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Chapter 1 Complete

Cre 2 complete chapter- 1

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sarthak doomra
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© All Rights Reserved
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CHAPTER. INTRODUCTION TO HETEROGENEOUS REACTIONS Heterogeneous reactions are those in which, more than one phase is involved to proceed. ‘Accordingly, there may be two phase and three phase reaction systems. ‘A heterogeneous reaction involves substances which exist in different phases and reaction usually takes place at an interface between the phases or in one of the phases. Heterogeneous reactions may be catalytic or non-catalytic. In catalytic heterogeneous reactions usually the catalyst is a solid. Some examples of catalytic heterogeneous reactions : ( Gas-solid reactions : Synthesis of ammonia, catalytic cracking of crude oil, oxidation of SO, to SO; using V0, catalyst in the manufacture of sulphuric acid. (ii) Gas-liquid-solid reactions : Catalytic oxidation of liquid hydrocarbons (e.g. ethanol) using air or oxygen to acetic acid, catalytic hydrogenation of acetone to propanol. A heterogeneous catalytic reaction occurs at the interface (between the phases) which is the surface of a solid catalyst immersed in a gaseous or liquid reaction mixture. Some examples of non-catalytic heterogeneous reactions : () Gas-solid reactions : roasting of sulphide ores, combustion of coal. (i) Gas-liquid reactions : chlorination of liquid aromatic hydrocarbons using chlorine gas, Purification of gas mixtures, manufacture of ammonium nitrate by absorption of ammonia in aqueous nitric acid. Gil) Liquid-liquid reactions : nitration of organic compounds with aqueous nitric acid, formation of soaps by the action of aqueous alkalies on fats or fatty acids. (iv) Liquid-solid reactions : production of acetylene by the action of water on calcium carbide. 7 Apart from all differences, heterogencous reactions have one thing in common : Before a a : ineuntal reaction can occur, the reactants from the bulk of one phase must be transported tothe ‘ace between the phases or into the bulk of other phase. (14) Chemical Reaction Engineering - It __Introduction to Heterogeneous Reaction, For heterogeneous systems we have to consider the following factors in addition to thos| normally considered in homogeneous systems : (i) ‘The modification of the rate equation resulting from the mass transfer between phases, Gi) The contacting patterns for the reacting phases. Rate Equation for Heterogeneous Reactions : A heterogeneous reaction (catalytic or non-catalytic) takes place in a number of steps - oy) or several chemical steps (i.e., one or several chemical reactions) are always accompanied steps that are physical in nature. These physical steps are associated with the transport of mat from one phase to the other. The concentration of matter in the bulk of one phase and at th! interface is different and the concentration difference is the driving force for these physica} transport processes (diffusion). Heterogeneous reactions are treated as consisting of a series of steps or of series and paral (mixed) steps. In a heterogeneous system (in which the overall change is brought through various steps), tr] overall rate equation in general will consist mass transfer terms in addition to the usual Kinet term. If a heterogeneous reaction consists of parallel steps, then the overall rate is equal to the of all the individual rates : Toveral = Et ist the overall change results from a number of steps that take place in series), then at steady-s conditions, the rates of the individual steps in scrics arc all the samc and equal to the overall of reaction : Tf, on the other hand, a heterogeneous reaction consists of several consecntive steps =| Toverall = T= 12 Th Here, the rates of the individual consccutive steps adjust themsclves to that of the slo step. When rates of the various steps are to be compared or combined, then they mq eed identically (i.e., the rate equations of the individual steps must be written on the § asi) __ Thus, when mass transfer takes, the rate is defined in terms of molar flux (moles pet 4 {ime Per unit surface), the rate of chemical reaction should also be based on unit surface instead on unit volume. Based on unit volume of reacting fluid : ot, = -2.9Na _ __mol A reacted V dt * Volume of fluid - time {otroduction to Heteroge Based on unit mass of solid : 1 _ _ 1LaNg _ __mol A reacted