NOTATION minimum value n number of the reactor 5 initial amount or condition é overall e product k recycle condition : 3 surface i transformed variable % combustion t total PRR plug flow reaction DPFR. dispersed plug flow reaction superscripts standard state surface concentration steady-state quantity in defining perturbation variables 4. Introduction and Fundamentals What is electrochemical reaction engineering? Some would argue that it is merely a branch of catalytic reaction engineering where chemical transforma- tions are initiated by an applied potential field. Certainly it is a branch of ‘chemical or process engineering concerned with the application of clectro- chemical technology to industrial processes. More specifically, electrochemical reaction engineering is to electrochemical engineering what chemical or catalytic reaction engineering is to chemical engineering, i.e. that activity Concerned with the exploitation of reactions on a commercial scale. The design of a reactor is a unique activity in engineering and more so the ‘electrochemical reactor which, as well as using the knowledge and infornration froma variety of disciplines (e.g. mass, heat and momentum transfer, chemiei kinetics and thermodynamics and, notably, economics), must also incorporate the principles of electrodics. ‘The rate processes in electrochemical reactors can be very complex bringing together chemical and surface reactions, electron exchange, adsorption and mass transport. Consequently, the rate processes are not only dependent ‘on parameters such as temperature, pressure, concentration, surface charac teristic (catalyst) and pH, but also the potential at the solid—solution interface and inherently, the factors which govern this. The synthesis of all these factors into an economically operating, safe, controllable physical unit capable of chemical transformation at specified rates is electrochemical reaction engineering. The achievement of this goal can be an extremely difficult task, the interaction between the various factors and their subsequent analysis being a complex problem. Hence the approach taken is to begi with the simpler systems, build up the analysis from basic principles and bring in additional factors when and where required, The starting point of this chapter will be a review of some fundamental principles of chemical reaction engineering. 4.1 FUNDAMENTALS OF REACTION KINETICS One of the most important factors in reaction engineering is to know how fast a reaction(s) is proceeding. Fundamental to this is the definition of reaction rate which must be expressed in a usefubwav. For any componentJ, the rate of change of the crate of reaction nosany RUMBEE of moles due to reaction is dd and it volume of reacting fluid is defined as Rw. Y= DG Mol of j formed m=? 5-1 ay For reactions based on unit suri Place at a surface (heterogencous) the reaction rate, init Surface area $ is 1 dN, R= 5° SGe_ mol of j formed m= As will be seen thisj rate ia ‘ a2 general leads aaa ‘© ain interrelation between the reaction spatants, k. The latter term is traditionally introduced to define the proportionality between rea of a reaction conynet Nee Faction rateand some measure of concentration F Or example, with a stoichiometric equation of the type A+ B= products a3) ion (formation) of A is given by Ry Ie reaction is said to be elementary in thatthe rate of Proportional to the numberof collisions of molecules of 4 and Brakios te {im s Proportional io Me eoneenrations Of consiucnts rand 8 The ae of xetion iin this instance sid tobe frat order n both he coneentations Of 4 and B. The “order of rection” therefore sles to the eapenent a a concentration (or equivalent measure) oft particular consttscot found ta e Fate equation. The more general type of rate equation often found so ve 4 good representation of the reaction rate can be wien ia KCAL cr) Ry = -kOACS as) Stier ab reflect the concentration dependeney ofthe particular component om the teaction rate and ean have values ess than, equal to OF great than 10. Such “constant” coeicients must whenever ponsible be determined esperimentally by empirial means and frequently 1 wil be found that they Peat no resemblance to the stoichiometric coelicients, The analyse et tal dita to yield empirical rate equations Is fandamental to any "eaction engisesring. in this respect, electrochemical reaction ie no liferent mmethods of reaction kinetics for analysing rate dats, namely integral methods, are well documented {1} and will no 4 FUNDAMENTALS OF REA® TION KIN, secon he For acon ih tein al scores Saiaprnhenel RO. foal em ‘mined reaction mechanism may well fall short of the final empirically deter “actual” chemistry but the justification for its results based on the mechanism agree with experiment. Th Steps and reaction intermediates postulated in reaction mechanisms are generally suggested by the known chemistry of the material, homologues or species with similar chemical or physical properties. For example, the class of intermediates consisting of stable molecules with one or more unpaired electrons called “free radicals” are as a rule unstable and highly rewctive ‘The electrochemical reaction engineer will almost always tend to view reactions in electrochemical reactors as first order or linear processes. This, as well as satisfying the physicochemical phenomena, makes subsequent solution of what can be quite complex problems much simpler and more easily interpreted, ‘The rate “constant” & appearing in equation (1.5) has the gene dimensions of s~' (molm~*)'~* for a chemical reaction with an overall order of reaction n. The value ofthe rate constant, although often independent Of the reaction constituents, frequently depends on other parameters in a reacting system such as temperature and pH (and as we will see for clectrochemical systems the electrode potential). For example, in the eponid:i- tion of olefins with bromine (which can be formed electrolytically by the ‘anodic oxidation of bromide) the rate of reaction to produce the bromohydrin is first order with respect to both bromine and olefin [2]. The rate constant , however, is dependent on bromide ion concentration, Cy, . sceording to aan expression of the form [3] a (16) jon will clearly have a significant bearing in k [0.967 ~ 0,583 Cy,- ~ 0.368 C} This type of rate constant vari a reactor analysis In general the rate constant will depend on the type of reaction taking place. Usually in electrochemical systems either homogeneous reactions and/or surface reactions occur and in general the interrelation between rate constants is given by kVakS. ayypo OC power supply s ores \ , - ‘ ep - Las) 1) diapheagm: c where @ represents the surface area per unit volume or spec : specific surface of the cathode ae Str. parameter han spa spunea SPE Sei ees te production capacity ote sneer econ cxlcomponents before comsidring the rate ofcectoehe ns ek terms “cell” and “reactor” are synonomous in electrochemical react ‘i engineering. The former is generally more wid ‘ranging as it covers galv: ae prose which chem tanstormation se ent aa energy (electrical) and corrosion processes. However, as the Philosophy of caer wl be adhered Yo in pre on momentum transfer, the term | surface where they may possibly be exposed to undesired degradation .acior will be adhered to in preference to ed degradation Ea - an reactions of one form or another. To