2 ( = 5.000 To 1.076 & - 0.2(2.2-Cy)? 2.25 - 0.20.7)? 0.500 ki = P3.02.08, DATA OF RATE VERSUS CONCENTRATION For the reaction, A » Products, measurements of the rate as a function of the concentration were made with a CSTR. G 1S 1.3 11 6.9 0.7 05 0.3 r, 28.0 20.0 12.8 7.7 4.1 18 0.5 Find the order of the reaction and the specific rate, Assume a power law rate, s0cen yaloets) 2ec.ooane3eo0 Fa = KC sceossers and in linearized form — in(r,) = Ink) + q In(C,) = 2.319 42,504 1n(C,) vhich makes the rate equation r, = 10.166 CoS The plot is a good linear fit of the data. aitP3.02.09. DATA OF CONVERSION AND EQUILIBRIUM. SIMPSONS RULE. The liquid phase reaction, 2A B, has equilibrium constant K,= 5 and Initial concentrations Cy = 0.6, Cyo = 0.05. In 30 minutes, 50% conversion of A is realized. What is the specific rate of the forward reaction? Cy = Co + 0.5(Cyo-Cy) = 0-05 + 0.5(0.6 -Cy) = 0.35 -0.5C, ac, at kc? - 0.2(0.35 ~ 0.Sc,)] 1 oe, ac, w= peo Se EC, 24 0.1C, -0.07 The integrand is evaluated at three points and the integration !s accomplished with Simpsons rule. ) [2.857 + 4{5.634) + 20.000] = 0.076 For comparison, integration with the trapezoidal rule with 100 intervals gives k = 0.0716. P3.02.10. TIME-CONVERSION DATA A second order reaction, A + B » Products, is found to be 25% complete in 50 minutes when both starting concentrations are 0.2 mol/liter. Find the specific rate and the half life of the reaction. ac, 2 ~ ae = Me ee te ay et ty © 0.0339 Titers. Tro Ce = 500.2) 075 =o ol min 1_(Cao - 1 -ae ‘ tye = gag” Y= graggarsay(2 ~ 1) = 150 min 3.02.11. CHLORINATION OF TOLUENE Data of the reaction of toluene (A) and chlorine (B) in glacial acetic acid were taken by Brown & Stock (JACS 79 5175, 1957) with time in seconds and molar concentrations . Find a suitable rate equation. Assume first that the mechanism corresponds to the stoichiometry, thus second order. aA _ 4 ~ Ge = KAB = KA(A~0. 1595) = 1 0.1908 aA kee 8 ATA-0. 1595) The integration is done numerically and values are given in column 4 of the table. The average value is k = 5.248(10*) Liters/(mol) (sec) uz3.02.12. ETHYL ETHANOATE AND NaOH A quantity of ethyl ethanoate (A) is reacted with an excess of sodium hydroxide (B) at 25 C. 100 cc of the reaction mixture required 68.2 cc of Of 0.05 mol/liter HCl for neutralization at the beginning of the reaction. After 30 minutes, 100 cc of the mixture similarly required 49.7 cc of the acid, and when the reaction was complete, 100 cc of the mixture required 15.6 ce of the acid. The reaction is not reversible. Find the specific rate. A +B » Products 15.6(0.05) T00 . _ 68.2(0.05) Initial NaOH, By = “—~Sog-> Ao = 0.0341 - 0.0078 = 0.0263 When t = 30, Excess NaOH = By - Ay = = 0.0078 mol/liter = 0.0341 a = pep = (68.2-49.7)(0.05) _ AgmA = Bo-B = Sa G = 0.00925 x 2 F = k(0,0263-x) (0.0341-x) 0.00928 1 9.008: ax 0.500 Liters k= 35 Jo 10. 0263-x) (0. 0341-x) iol nin | 73.02. 1 In a study of the alkaline hydrolysis of ethyl 2-methylpropenoate in | 4.7% ethanol, Thomas & Watson (JACS 77 3962, 1956) obtained the data of the first two columns of the table, t in sec, NaQH titre/cc. The Initial concentrations of both ester (A) and alkali (B) were 0.058 mol/liter. 