a4 2- 2 od ine ‘a = —Wrdt = mass of solid « time Based on unit interfacial surface / unit surface of solid : _ LAN, _ ___mol A reacted S dt ~ interfacial surface - time ‘These rates are related by mol A reacted ‘ " “ime = Ga VEC) WaCr)S we Ev Wa "ov 5 Consider steps in series. In combining rates as we usually do not know the concentration we have to eliminate these concentrations and express the materials at intermediate positions, nce. This is easy to do if all overall rate of reaction in terms of the overall concentration differe ar in concentration, i.e., the rate expressions for mass transfer and chemical the steps are line reaction are linear in concentration - first power in concentrations or concentration differences. [CONCEPT OF RATE CONTROLLING/LIMITING STEP ‘We develop an expression for the overall rate of reaction and then we st the simplest forms if we assume one of the steps to be rate controlling. ee how it reduces to A(g)+B(s) > R(g) A gas is transported from the bulk of gas to the solid surface, surface and finally, product R is transported from the solid surface to is first order with respect to the gaseous reactant A, and no ash is forme the reaction occurs at the the bulk gas. The reaction .d on the solid surface. The overall rate can be formulated by considering only first two steps involving A. The rate of disappearance of A can be expressed in two ways as the rate of transport of A to the surface of B and as the rate of reaction of A at the solid surface. The rate of mass transfer of A through the gas film by diffusion per unit surface, ie, the flux Of A, to the surface of B is » -1dN, “ty = Bae =k (Cu Cad) aa) 14 Introduction to Heterogeneous Re, Chemical 1g ‘These steps are in seties. So at steady state, the rates of mass transfer and chemical reaciy steps will be the same. Flux of A to the surface = Reaction rate at the surface ath, = Te This equality can be used to develop the overall rate equation in terms of concentration of, in the bulk gas. Ky (Cap— Can) = "Cau ky Cap = (k" +k) Cay Cas = rE Car =(E ‘The rate at which the overall process of mass transfer and chemical reaction proceeds can| found by substituting C,, from Equation (1.3) into Equation (1.2). ‘The overall rate of reaction (-r, )is ai Biywae ete Ta" at Cn For steps in series : r, = r) = foverath dividing the numerator and denominator of the aboy equation by k" k, gives a k, +k This is the expression for the overall rate in terms of the bulk reactant concentration. (ld By analogy with the mass transfer coefficients, the sum in the denominator of ‘Equation (14 may be regarded as the sum of the resistances offered by the individual steps of a heterogene04 Process. [Denominator is the sum of the reciprocal rates of the individual steps.) and . ee {ale of @ heterogeneous process is determined by the slowest step and hence it Overall change, Very hen asthe fate controlling step presents a maximum resistane . Very often we find that on a - tat israte controlling or rate limiting, fe or other of the two steps (provicing major resistalt If, under operating conditions, keg >> ke, (rm ov # specific reaction rate constant) then th {mass transfer coefficient is much greater tht the overall rate reduces to ll Which implies that the chemical reaction . 3 controlling the overall process), 'S the rate controlling step (the chemical react cponiealeacton Engineering-|____1.5.___ Introduction te Hetero {k,>> K" 7 80 Ik, is very negligible compared to 1/k* and hence it can be neglected from aiion (1-4) and it then reduces to Equation (1.5)). Inthis case We have rapid diffusion with respect to surface reaction - the reaction is so slow vinwally no concentration gradient exists in the gas phase and mass transfer effects are not ortant - when reaction is slow. If, on the other hand, k" >> k; (the specific reaction rate constant is much greator than the mass transfer coefficient) then the overall rate of reaction is given by ty = Ky Cap w= (1.6) [k" >> ky ~ $0 I/k" is very small compared to I/k, and so I/k" can be neglected from the overall rate expression] which implies that the mass transfer step is rate controlling. The reaction jgso rapid that the rate of mass transfer to the surface limits the overall rate of reaction. If the ieaction takes place in the region intermediate between the chemically controlled region and the mass transfer controlled region, the overall rate of reaction will be composite of the two steps and is given by Equation (1.4). (CONTACTING PATTERNS (SCHEMES) FOR