prevent this the react b conveniently divided into two compartments by the use of an apprepriate commonplace in electrochemical | diaphragm or membrane. This procedure is commonpl: J reactor design in, for example, the chlor-alkali and metal refining industries. fig. 11. A simple electrochemical reactor o¢ cell HE ELECTROCHEMICAL REA Ge eee Figure 1.2 shows, schematically, a typical membrane arrangement used in Theclectrochemical reactor i a unique unit in which two often quite separate sets of reactions can take place simultaneously. These processes are iments electrolytes by the transfer of charge to or from electrodes (electronic conductors) placed ee inconducting quids or salts One proces involves the redeeeen cy eae ie by the “emission” of electrons at a cathodic surface whilst the other press 2 RNS involves the oxidation of species by the “withdrawal” of electron ae ak anodic surface. Natufally both electrochemical processes must occur smal, taneously with a balance maintained between the amount of reduction at « erode cathode and the amount of oxidation at an anode. A typical electrochemical oe reactor is shown schematically in Figure 1.1 in which the simultancece ssneration of a gaseous product and a metallic product occurs. It is apparent from this figure that there are two other important constituents which make | upan electrochemical reactor. . “A power supply, usually direct current, is necessary to supply the required driving foree, or emf, for electron transfer to occur. The potential difference between the anode and cathode causes the movements of ions to their respective electrode. As a result of the discharge of these ions, dissolved product species accumulate at the electrode-clectrolyte interface. This in {umn gives rise to the driving force which removes the product species from thecleetrodes. These products may eventually move to the opposite electrode membrane electrolytes flow in, 12. A chloralkali membrane cellwe modify the reactor amount of unwanted is not directly involved in product n be done in a number of 20H, = CHEN 222" (cHcH.cN), (19) n undivided electrodes was introduced in the energy cost (see Table ion. This si 12 DIAPHRAC Ste, ofthe Monsanto 1968 divided cell process wy ‘Comparison of he Me process 1 rato un the recent Monsa Divided cell Undivided cet eS et Sora eee Energy consumption (kW h ton~") er oe “catholyte Fg. is brief discussion on diaphragms consider an at fe mode of operation. In principle the use of two, often compl the catholyte and anolyte. Why not To conclude energy an Fa there are a number of inher, is approach, not least with the project engineering. Syn lar reactants, products or operating conditions are fe. An example is the chlor-all generated at the anode 21> + Cl, + 2e7 and the hydroxide generated at the cathode 2H,O + 2e- +H, + 20H~ both have uses in pulp and paper manufacture [6]. A pi application is in organic electrosynthesis, Figure 1.3 describes two ive ventures where both a common reactant (glucose) und a commo Product (glyoxylic acid) [7] are involved, The design of reactors with and quan_——s—sowv NOW AND FUNDAMENTALS ee Goconié acid ‘\ J X\ lear oc ¢ Hey ah ie | ache: 1 t acid glyoxat s (a) ‘ 13. Simultaneous synthesis of (a) sorbitol an ras 5 nnthesis of (a) sorbitol and gluconic acid and (b) gloxylc acid 14. THE RATE OF ELECTROCHEMICAL REACTION ‘Therate of reaction in electrochemical reactors is conv. of the current, J, flowing between the electrodes. Thie reactions at the anode or atthe eathodes whet ‘equal. From sven by aw, for a single reaction the local rate of reaction rv ; C2), '¢ number of electrons involved in the reaction and F is the fant, The total number of moles, Nj, produced in a given time en by iety of products. A number of design fi red which quantify both reactor performance and product quali sali aii ee Bia lala ae a 1.5 CURRENT FICIENCY 115 CURRENT EFFICIENCY I reaction takes place For any reactor in which more than one electrochemical i at an electrode surface, the total current flowing in the cell is the sum of the currents associated with all the reactions, i 1=D4 fate of reaction [,/n)F Each partial current J, therefore relates to the local rate Ly/ny forthat product and the total number of moles of species produced is given by sate (E4} Current efficiency is a measure of a reactor’s ability to utilize curr favour of one specific component and can be defined on an overal basis, ‘The local (point or differential) current efficiency is defined as (ts) (16) (Ce ),= 4 100% ‘The overall current efficiency is the ratio of the actual moles of species produced to the maximum possible if all the current is consumed in that tion, te fire fire the point and overall current effi are only equal when the currents of each reaction do not vaty wi € efficiency can only be determined from quantitati x 100% (CE) = 2C1 + Cl + 207 GHCIO + 31,0 +3/20, + 4CI- + 2105 + 12H” + 6e™T INTRODUCTION AND FUNDAMENTAts in solution Ch + HAO +HCIO +H 4 c- (120) HOO Ht + c10- (ay 2HCIO + CIO- + C103 + 2c + 2H 129 Notice that chlorate. ea eaus a (©) From the analysis of ar chlorate is 1:12. What is Solution Combinin, tion of chi nt efficiency for the formation of chlorate? teacoroutpat sueuns the mls of oxygen t the current efficiency? s + 9HO — 3/20, + I8H* +2C105 + 18e- (1.23) Eg Faradays of wie Be ate feauired to produce 1 mol of chlorate by the overa med Bea J his when compared to reaction (1.22) where ony 6 Faraone Fe consumed gives a current efficienty of cS) anes: (cx), = 78 x 100 = 66.79% (>) Oxygen is formed by reaction (1.23 ) kequiring 12F per mol. Chlorate is formed by reaction (1.23) and preferably by reaction (rej oT Pe ol total there is 1 mol oxygen and 12 mol chlorate Th: quantity of electricity required to produce Onvgee on 12F = 12 F he moles of chlorate produced by reaction (Laake e/g care The quantity of electricity required = 10 2/3 x 6F = 64F. i The total quantity of electety consumed for 1S mol oduct =J2F + 12F + 64F = 88F, Thecurrentefticiency = 100 * quantity of electricity producing chlorate nt efficiency = ——~ TANT TY O° Seeiricity producing chlorate total quantity ofelectricity 12+ 64 88 A ‘goal in electrochemical reactor engineering is to achieve current efficiencies near 100%, a target which is approached for a number of processes, Current efficiency losses are not only associated with competitive electro. chemical reactions at the working electrode of interest, but also with chemical side reactions, physical losses such as evaporation, entrainment and diffusion through diaphragms and processing losses in product work-up, etc. As such, other factors are used to characterize reactor performance. 