10 cc of the reaction mixture were removed from the vessel at the time stated, pipetted into 10 cc of 0.0668 mol/liter HCl and the excess titrated with 0.0511 yel/Iiter NaOH. Find the mean value of the second order specific rate. EMP2 (A) + NaOH (B) » Products y = titre, cc, column 2 of table {20H balance, 1 B= 0.0668 -0.0511(, 4) ( G.0668 -0.0005ily, mol/liter 1000°°0.1 The values are tabulated in column 3. dB ~ oe 7KAB ela 1 k= =~ aos08) The values are tabulated in column 4. The mean value is k = 0,198 liter/(mo1) (min) 1138.0462 25/5.11 0.0407/0.195 40]5.98 0.0362/0. 198 60/6.86 0.0317|0. 198 80/7.57 0.0281|0.199 110|8.36 0.0241|0.198 3.02.14. CIS~TRANS ISOMERIZATION The cis-trans isomerization of 1,2-dimethylcyclopropane at 453 C is a reversible first order reaction. The percentage of cis is shown as a function of t in sec in the table. Find the constants of the rate equation. cis (A) $ trans (B) L _ column 2 = Mh = Teg 2 £ B= AgtBy-A = AgwA = Ag(1-£) A df _ “(141 ~ Ge = ~Aogg = RiAolf -(1-£9/K.) K, K, wy = ke ph at tan a 2 Ev (Kptyf-l ~ TK 41 (KFT K, = BA, = 70/30 = 2.333 The values calculated from Eq (1) are tabulated. The mean values are k, = 0.002402 /sec, Kg = k,/K, = 0.001029/sec t Data of the hydrolysis of ethyl acetate in the presence of a constant amount of HCl have been obtained by Knoblauch (2 physik Chem 22 268, 1897). EA (A) + H,0 (B) $ Ethanol (C) + Acetic Acid (D) Initially the mixture was 1.00 molar in EA, 12.215 molar in water and ethanol, and free of acetic acide. The data are of time, min, against acetic acid, mol/liter. Find the constants of the rate equation. The equilibrium constant is (42, 215+0. 2644) (0.2644) Ke = (a=. 2684) (12. 215-0. 2644) ~ 09799 The rate equation is ap Se = Ks(AB-CD/K,) = ky [(1-D) (12.215-D)- (12,215+D)D 0.3753! 114‘The integral is solved for the specific rate, a ky = SQ DYE BIS Dy a CST DISD Integration is done numerically and the values are in column 3. The approximate constancy of k, confirms the assumed rate equation. t, min 10%, 3.02.16. A SULFONE AND HYDRAZINE ‘The reaction of phenyl a-disulfone with hydrazine, PhSO,SO,Ph (A) + NgH, (B) * PhSO,NHNH, + PhSO,H wes studied by Kice & Legan (JACS 95 3912, 1073). I runs with initial concentrations of sulfone of 3(10°5) mol/liter, the reaction is pseudo first order. The values of Kapp, i/sec, vary with {NjH,] mol/liter, as tabulated Find the rate equation. Try the rate equation, Kappa Inky, = ln k + @ In Cy The linearity of the plot confirms the assumed rate equation. The correlation is Kypp = 43.1 Ch? ° Data: os 1 1.6 2.0 3.0 40 0.085 0.176 0.30 0.41 0.67 0.95 7 . 5 ‘ fs 100 Patt 2 ra) we 115Butadiene is dimerized at 350 C in the gas phase according to second order kinetics. Data were taken at constant volume, time in minutes and total pressure in Torr, starting with pure butadiene. 2A > B ny = 0.5(nyo#n,) RT RT w= ny AE = (ngotng) BE =, Rt To = Pao Dy _ 2m = Mo _ 2n -500 vo RT RT T = 62.3(350+273.2) = 38834 liter Torr/mol The rate equation in mol and pressure units is 1 any 2 Fae = k(n) 2dn__k 2 - 2 Mt = Ean - 500) RT at ~ Gy Integrating, ye = 2RT soo dx, 98894, 1 1) t ‘ne Gesooj? & . 