TWO-PHASE SYSTEMS Tn heterogeneous reactions, contacting patterns affect both physical and chemical rate processes. There are many ways in which two phases can be contacted. Each of the contacting pater is having a unique design equation. In ideal contacting of the phases, each phase may be in one of the two ideal flow patterns, ie., in plug or mixed flow. Equi that imp A > A 1 A > —_—— B B | B Plug A + Plug B Plug A + Plug B Plug A + Plug B Countercurrent Cocurrent (parallel) Crosscurrent (cross flow) @ (b) © Micro-micro or macro-micro ‘Micro ‘or macro | Reaction occurs As [_, inelther A or B plese: A |S. }— Reaction occurs in either A or B phase E B (d) Plug A + Mixed B (e) Mixed A + Mixed B Fig. 1.1: Various ideal contacting patterns (schemes) for two flowing fluids With ideal flow of both phases, many ways to contact the phases are Possible / combinations of contacting patterns are possible. Ideal contacting patterns for two-phase syst are shown in Fig. 1.1. If one of the phases is discontinuous (€-8.» droplets oF solid partcigy it will be treated as a macrofluid. Distinction between macrofluids and microfluids ‘is ne only when the phase is in mixed flow. It is possible to develop design equations for ideal fg, patterns but when real flow deviates considerably from these then either we may develop moi to mirror actual flow closely or may calculate the performance with ideal patterns which ‘brag actual flow. Fortunately, many real reactors that are used for heterogeneous reaction systems ¢ be approximated in a satisfactory manner by one of the [ive ideal flow patterns of Fig. 1 1 (obig can be seen by comparing these flow patterns with the sketches of typical reactors for fTuid- and fluid-solid systems). SOLVED EXAMPLES} Example 1.1 : The irreversible reaction A(g)+B(s) — R(g) «(first order w.r.t. A) takes place on a flat surface as shown in Fig. Ex 1.1 (a). Dilute A diffuses through a stagnant g {film onto a plain surface consisting of B. On the surface, A reacts with B to produce gaseous! which then diffuses back into the main gas stream. Develop the overall rate expression for th GS reaction. Plain surface of solid B Main body of gas Equilibrium concentration ‘of Aon the surface = 0 Fig. Ex 1.1 (a) Solution : A(g)+B(s) > R(g) Given : Irreversible first order G/S reaction w.r.t. A. Plain surface of solid B Main body Fig. Ex 1.1 (b) _Introduction to Heterogeneous Reactions ‘This overall process comprises of two steps in series : (1) Mass transfer step : Diffusion of A through the gas film to the surface of B. 2) Reaction step : The reaction of A with B on the surface of B. (Diffusion : The mass transfer step : The flux of A (by diffusion) to the surface is given " 1dN, @ tq = SG = Cas Cad =k (Cag Cad WM =r), is in moV(m2.h), Cagis in moV/m’, k,is in m/s [m* gas/(m? surface « s)] ~ mass transfer coefficient of the gas film. C,gis the concentration of A in the main gas stream, mol/m’. (ii) Reaction step : The reaction is first order with respect to A. The rate of reaction based on unit surface is given by ” 1dNa = 3 aE Cw 2) 11, is in mol A/(m?surface - time), k"is in m/s and Cq,is in mol/m*, Now, we will obtain the overall rate of reaction in terms of kyy k" and Cag (as the concentration of A-on the surface, i., Cy, cannot be measured). As both steps —-diffusion und reaction are taking place in scrics, at steady state, these steps will proceed at the same rate. Thus TA overall Ky (Cag—Cas) = kK" Cas K Cag = Cas ky’) k, Ca = gee G& me) Substituting C,, from Equation (3) into Equation (2), we get | Let x * 7 ‘This is the overall rate expression accounting for both the mass transfer and reaction st fs, »mol/(m?.s) — ample 1.2 : Dilute A diffuses through a stagnant liquid film onto a plane surface of soy gE 2: ilu ” : n this plain surface, A and B react to yield liquid product R which then diffuses back thr in thi * . : the film into the main liquid stream. Develop the overall rate expression for the L/S reaction, A()+B(s) > R(l) _...first order w.r.t.A Solution + A(D+B(s) 9 RM «+. Irreversible L/S reaction ... first order wary Plain surface of solid B Main body of liquid Equilibrium concentration of Aon the surface = 0 Fig. Ex 1.2 Steps in series : @® Diffusion of A through the liquid film to the surface. (ii) Reaction of A with B on the surface of B. Mass transfer step : ‘The molar diffusional flux of A to the surface is given by 1 AN, D 3d = ay Caw) =k Cu Cu) where ky ~ mass transfer coefficient of the liquid film, m/s fay > Molar flux of A, mol/(m?