100 « = 86.36 16 CONV, 1.6 CONVERSION jichiometric equation sug In any single electrode reaction governed by astoichiometric equation v4 + vgB + vpP + VQ d rease while those of prog fractions of reactants x, and xp decrease aera increase during the course of the reaction. Fora fixed amouy xp and xq incr : reaction mixture we can write Xa + Xp + p+ Xo = constant or generally ¥ x) = constant tt ion has proceeded we can introi measure the extent to which a reaction has proc the degree of conversion” which i the diference between the inital rc ofa component and the fraction at any time during the reaction B= ey ‘ The values of € for different components in the reaction are related thro the stoichiometric coefficients, The concept of degree of conversion can also be extended to prod, species. It is often more convenient to measure the extent of reaction in ten of a relative degree of conversion or “fractional conversion”. X,, given b aye den Fhe & a which simply defines the fraction of a particular reactant converted. Throug out this book the concept of fractional conversion is used frequently reactor analysis. It is therefore informative to see what bearing it has on rate equations previously discussed. For a general reaction in the form equation (1.24) the rate of reaction (consumption) of process is given by for a reversi Ra =k CACS ~ CECE in which the initial concentrati ions of A and B are C,, and Cy, and those Pand Q are zero. If we note that the amounts of 4 and B reacted at an1 INTRODUCTION AND FUNDAMENTALS time are equal anid given by Cap Xq = 14 C00 Xp we can write for a constant volume reaction si mami “R= hlCu~ CuoXi"( Cu "86, 1) (Sak By defining the:ratio.of initial molar con becomes centration’ as M HR = hiCist — Xara Ye ~Keae( ex ‘Thus we can uniquely consider rea i function X. Other rate forms can alse bene i also be interpreted similarly. 47 YIELD AND SELECTIVITY undesired products can seriously reduce the market value of thy not rmoved or can considerably increase process plan cons threogh allo separate and purty the product. ‘ ‘one n reaction engineering it is common to discuss the relative production in m rms of two factors, yi Seti, both of which are of utmost importance in the foal coonoaie a . Unfortunately there is some ambiguit : te cll anately there is some ambiguity regarding the use of the We will define an overall matérial yield ¥, as y, = Moles ofstarting material converted to a desired product moles of starting material consumed which can also be defined as moles of desired product Pformed v4 %e moles of A consumed Ye (1.39 = (Coo/ Cay) thi terms of one operating {U7 YIELD AND SELECTIVITY jionally the concept of instantaneous yield is introduced which describes fraction of reactant A disappearing at any instant to form product, P. _ mols P formed Sms eee (1.34) ‘mols Areacted x during the operation of a process unconverted reactant A cannot be ‘overed and is wasted in the operation then a yield based on the amount ‘4 initially present or fed to the reactor is the important economic factor. id is referred to.as the product or operational yield defined as y, ~ moles ofreactant converted to desired product 7 ‘moles of reactant fed id is related to the overall material yicid through, Y= XY (1.35) A factor which describes the relative formation of products during a reaction Is the selectivity S, which for a system where two products, P and R, are formed in separate reaction pathways is given by amount of P produced amount of R produced S= (1.36) Ace than two products are formed we can define selectivities foreach {if easily understood that selectivity is the ratio of the yields of P and R. In a similar manner to point yield, a point or differential selectivity can he defined. It is worth noting that current efficiency and material yield are not synonymous. Processes which have a yield near 1 (or 100%) can have current efficiencies much lower than 100% due to the competition by side reactions for current. A typical cause of this in clectrolytic reactors is electrolysis of the solvent to produce oxygen or hydrogen gases. This is a I problem in electrochemical engineering and manifests itself in a waste of electrical energy. This factor is of prime importance and is considered later in the light of two important aspects, material and energy balances and thermodynani The first and second laws of thermodynamics when applied to the chemi insformation of matter provide a reliable base from which the relationship of chemical equilibrium and the heats of transformation can be determined. Not least thermodynamics will tell us whether a reaction is spontaneous or has to be driven and what minimum driving force or open circuit voltage is necessary. : Wher paiNTRODUCTION AND FUND AMENTais “8 -THE MATERIAL BALANCE Fate ofmass input Ts balance is true for any and a ime. The system being defined ae any unit _ Fate ofmass rate of mass output + rate of accumulation Production = G. ofmass isthe ass OF in the System, A®, is the net input of j into the Fhe’ OF and MyR, is the mass rate of production {chemical reaction. The final term is the net mass fa nomhernctoe OF J by electrochemical reseton: sams the net mass raz control wopeneeus Which is the case for eerinie reese me ich itaccouse ue AV is generally used, Equation (138) torre ene accounts for spec »n by both chemical and electrochemical is used as the basis for developing design en or closed. A closed system is one in Evidently the apy to the overall mate balance for a reactant in a closed system, losed system AQ, = 0. To develop the mater: = M/G¥ ‘and that V = mip whee 38) becores a 4 ay, lance on a molar basis we the fluid density, Henoe MR, MCE), oF 19 THE egy is rearranges tO For a constant mass ™ actor from which jon for a batch react “This in exsencs stymin which the density ofthe reaction to note that only for change of concentration wi ray eases, the density changes Chapter 2. This equation is apy 19. THE ENERGY BALANCE ance is formulated in much the same way as the ma talance of equation (137) by.simply replacing energy for mace Hess only one talanes ex fora particular system Or sono volume Fons form of the balance should take into account all forms"of energy: potential, electrical, magnetic and kinetic [8]. In electrochemical engineering the work done on the surroundings and the therm major factors. For a closed system the first law of thermod: that the heat supplied to a system, Q, minus the work.done, W, surroundings by thesystem is equal to theincreaein internalenee 4 au =0-W Also the enthalpy change, A, related to the internal energy change AH =AU + a(PY) f where P is the system pressure. Evidently for a constant volume stem AH =Q-W—vap.electrical work convertor Fadiation 1 Fig. 14 [nergy balance for a batch process For an open system the requirements of a therm depicted in Figure 1.5 and summarized as follows; CMeTSY balance are accumulation of __enthalp, — enthalpy flow thermal energy = into the reactor — enthalpy flow outof the reactor enthalpy out P in convection radiation (Grotnernic reaction or” enthalpy out (endothermic reaction) enthalpy Flow out enthalpy flow in enthalpy in Joule heat Fig 15 The thermal energy balance. 