2m-S00 ~ 500 ‘The four values are tabulated. Their average is k = 1.95 liter/(mol)min} Data for the dimerization of gaseous butadiene to vinyl cyclohexene were obtained at 326 C in a constant volume apparatus by Vaughan (JACS 54 3863, 1932), with time in minutes and total pressure m in Torr. Find the constants of the rate equation. (a) Assume a rate equation in terms of the partial pressure, ~ OB x gp? at The result of integration is eid ll bot EG pp a The partial pressure of butadiene is related to the total pressure by p = 2m ~ ti = 2m ~ 634.1 The plot of Eq (1) has the equation 1000/p = 1.5801 + 0.023097 and confirms the assumed rate equation, making ap 2 ~GE = 2.3097 p' Also, dn _ 2.3097 2 oT 7 (anny) (b) Another method is make a curve fit of the data and then find dp/dt by differentiation. if the plot of In (dp/dt) against p is linear, the 116constants of the rate equation will be known. POLYMATH is used to fit (p,t) data with a cubic spline fron which the derivatives are obtained also by POLYMATH. The cubic spline plot and the (rate, p) plots are shown. The derivative is in column 5 of the table. The linear plot has the. equation ~ SP = exp(atb In p) = exp(-10.194 1.919 p) 1.919 = 3.74010) p' This formula and the one derived in part (a) give about the same results. DATA 1000/p|-dp/at 08.0 54a. 88 103, BB P 388 (8.381 a a (68. 88 128. fe (88 248, 88 38H. BF adp/dt 1000/p 3.02.19. SULFURIC ACID AND DIETHYLSULFATE Data for the reaction HSO, (A) + (CoHlg),$0, (B) $ 2 CoHgSO.H (R) were obtained by Hellin & Jungers (Bul? Soc Chim 386, 1957}. Initial concentrations were Ag = By = 5.5 and Ry = 0. The rate equation is to be found. 17Try the stoichiometric form, ~ B= 21, (5.5-0.5R)? ~&,R*} mM = 2k, [(5.5-0.5R)* ~ RK] (2) From the tabulated data, 2 K= 8 57 4.976 (3) (5,5-2.9) Integrating Eq (2), aR 2akt = SF (@ © (5.5-0.5R)*-R°/4. 976 The integral is found numerically and is tabulated in column 3, The straight line plot of (J§, t) has a slope 2k, = 2.268(10°5) from which k, = 1.134(107°) The assumed rate equation, Eq (2), is confirmed. ° 1680 0.0244 2880 0.0543 4500 0.0947 5760 0.1250 7620 0.1651 9720 0.2095, 10800 0.2424 12720 0.2870 16020 0.3596 19080 0.4338 22740 |5.35|0.5080 24600 |5.42)9.5422 @ |5.80 P3.02.20, HYDROGEN PEROXIDE The catalyzed decomposition of 1,0. in aqueous solution is followed by removing equal volume samples at various times and titrating them with KMn0, to determine the undecomposed HZ0,. The results are tabulated. Confirm that the reaction is first order and find the ce of KMnO, required for the titration of the sample removed at t = 0. For a first order reaction 1 pride a =e le = es ln (37.170) The values are tabulated in column 3, and are nearly enough constant to confirm first order, the average being k = 0.0438/min. When t = 0, C = 37.1 exp(Sk) = 37.1 exp(0.219) = 46.2. Ky ue3.02.21. ACID HYDROLYSIS OF METHYL ACETATE The rate of hydrolysis of methyl acetate is reversible and proceeds according to the equation GE = ky [Acid] (a-x - °K) where [Acid] is concentration of the acid, a-x that of the ester and x that of each of the products at time t, In aqueous acetone at 80.2C methyl acetate initially 0.05 M was 90% hydrolyzed at equilibrium. The data of the table were obtained by Newling & Hinshelwood (J Chem Soc 1357, 1936) for hydrolysis in the presence of 0.05 M HCl. t is in sec, and y is % hydrolyzed. The mols converted per liter is x = 0,05(0.01)y = 0.0005y The equilibrium constant 1s x, = _10.0005(90)]* _ . oO! 005 (90) The rate equation becomes 0.0005, x = 0.05k,[0.05-0.000Sy - (0.0005y)*/0. 