-s) ~ concentration of A in the bulk liquid, mol/m? ~ Concentration of A at the surface of B, mol/m? _1,9.______ Introduction to Heterogeneous Reactions Reaction step = ‘The reaction is first order w.r.t. A. The rate of reaction based on unit surface is given by "1 dNy Te = Ss at R'Ca - 2) [Atsteady state, these steps will proceed at the same rate (steps in series). Thus, Ta overall Kj (Car Cas) = "Cas KiCar = (k" +k) Cay = hu k+k Substituting the value of Cg, from Equation (3) into Equation (2), we get Gu .-G) , mol A/(m?-s) or Keven! Car where Koveran = L/CU/ky+ UK") Example 1.3 : Repeat Example 1.1 considering the reaction step to be second order with respect to A —all else remain unchanged. Solution: A(g)+B(s) > R(g) _ ... Irreversible G/S reaction with second order rate. Diffusion-masy transfer step : Diffusion of A to the surface through a gas film, The diffusional flux of A to the surface is given by « 1 dNg =n Sat = Ke Cap Cad) oo (D) Reaction step : The reaction at the surface is second order w. ‘The rate of reaction hased on unit surface is given by GN yw at, 2 Mid 2 Q) fa the processes - diffusion and reaction at the surface occur in series, at steady state, these Steps will proceed at the same rate. Thus, KelCag— Cas) = "Cas K' Cas +h CuK Cug = 0 Chemical Reaction Engineer! This is a quadratic in C,y. ‘The roots of this equation are : -k+4 = aie" CkCu) Ca = OK" The positive root is -k+\ i+ ak", Cas OK Substituting Ca, (as it eannot be measured) from Equation (3) into Equation (1), ye following overall rate expression : ® —k, +k + 4k" k Ca, -f,, = KL Cu- 2k" _ k, Vke+4k"k&C, n-1, = ufeye dy EMG ies 2k" ‘Taking 2k" common from the denominator gives -r. = [2k Cag ky 9G + 4K" ky Cag | Equation (4) is the desired overall rate expression that takes into account both te transfer and reaction steps. Cas Example 1.4 : Gaseous reactant A diffuses through a gas film to the surface of where it reacts with B according to a reversible first order rate, 1, = K"(Cys— Ce), mol/(m?-s) where Cy, is the concentration of A in equilibrium with the solid surface. Derive an expression for the rate of reaction of A that accounts for both the mast and reaction steps, f Solution : 1. Mass transfer step : ‘Ihe flux of A to the surface by diffusion (9 transfer of A to the surface through a gas film per unit surface) is given by, ” 1 dNy “ig = BG HK (Cag Cad Cagis the concentration of A in the main body of gas. Casis the concentration of A at the plain surface of a solid. 2 Reacti i : it ft ace “ton step : The rate of reaction of A at the surface based on utit dN, ; “AK Ca Cyy) chemical Reaction Engi At steady state the flux of A to the surface is equal to the reaction rate at the surface (steps in series so both the steps will proceed with the same rate.) fy = Tay = Tay Fy(Cig— Cad = K" (Cu Cr) KgCag t+" Coo = Cask" +) yng ke" Cae Cu = 2 Substituting C,, from Equation (3) into Equation (2), thus eliminating Ca, from the rate expression, we get K, Capt k" C, we fSe# SH.) eke [aot K" Cap" Cae— Bs) K"+k, Bak Cun Cn) Dividing the numerator and denominator of the above equation by k" k,, we get | (Cag~Cad Ta FE = mol/(m?-s) w= (4) or = Koverat (Cas— Cao) where Keer = (Ik, + Uk") Equation (4) is the desired expression for the rate of reaction of A accounting for both the ‘uéss transfer and reaction steps, eae In slurry reactors, pure reactant gas is bubbled through liquid containing ho in Fig = aan In terms of the two-film theory, these kinetics can be viewed as lig fn eg tenes 10 reach the surface of Sli, the reactant must diffuse through the Paice ne it body of oud and then through the fl surrounding the catty netics. Develop an e: ¢ of the catalyst particle, reactant gives product according to first order ‘xpression for the rate of reaction in terms of these resistances. alli Liquid ticle 6 interface, NI catalyst surface Pure gaseous reactant A Fig. Ex 1.5 Here three resistances act in series : liquid film film surrounding the catalyst particle and re: resistance (and for this Ca,= Ca)]- Solution : surrounding gas bubble, action. [As pure A is used there is no gs ‘The rate of transfer of A from gas to the surface of the catalyst particle is given by th expressions : (Liquid film-surrounding gas bubble : Kar a (Cai Ca) where —r,” is in mol A/(m® reactor-s) gas-liquid interface = fm? a = “Jolume of reactor * ™”™ ki liquid film mass transfer coefficient in m? liquid/(m? surface - s) ie. in mis. ‘kg aj is in m? liquid/(m? reactor-s) (ii) Liquid film-surrounding the catalyst particle : ix = Kaede (Car Cas) where kycis the film coefficient about catalyst particle in m? liquid/(am? cat's) a 3 external surface of particle fe volume of reactor * ™/™ (iti) (ii) The reaction step : The surface reaction is first order with respect to A. ‘The rate of reaction is given by ma Krag Cay Cag is in mol/m liquid, a, is in m2/m? of reactor, yis in m® of liquids(m? cat - 5), ‘ At steady state : al Reaction Engineering -Il__ Cy- Car = Car Cas 1.43 Summing Equations (5), (6) and (7), we get un kara we 1 Kaa Krai (Cai- Cad = Kas de (Car Cas) __Introduction to Heterogeneous Reactions, 1 Ae Cas oA wail) .