1.9 THE ENERGY BALANCE terms of the stability and control of the reactor and plant. The time variation ot of energy is usually manifest in changes of temperature of the system (b the hardware and the process fluids) which must not exceed predetermined specifications made on the basis of safety, stability and satisfactory operation. Batch processing through the perpetual intermittent operation is a clear example of a system requiring the application of the energy balance, not only in the start-up or shut-down, but also throughout the reaction phase of the batch cycle. Here it may be desirable to vary the temperature continuously with time to obtain good yields, which may not be possible during isothermal operation. ‘The enthalpy flow into the reactor is from two terms: the rate of energy input from the power supply, the joule heat and the rate of energy input associated with the enthalpy content of the inflowing process fluids. Enthalpy generation due to viscous dissipation, i. fluid pressure losses, is usually insignificant. The rate of enthalpy outflow is composed of the enthalpy content ofthe outgoing process fluids and heat losses from the surfaces of the reactor. The final contribution to the energy balance is the rate of energy generated due to chemical transformation. This may be negative for an endothermic process (output) or positive for an exothermic process (input). It is important to realize that reactions at both anode and cathode and in bulk solutions need to be accommodated. In divided reactors some consideration should be given to the transfer of energy across the diaphragms. In a number of systems the net enthalpy change from the overall reactions is often negligitle. ‘The thermal analysis of reactors and the resulting degree of complexity depends to a large extent on the operating characteristics. Just as with the material balance, the system may not be homogeneous and a microscopic r differential balance may be required resulting in often quite complex ferential equations. For the above energy balance it is possible to formulate a fairly general macroscopic energy balance for an electrochemical reactor as 4 are | Lule Fe = PRY RAH, + TD WCylG—TI-O. (1.46) where J?R, is the Joule heat input associated with the internal electrical resistance R,, Y,R,AH, is the enthalpy change due to all reactions, YW,Co,(T; — Tis the enthalpy change from inlet to outlet for all components with mass flow W,, Q, is the enthalpy heat losses, and T, T; are the system temperature and the inlet fluid temperature, respectively. LmjCp,(4T/dt) is the accumulation of energy in the system. At steady state this term is zero and the solution of (1.46) gives the operating mperature. In batch processes, where isothermal operation may often be7 EN 1 INTRODUCTION AND FUNDAMENTALS desirable, the energy le, the energy balance can be used to determine the rate of heat loss required to maintain ai ‘wired to maintain an approximate constant temperature via PR.=Y RAH, +0, 4 Oy (147) where Qy represents "© Ox represents the rate of heat removal, by say, a heat exchanger. 1.10 THERMODYNAMICS 1.10.1 Heat of Reaction For a reaction of the form. \sA +B P+ 190 | (148) there will generally be a difference between the absolute enthalpies of the sum of the reactants and the sum of the Products, This difference is referred to as the heat of reaction, AH,, at a particular temperature and pressure and is the heat absorbed by the system when the reaction proceeds completely {rom left to right. As such, reactions which liberate heat ie. are exothermic, have negative values of AH, i Enthalpies of reactants and products increase with temperature and, hence, heats of reaction also vary with temperature. To allow calculation of heats of reaction at any temperature a standard heat of reaction, AHfs, is defined, 's of which can be calculated from standard heats of formation, (AHF). or standard heats of combustion, (4/13) for the reaction constituents [91] The heat of reaction at any temperature T is calculated from AH? = AH:, +f AC, aT (1.49) where T, is the temperature of the standard chosen. In the same way the heat of n can be calculated for any new temperature, Tz, as illustrated in Figure 1.6. This is essentially an application of the conservation of energy law. AC, is the difference in the molar speci reactants, ie. heats of the products and AC, = D(v4C,,) products — F(v/C,,) reactants (1.50) C,, values are generally functions of temperature but over relatively small ton also vary with pressure but for liquids the effect can usually be * Generally heats of| ed. 110 THER enthalpy products —p jaHr2 (He Hp ¢ (te T; “Temperature = fig. 16 An enthalpy-temperature diagram. perature ranges experienced with liquids they can often be taken at s appropriate mean value. PETpe equations above allow us to calculate heats of reactions essential the computation of energy balances. In electrochemical reaction engine we must also be able to determine which direction a reaction proceeds in, 1 final composition of the mixture at equilibrium. 1.10.2 Reaction Equilibria Reaction equilibria are best viewed using the concept of Gibbs free energy [10}. A reaction proceeds on its own accord when the G + ture decreases, ic. a negative change in Gibbs free energy, A. spontaneous reaction, A zero AG value defines the equilibrium of The second law of thermodynamics provides us with a number of re for the calculation of equilibria AG’ = AH? — TAS* where AS* is the entropy change at the temperature standard ‘J, given by T AC, asr=asz+ ["4Ceq 3 [i T Tr a and . AG = -RTInk where K isthe equilibrium constant and R the universal gas eons1 InTRODUCTION AND FUNDAMENTALS lated from stand: ie namely andar tre enersies of formation, Products — F (1,6) reactants (ss) ibrium cor ues. “ORStant, K, at standard conditions can be (1.55) for activity coefficient “a”. ium constant and hence equilibrium wing way by combining equations dink _ AH: aT RT? (1.56) lest form the integration of this for a mean AH? (temperature ) gives (£2) eel [ills K, ReLT T which relates the respective equilibrium constants at the two temperatures id T,, Values of the equilibrium constant make it possi ¢ it possible to predi ction will proceed. The typical influence of ture on constant and the equilibrium conversion, X,,, is illustrated éndother mic T 4 Fig. 17 The effect of temperature on equilibrium conversion and equilibrium constant. 141 EECTROCHENICAL THERMODYNAMICS Alternatively, equilibrium conversion (or composition) calculations deter- mine whether the desired reaction will proceed. It is worth stressing that the procedure only determines the desirability of a reaction, not the rate ich the reaction proceeds which is generally the factor which governs 1 selection. Having briefly reviewed the chemical aspect we shall now turn our attention to the thermodynamics of electrochemical reactions. 4.11 ELECTROCHEMICAL THERMODYNAMICS |As with chemical reactions, thermodynamic calculations for electrode reactiors determine whether or not a reaction is spontaneous. However electrochemical reactions are somewhat unique in that non-spontaneous processes can be made to occur by doing work on the system via an electromotive force (emf). ‘The emf which is sufficient to cause an electrochemical reaction to occur at an infinitely small rate is referred to as the open circuit cell voltage, E,. 111.1 Open Circuit Voltage Consider the simple electrochemical circuit depicted in Figure 1.8 which consists of an anode (positive electrode) and a cathode (negative electrode) both immersed in an electrolyte and connected to an external circuit. If we now take this to represent a galvanic process operating at zero current and recognize and accept that there are electrical potentials (or interfacial potential differences, known as the galvani potential differences) at both electrodes, denoted by E* and E~, then the usual convention, and that adopted here, is to define the open cell voltage as E,=E--E* (158) Clearly the situation depicted in Figure 1.8 is idealized in that there is no potential drop across the electrolyte solution (or diaphragm). Fig. 18 Open circuit voltage of a reactor.calculation of cell voltage. Pen circuit voltage, giving AG = — nF ge determine whether o: F not a reaction as written i E*). An electrochemic: ae reaction with a positive E* n the cell in the form of an -d emf from ox rom thermodyn: iamics to extend the analysis to estimate ‘ermal conditions and to calculate This, however be driven by an applied applied and electric current flows, the ive due to composition changes induced then said to be “polarized”. 