405} Integrating, ay 70.405 The integration is done numerically, trapezoidal rule, 200 intervals. The almost constant results of column 4 confirm the rate equation and have an average value k = 36.26 3.02.22. SAPONIFICATION OF METHYL ACETATE The rate of saponification of methyl acetate at 25C was studied by making up a solution 0.01 molar in both base and ester and titating the mixture at various times with standard acid. The data are tabulated. Show that the reaction is second order and find the specific rate. C = concentration of MA 119wt kee > nor The values are tabulated and appear to be nearly constant, thus confirming the second order mechanism. 0.01 0.0074 |11.71 0.00634] 11.55 0.0055 |11.69 0,.00464| 11.55 0.00363) 11.70 0.00288) 11.77 S 0.00254] 11.75 REASrawe 3.02.23. SODIUM THIOSULFATE AND METHYL IODIDE The table gives kinetic data (Slator, J Chem Soc 5 1286, 1904) for the reaction between Na,S,0, (A) and CH,I (B) at 25 C. The concentrations are in arbitrary units, the time in minutes. Show that the reaction is second order eB ~ Ge = RAB = (17.14) ad pos ap in 18:25(17. 148) tls BG7.TB) * iF it 35.358 The values are tabulated and appear to be nearly constant, confirming the second order mechanism. Average value is k = 1.98(107°). P3.02.04. HYDROXYVALERIC ACID The conversion of hydroxyvaleric acid into valerolactone at 25°C in 0.025 N HCl was followed by titration with standard base. Given the tabulated data, find the order and specific rate of the reaction. Assume that complete conversion occurs as t + 0. 10a, 19.04-V x = fraction of lactone formed = 7535-75 If the reaction is first order, 120The calculated values are in column 3 of the table. They are nearly enough constant to confirm a first order mechanism P3.02.25. DIFFERENT SOLVENTS Data for the acid hydrolysis of methyl acetate (A) at 25°C CH,CO,CH, + H,0 + CH3COOH + CH,OH have been obtained as t in minutes and conversion x in mols/liter. Find the orders and specific rates of the reactions in the two solvents. (a) For aqueous solution with initial 0.1 mols/liter for HC1, $2.19 for H,0 and 0,7013 for A the data are in Table (a). (b) For aqueous acetone with initial 0.1 mols/liter for HjS0y, 0.933 for H,0, and 2.511 for A the data are in Table (b) Assume that the rates are proportional to the concentrations of the acid catalysts, and that the stoichiometry represents the mechanism, thus second order X = conversion of A, mols/liter ax S% = k(acia) (A) (H,0) Part (2 GF = ie (0.1) (0.7013+«) (52. 19-x) - 1 ie ax Ker goat Lo (6. 7O13x) (SETI © If the slight change in water concentration is neglected, = 1 x dx Kea = gapszisy fo O-7015x (@ Part (b). ar ax = one [0 (SITIO IER @ All three integrals are evaluated numerically and tabulated. The pseudo first order kag 1s as nearly constant as the second order value, ky, (a) Aqueous solution

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