- (6) - .8) Equation (8) is the desired rate expression for the rate of reaction in terms of three Tesistances in series. Example 1.6 : Gas containing A contacts and reacts with a semi-infinite slab of solid B according to the reaction : A (g) + B(g)->K(g) + 5 (8) _ As reaction progresses, u shurp reaction plane moves forvard into the solid leaving behind it @ product layer through which gaseous A and R must diffuse. For this situation, three ‘resistances that act in series (- gas film, ash layer and reaction step) are as shown in Fig. Ex 1.6. Taking tuo consideration that the rate of thickening of the ash layer is proportional to the Fate i 7 '© of reaction at that instant, i.e., di/dt = m (~r, ), show that the time to reach any thickness | is the 5 . 3 um of the time needed if each resistance acted alone, or | foot = fin ine * Fs soe * trnton lone Le | Introduction to Heterogeneou 8 Reg, Receding reaction tron, ome reaction rate = kc, sion rate = Kag Cy ' Unreacted solid Gas - solid interface. | Diffusion rate =, ACy 7 ExL6 Solution = A(g)+B(s) + R(g)+S(s) Irreversible G/S reaction ... first order w.r-t. A. Refer Fig. Ex 1.6. Processes or steps in series : @) Diffusion through the gas film, (ii) diffusion through the ash layer/product layet Gi) reaction at the surface of solid. ‘The rate of transfer of A from gas to the surface of solid is given by the following expressions : @_ For the gas film: (ii) For the ash layer ; De ay = To (Cas Cae) MOD = Cy.—Cyg ‘The rate of reaction based on unit surface is Chemical Re’ ‘Adding Equations (2), (4) and (6), we get .. steps proceed at the same rate sy a % tate = Cw "flo. od oy leraa ] = Cry 1 Ta 1| kt otk" 1 Koverat Cag» Keverat Tat gt ate Given: ag = m(4,) dl = mM (KoyeraitCag) dt 1 t fal = meat Ca) fat ° ° at a © = Tn Kent Cag taewal = akote «(7 We have a =m(r,) Now we will obraln the time needed if each resistance acts alone, i.e, if a single resistance alone controls the reaction, @ The gas film resistance controls (if gas film resistance acts alone) : In this case, no f28e0us reactant is present at the surface of solid, The concentration driving force Cy, ~ Ca, becomes Ca, and is constant at all times during renetion, Here +» (8) Cy = Cy KC tion Engineering =I @ dt dl mk,Car ro t = thimaine = TACa, ') The resistance of ash layer controls (diffusion through ash layer Controls) ; 5, =dt Cas = Cag and Cae = 0 ‘The concentration driving force is : Ca, ~ Cac = Cag » De De a PAC = T Cu dl a= ™Cr,)=m (3) Cag Integrating, we get (le t= Game — Cy, (Ze (iii) The resistance of surface reaction step controls : Here Cag = Cas = Cac ER" Cae =k" Cay dl dt of m a )= m(k" Cy) " Integrating, we get L : Adding Equations (9), (10) and (11), we get Yetmatoe + tah a -ace@)+ak (A atx &) nina ant = Ee (f) + he (ala) eae (E wha od mC lee Del * 7 Rearranging, we get to Heterogeneous Reactions chemical Reaction En but Keven = team alone + tosh atone * reaction alone = Kean: Cay .. (12) Compare Equations (7) and (12). RHS of these two equations is the same, From Equations (and (12), therefore, we can write trctuat = tim atone + tosh alone + reaction alone .. Ans. Example 1.7: For the reaction A diffuses through a gas film and then reacts at the surface. A(g)+B(s) > R(g) -» ‘Mass transfer step : -r) = hg (Cg- Cy) Reaction step : oer (i) Linearise the second order rate expression. (ii) With this approximation, obtain a rate expression (accounting for both the mass transfer and reaction steps.) Hint : Tt is decided to carry the reaction at conditions such that the concentration of gaseous teactaut at the surface is somewhere in the viscinity of Cy = 2.5. ‘The Taylor expansion of any function a in the mnt of Cois £(C) = £(Co) + fo We +£ 7 : £"(Co) + vee Solution: A (g) +B (s) > R(g) Ineversible G/S reaction ... second order with respect to A. 1. Mass transfer step :

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