1112 PRACTICAL CELL VOLTAGE REQUIREMENTS AND POLARIZATION go hand in hand in electrochemical 1e degree of polarization of a cell is n is due to three effects, which make up ion polarization. This ‘ed with the phenomena of electron transfer across ion of values of E, the open circuit voltage is related to (1.59) ard (oF reference state (298K, atmospheric (1.60) the electrode~el certain amount of energy at the electrode. This energy 1112 PRACTICAL CELL VOLTAGE REQUIREMENTS AND POLAy, nm said to rolyte interface. An electrode is ma oe fate the change of state oc rreversi the form of an activation or surface overpotential. Concentration polarization, att indicat of the concent electrode from their bulk concentrations. ‘means of reference electrode, as shown in of the current flowing in the cell. voltage Source importance in the rate processes occurring in the cell and is me: Se nea ture 1.9. The potential diffe, between the electrode of interest (working electrode) and the refers electrode is known as the electrode potential (E, or E.). this is referred to as the rest or equilibrium potential. To measu the reference electrode must be almost completely reversibl act as either an anode or a cathode, regardless of the polarity of the w. clectrode. The reference electrode is capable of reaching e tancously and exhibits a stable and reproducible potential, which is independ. Fortunately there ate a number of electrode systems which exhil above characteristics [12], of which the standard hydrogen electrode working ele: reference electrode Fig. 1.9 Measurement of electrode potential mutable to changes in compo, P lectrode surface. The v of reacting spaties near the electro a a ian wll re is that due to the electrolyte, diaph and electrode materials and electrical connections. Tn an open cir . be rium secondary electrode1. INTRODUCTION AND FUNDAMENTALS ‘Table 12. Standard électrode potential at 25°C Tear ponemnial aac geret___troemiin___ ii fee” ree 8 From such.data we can evaluate the ‘minimum voltage requirement for any two reactions Emin = E. + (~E, (1.62) ‘As mentioned earlier more practical systems will require correction for the of participat ia the Nernst equation. Returning now to the cell ‘voltage which is defined as follows Er = Ey +n.—n.—IR, This voltage will be negative for electrol the prime concern of this book. From eqi reactor performance in terms of an energy efficiency, which the unavoidable energy or voltage energy or se requirement Ey. However ined from this as significant currents are required in processing and values of Ey are general greater than E,.. What we clearly need is possible. This can be done by, keeping cxample using sm (1.63) ic (driven) reactions, which are 1¢ ratio of An alternative way of reducing the cell voltage is to change the counter clectrode reaction and reduce the E, value. Two examples of this approach, one for a cathodic reaction and one for an anodic reaction, are now considered. uzATion {L12 PRACTICAL CELL VOLTAGE REQUIREMENTS AND POLARI2 3 ear vouage er Clone Call ‘membrane or diaphragm cells, th chlorine ions to chlorine .¢ anodie reaction is the reduction of 64 2Cr + Cl; +207 BE= ITV (1.64) and the cathodic reaction is the reduction of water _ 2H,O +227 +H, + 20H”, Et = —09 Jd the overall reaction 7 66) 2H,0 + 2CI" + Cl; +H, + 20H is approximately 60-70% of rat chlorine reactors, Industrial reactors are mn voltages and hence, at the production level ang the overpoteatial contribution pe 10 use a cathode based is minimum voltage requirement fo Seman i ened vo mina other fi I of effort has gone it 2H,O +0, + 4e7 +40H™ EP = 032 V ‘This therefore gives a value of B= Et t= -095V is very atteacive giving a saving of some 12V. Indeed, in the Tocelfallbusises it very import re Spnology. At present, however, there are a number of drawbacks rega reactor process design. EXAMPLE 14 : ing Voltage for Metal Winning Srna ing processes for metals such as copper and cobalt the cathode reaction is written as. M?* 4207 + M fhe usual anodic reaction is the generation of oxygen according to H,0+2H* + 40,1 +2" Bp= 1.26 V fhich (1.68) 69) ‘The overall reaction is therefore M?* +H,O-+M 42H" +4031 Values of E*(= 6? — E2) for copper and cobalt are, respect EQ, = -096 V, Bt, = —1.54V It however alternative anode reactions are used such as: dioxide [14] (1.70) SO, +2H,0 +4H* + S037 + 2e” E2= 0.13 V"INTRODUCTION AND FUNDAMENTALS and hence F&=O1TV and £2, = —041V ©F (ii) the oxidation of Sulphite to sulphate [15 SO} + H,0802- 4 2H> 4 26- Eye OV Cae Biving £2,=019V and £2, = 039 V incon Rts in cell voltage requirements ae achieve. Tn the cae ‘of copper winning ‘A major drawback with the abo Process viability and cconomice hy Product ammonium sulphate is ve approach is that reaction chemistry must match in the case of sulphite (ammonium) oxidation the of value as an intermediate in the formation of 1.13 ENERGY CONSUMPTION "aving discussed the components which make up the overall cell voltage, @ SPgs8 ctor of great significance and which is proportional to this paranveter unit aenstey Consumption. This is the electric energy needed to produce a unit weight of product and is written as nEE 36-M-(CE) {here M is the relative molecular mass of the produets. Every effort should be made to keep this value as low as possible for any operating caneat Clearly, electrolysis conditions should be selected which make manimvum ace cof the reactor current for the desired reactions, ie. high current efficiencies are needed, Energy consumption in commercial processes such as chlor-alkali and cobalt electrowinning are of the order of 25-3.0kWh kg". By application of the anodic oxidation of sulphite to sulphate (reaction (1.72)) im cobalt clectrowinning, it is demonstrated [15] that energy consumptions cae be reduced to the order of 1 kWhkg~! In the previous section it was assumed that at each electrode only one desired reaction occurs. This, as has been indicated through the deivites of current efficiency, is frequently not the case. From a thermodynanvie viewpoint such undesired side reactions will occur ifthe associated equilibrium Potential is less than the potential of the electrode. We can assess such situations with reference to tables of standard electrode potentials (Table 1.2), We know that the more positive the potential, the more readily the reaction takes place at a cathode and vice versa. According to Table 13 Energy consumption = KW hke~? (1.73) sok CLASSEICATION, CONFIGURATIONS AND PROC, 1 REACTOR CIA more readily than hydrogen evolution, Mgr sem favourable Fortunate sive apart hate-sulphurie acid solution depostiompalt in aqueous cobalt sup ve deposit cobalt Pe concentration can be established which fe’ of pH and cobalt ress hydrogen evolution to an extent deposition and SPP iGo % [16]. Conversely, the copper depose’! efliiencies PPro namically favourable, cam become unfavour, athoUEh ers Generally, the relative magnitude of competing sie nerally, € concentrations Getgy thermodynamics, but also and mor: imper is not just govern oth kinetic and mass transport) occurring ing the rate process cet iris worth noting a class of reaction systems yal AER ong 2 Se se f onganie halides [17]. The reactor is based on fuel cell cchnojy Seen hydrogen electrodes in conjunction with olefinic catalytic. ‘copper depositio 1:44 REACTOR CLASSIFICATION, CONFIGURATIONS AND PRODUC, : CAPACITY cactors may be classified in a number of ways; usually in tem characteristic the number of phases present or by modes af the latter case reactions can be classified as either batch or conten scale processes tending to be performed on a continuous mode ihe There is however a category of reactor lying somewhere in tee classification, ie. semicbatch, Hlere one or more of the reacine ey is fed to or is continuously withdrawn from a batch vessel, 1S shy Figure 1.10. By including semi-batch operation as. distinc can have defined a batch reaction as an intermittent operation n nih 's supplied and withdrawn during the reaction eycle. Clary see semi-batch modes ean be carried out indefinitely and operation is necessary. Of the three semi-batch modes ype isthe more likely to be adopted for electrochemical reactons ine 1.44.1 Flow Characteristics cd ‘The classification of reactors in terms of flow characteristics is not sou as by other means because, in a number of systems, siich Unknown or ill-defined. From an engineering viewpoint the division into two ideals, either plug flow (or piston flow) obLontinuous a— + oe] [+] Pap) ‘ 6} _P A B A aot bd ed f+ (AB feed (i) Binitially (i)constant continuously dumped ty crete aad ¥ Ha ~~ ]- “Lanier composition eee cone > ce distance feed ol product 5 110 React ications: (a) mode of operation; (b) flow characteristics Jeal mixed, well mixed or continuously mixed) is fundamental to i reactors (see Fig: 1.10(b)). 4 lamental to; the, dasisn. 1 The Plug Flow Reactor (P.F.R) isacontinuous réactor operated, in most cases at steady state conditions. is usually in the form of a well defined flow channel, either inular or rectangular in cross séction.—Fluid-flow-through the such that once an element of fluid enters, it neither mixes with lement in front of or behind it. Distributions of velocity and species across the reactor are uniform. Each element of fluid entering 4:14 REACTOR CLASSIFICATION, CONFIGURATIONS AND PRODUCTION CAPACITY the reactor behaves identically throughout steady state operation and only along the reactor fed Tank Reactor (CS.TR.) is an ideally mixed vessel, operated continuously, in which the wn of the reaction mixture is assumed to be uniform. Thus the Wn of the product stream is equal to that within the vessel. Mixing jough gas jets oF ‘comp is usually accomplished mechanically using stirrer bubbles are sometimes used. 1441.3 The Batch Reactor (BR) This reactor operates in an ideally mixed mode having at any one time, a uniform composition. Processing of a fixed mass of feedstock is carried out in batches, which is generally only suitable for small production scales. A mode of operation common to electrochemical reactions is referred to as recycle batch operation, where a batch of feedstock is reacted in a closed « design engineer mus aware that these flow characteristics (cideal behaviour and that real performance may differ significa ‘The designer must assess whether the actual behaviour is g00 enough to be taken as ideal and, if not, act accordingly. Such action may to more closely approach the ideal or to determine cnown example of jeal flow in reactors is that experienced in fluidized beds, Such systems ed in the area of €Tectrolytic metal, recovery 14.2 Heterogeneous or Homogeneous A third way of classifying reactors is in terms of the number of phases present. Homogeneous reactors are those in which only one phase is involved in the reaction, for example, a chemical reaction in a liquid medium. Heterogeneous reaction systems are those involving more than one phase, i liquid-liquid, or gas-liquid—solid, even though the react proceed in effectively one phase (homogeneous). Heterogeneous systems al encompass reactors which, although they only process a single phase, the contact between a second solid (or liquid) phase, typically a cal Electrochemical reactors are in this category. ‘Within heterogeneous systems we may also categorize reac in terms of the mode of contact of the phases. Indeed, two fluids m:7 “lems a eer 7 INTRODUCTION AND FUNDAMENTALS tapes) CouMer-curently of co-curreatiy, one may be mixed (or nearly benppry ar tilst the’ other isita plug ssw: ta duidiae Gols, ihe soba ae ‘PProximated toideally mixed whilst the Aud may be near to plug flo. 1143 Production Capacity hs Production capacity ofa reactor may be defined in a number of ways speach the same way as reaction tate The rate of prodection of a species Pet unit volume of reactor(mol m-* s~ or equivalent units)isrelerred to as the space time yield. Fe rogencous systems we could equally well consider production cap: 5 of uni of catalyst, unit surface Of catalyst or even specific STY. = mol m=357? 100nF E,jie SOC Ee gm 3h? 1.75) 100nF KB 1.75) electrode kinetics and mass transport. It also tends to control the curr efficiency obtained. The specific surface, however, depends on the type of cell Proposed and on the electrode structure. Clearly high specific surfaces are desired to achieve high space time yields, espe electrodes based on parallel plate or other configurations. A variety of reactor dt CLASIICATION, CONFIGURATIONS AND PRODUC 114 REACT clectroiytef flow in ‘Nalco packwed bed [repro ganic Synthesis, ed. NL. Weinberg ted and adopted indus just as in heterogeneous catalysi opting for high surface area reactors, does Problems of flow distribution, concentration variations in the bed need to be solved. in three-dimensional electrodes there may also be a non-unife n of current density and electrode potential in the structure, bution and temper1 INTRODUCTION AND FUNDAMENTALS dimensions. This non-uniform distribution problem to analyse and solve. In essenso'y ofthe available electrode area i can be seen as an su ronan ean aida here rate, This factor referred to as the eflesie rm reac ness, #, [20] is defined as ‘deal rate based ona uniform current Ustabation later in Chapter 7. ‘ith two nc © the '0-dimensional electrodes, distance bet ler of 300-800 kgm-?h-!, sed inthe cletosyathesis of also give rise to low ther factors, such as , i ci mass transfer rates, gas evolu ind mechanical design requirements must alse pe inexpensive, as us ter-electrode gaps (145. BASIC ELECTRODE KINETICS _Wehave seen how, in principle thermodynamic data can predi ~ of a reaction occurring. At what rate, and indeed whether or et ‘depends on experimental conditions. To be able to quam -atial at the metal-solution a stable and reproducible pot 'e change in potes clectrode needed to change the tude of the current de ‘measuring the potential difference between the reference and worko There are a iber of practical points to be followed when ls [21]. z ion of a reference electrode adi fere with the flow of curren ice reference electrodes are 12)and connected to the: at atypical distance of appt advantage of mi jacent to a working electrode is of reaction rate is often a dificl , the specific surface ween the electrodes. Thus the nee ene ily the processes at 1135 HASIC HECTRODE KINETICS ert omar (b) e ie Lise asf MW. 1 se. we ‘ a Re + 2 Measurement of electrode potential-current density relationship: (a) galvano- potentiostatic, ice and working electrode, associated with the ohmic resistance of the is way a high degree of precision is obtained in electrode iship between current densi experimental measurement 10 approaches normally adopted (Fi \d electrode potential, required. There are fixed values and measured after an approximate steady state is reached: Potentiostatic, in which the electrode potential is set at fixed values and the resulting current densities measured, ‘The potentiostatic method is the one most commonly used. Details of imental equipment and techniques are well documented in the literature iostats can be run under computer coi igure 1.13, imple redox . could be a typical curve ert metal surface One BR 76) in the electrolyte solution. However the reactions by such equations as (1.76) can be misleading. Often they are multistep processes,[hot only involving lectrochemical steps, ut also transport of products and reactants and chemical transformation Additionally, phase transformation may be involved mewn _— 1S BASIC EU -taog, 1. INTRODUCTION AND FUNDAMENTALS as well as a bonding intermediate species. ‘Transport processes are apparent even in th reactions. For the electrochemical reaction te (adsorption) between the surface and O, R or an le layer. fig 134 The double ly " simplest” of electrochemical : ee oe pee oie rnecies O. TAS De fundamental importance in el istry and can dy {upPlied (diffuse) to the electrode and conversely, species R must be removed ia oa sge at the metal-solution interface, but to date Wey from the surface. If either of these two processes is slow in comparison structure to reaction kinetics are howeve {he electrode reaction then they are said to become “rate controlling”. T 3) asa ely the currently held (and convenient) view in clectcoches a ly held ( a ) as a rapid fall-off ly as electrode potential increases in ferface are not of over de potential where no permanent mace os in this region changes the charge oq f» layer characteris a "face in much the same way as a condensor. Species in coubss ters "trode are unevenly distributed due to the existence of chemical and shor carried by an of polar molecules, thus the lectrolyte solvent (eg. water) forms a layer at the electrode surface, Neiong is of double layer structure and measurements are svailab aXe ss strongly solvated than cations and consequently they can approach || umber of texts and excellent expositions on the subject [23st the ferred to as the inner Helmholtz plane | therefore we shall concentrate on the theory of electrokine! solvated anions. These anions can th a simplified basis for electrochemical reactor design.) layer of cations and unadsorbed ions plane: the complete region is known [| 1.151 The Electrode Potential~Current Density Relationship ter Helmholtz plane ae The basic electrochemical process of equation .76) is considered umber of prope such as differen O+nme=R can be measured to determine double layer capacity and interfacial tension. These charac where strictly speaking O and R are charged species.INTRODUCTION AND FUNDAMENTALS When « net reaction takes place th 1 cui difference between forward and reverse rates APR Ch exp (1 — one] Where C5 and Ci are the concentrati ten values ofa’ are cl the activity of the components should be used rather than th . but for the typical low concenteations ee in elect Kinetic measurements a ficients remain constant, ee 77)(1.78)4nd\(1.79)ean be conveniently combined to give MELKC3 ~ ky, C) where the rate constants are weitten as Kya = ky expl—a’nfE] Ker = ky expl( — )nfE} where f= F/RT. ‘As written the convention ado} cathodic currents are positive. The values of the rate constants k, and k. Potential chosen. The rate constant Potential £° or the equilibrium potent ted in equations (1.80) to (1.82) is th 4 depend on the reference can be defined. in terms of standard E, according to Kyy = ky expl—(E ~ E*)e'nf] (as: (1.84 = FRG, MPL -(E ~ Eng] Kor = ky expl(E —E*)B'nf] FC, exp[(E — E,)6'nf] 1145 BASIC ELECTRODE KINETICS is the standard rate constant. _ to give a degree of diverge from “sym- ‘The term fi is introduced (no: piricism when the rate equat metry” (ie. when f° +0’ = 1). Frequently values of E, (the potential when i= 0) cannot be measured present. In this case E” is .80) becomes yn may experimental is case equation useful reference point and in (1.87) where n= E— E,. ts briefly consider what is meant by the exchange current density. At equilibrium, the forward and reverse current densities are equal, ie. Fk C2 expl—a'nfE] = nFk_ Cy expl(1 — &)nfE} (1.88) and, as already noted, at equilibrium E = E, and hence from (1.86) nd (1.88) i, = nFk,C, expl—a'nfE.] (1.89) noting that with no current flowing the surface concentration and bulk concentration are equal. At equilibrium, the potential of the electrode is defined through thermodynamics from (1.83) and (1.85) as, Cok expl—(E — E*)ernf'] = Ck expl(E — E°)(1 — a)nf] which gives RT E=E*+—In| = oF “(&) which is the Nernst equation introduced previously in Section 1.11.1. Having earlier identified that electrode rate processes are governed both by kinetics and mass transport, let us initially consider the characteristics of equations of type (1.87) when mass transport limitations are absent, ie. when the reaction kinetics are rate determining. (1.90) 1.152. The Butler—Volmer Equation Consider the characteristics of the general rate equation (1.87) when mass sport is not rate limiting. As a good approximation, the surface concentrations are equal to the bulk concentrations, i.e. C=C, Cho Cn1 INTRODUCTION AND FUNDAMENTALS and thus we obtain #= Lexp(—a’npn) ~ exp((1 —«’)nf)] ast Imer equation. The current density-potential relationship ee parameters j, a” and E* In kinetics we are generally the meas of wi the Butler—v depends on only). soy xPerimentally confirm the Butler-Volmer (B-V) relationship and ‘indeed that ais independent ofn, equation (1.91) can be rearranged inthe form Fig Fig. 116. Plotof equation (.93)for determining kinetics ofthe Butler Ving, f= 4, exp(—enfn)Lt — explnfn)} (192) S a This, when plotted accordingly on a semi-logarithmic scale, ya an of a’ and i, (see Fig. 1.16). i I aoe | — an 1.93) \e Tafel Equation n(; =n) Po (1.93) [4353 the Tafel Equatior a aes by: ‘An important limiting case of the B—V equation is when rey °Y potentials are encountered and the reaction effectively becomes itt jy, (or may be intrinsically irreversible), 7 = 0, giving 5 Thi Which is known as the Tafel equation. It is generally a good appran exc to the B-V equation, at values of |7| > 50 mV, but obviously thea is an important approximation chat industrial operation is us ion rates and implicitly at high 7, ene ‘The Tafel equation is also amenable to kinetic analysis when ree suitable form, such as In(i) = In(i,) — anf is, when plotted on a semi-logarithmic scale, gives the values of Figure 1.17), The above current density~potential equation was lermined experimentally in the form wh n= a+b log(i) ae Msequently, electrochemists almost without exception discuss this ferms of Tafel coefficients and in particular the Tafel sloy Fig. 1.15. Effect of the transfer function on ButlerVolmer polarization curves. 2by ch em lew ai ure slope = nf Fig. 117 lot of equation (1.95) for determining parameters ofthe Tafel equat relationship between a’ and b is (in mV) p= 2303RT nF ( For a simple reaction, is approximately 0.5 and with n = 1, is characte by 2 Tafel slope of'120 mV decade~ ps charecterized Atlow potentials, the B~V equat between current density and potential imple linear relationshi = infin si This expression is generally of little use in electrochemical reaction engineering, except perhaps in defining limiting characteristics of operation. equation as presented above is derived for a simple redox used. If in the overal encountered, the general rate expressions are and where determining step must occur for the overall reaction to occur once. For a Tafel type of analysis of experimental data this will have 1LA5 ASIC ELECTRODE KINETICS bearing on the correlat the value of v will not be obtained. For a B—V lysis, based on (1.93), the experimental value of n/v (n/v now replaces n in equation (1.93) must be correctly chosen before a linear correlation is achieved. Thus by a trial and error procedure the value of v obtained, assuming 1 is also know! = 1.154 Mass Transfer Dependence of Reaction Rate So far, it has been assumed the electrode surface is appr iat mass transfer or diffusion are always present when curret surface result from the mechani of species O to the surface occurs i followed by reaction at the surface and then diffusion of products away from the surface. Thus, even for simple reactions there are a minimum of three rate processes to be considered, all of which may be rate Mass transport ist the concentration of an active species at to its bulk concentration and flows and concentration gradients at the depicted in Figure 1.18. Here, diffusion nally ascribed to three modes: trolyte. Electrolyte sol different or suppor experiments and preparative experiments, inch thesis, In these circumstances the migration contribution to diffusion 9 7 difftsion in Os E butik |e Solution Rs oe diffusion out electrode surface Fig. 1.18 The overall mechanism at an electrode surface.[Small and usually neglected. We shall, however, encounter systems ater where this assumption cannot be applied Convection: the movement of species by some mechanical means. ‘may be natural convection as a result of, say, thermal gradients forced conve tion is of troanalytical chemistry where a controlled or measurable degree of mass transport is required. It however, of importance in electrochemical engineering in cells used in hydrometallurgy of, for example, copper. In both discipi important to be able to quantify the eect of mass transport, Inroads into the mass transfer characterization of electrochemical reactors are being made, but a lot is still to be learned, especi scale equipment. (Gil) Diffusion: the movement of species'as a result of a concentration Bradient, In electrolysis this mechanism occurs between the electrode Surface and the bulk solution. The flux of a species to and from the surface is proportional to its concentration gradient at the surfa as defined by Fick's first law of diffusion, flux A = —p, 2G) 10 * AX leurtace o mol m7?s7! the diffusion coefficient of species j. The above equatior ¢ often adopted one-dimensional form, is the most geners ing mass transport rates and can be obtained by solving ‘more complex convective mass transport equations [27} In the absence of chemical reaction in the electrolyte solution, the concentration variations of reactive species near the electrode are almost linear. Thus, a mass transfer film thickness (diffusion layer) is defined, in which all the resistance to diffusion is said to occur. The Mux equation (1.101 then becomes a simple algebraic equation written in the form Nm klC,- C21 (2.102) sport processes i A, may simply be Seon 4155 The influence of Mass Transport on El in Figure 1-13, that as electrode potential incr current density, in IE rtration of species O decreases. fveng Sn here once Elta a alt on concentration of speci’ jtuation is such that as Soon as reactant Seti ee ation sch has S08 an id is given by the reaction rate ani Lone, oF is concept of limiting cur here is the limiting current density This concep 3 aa cer mal engineering forthe determination om heat transfer coeficents (28] “Assuming that the mass transfer coefficients (1.103) are identical these equations can be combined txpresion forthe surface concentration (immeasurabl =e, A similar argument can be applied to the product species R. ‘Usually the expressions for surface concentrations are combined rate equations, e.g. equation (1.87), to give general rate forms which « both Kinetic and mass transport events. Thus we obtain where i is the limiting current density of the reverse react ‘rearranged to give a similar expression to equation (1.93) 05 ‘Athigh potentials, when only the forward rateiis important, this reduces ‘This expression is of the Tafel form where i is equivalent to a current den: = a'nf, aea eee rece eee a JcHON AND FUNDAMENTALS ees a the absence of mass transport fl efletsof concentration Sfemuy Tocvauateclec ns iets a pe carotene he age. has been suggested [27], je. tO" Polarizal ‘aperinfental plots reveal the reaction order, ie i Note that the reaction order determinations should normally be made in the absence of mass transport In many cases the value of q = 0. Providing . hen the reverse reaction cannot be neglected, the following procedure may be adopted to evaluate reaction order. Starting from the Nernst equation and combining it with equations and (1.82), the exchange current density is obtained as (21) a.uay ue aFRcr-mercg exp( UE) aunts) Note that the term n/v has been introduced, as discussed previously to indicate the possible complex nature of the reaction, Equation ( also be written in terms of the standard rate constant, i ) can fe ka CCR Consequently since both £, and ky are constant, diagnostic tests of reaction order are Since w and m are readily determined, combination of these equations fives the value ofp. Such procedures are often of use in reaction mechanism mations. Two examples of the concentration dependence of are shown in Figure 1.19, Experimental data for copper deposition from ference [29] clearly demonstrat inCr le, th the reaction order can ‘acetophenone to although showing. mn over a limited range, indi bbe expected other factors, such heterogeneous (ca present will not is considered later in the following chapter.C350, concen (o) Fig 149 Gaamples of vaaon osc tsken om toca att Razag (30) oe E neering, Wiley, New York, em. Soe, 3260. pojsand AKN Reddy 1970) Moder Blectroskonay. va 10M. res, New York Gd CH. King ey, Ne Enc: ) Technique of Electroorgan Sug 2. Ideal Isothermal Reactors: Single El Reactions: gle Electroct Sc. Das Sakell OF, Cernm, 9p This chapter deals trochemistry, Chapman and Hal, chemin onda, plug flow reactors are treated in turn. A final Bperation of recycle reactors Without exception isothert Groumed with the underlying theme being the design a 3. HR Th IReademie Press, London. nd LR Faulkner ‘Wiley, New York. rion 1968) Double Layer and Electrode Double Layer, Pergamon Press, Oxfoid ‘and J, Penciner (1973) 79) Electrochemical Reactor Desi Engineer, Jan 39. rand Y. Kato( 198! respective total rates are cou [Processes use reactors i segregated. Such segr fand there between species from b jon and other more “complex” systems ‘This chapter will concentrate on reactor ther separated or not {rom the co consider the course of the desired reaction. This is sg the mode of current supply to the reactor; either ga