CHAMORRO | JUAN CHAMORRO ATLAS OF ELECTROCHEMICAL EQUILIBRIA IN AQUEOUS SOLUTIONS BY MARCEL POURBAIX ‘Translated from the French by JAMES A. FRANKLIN (xcept Sections 1, 1115 and 1116, which were originally written in English) NATIONAL ASSOCIATION of CORROSION ENGINEERS Houston, Texas, USA CEBELCOR BrusselsNational Asceain of Comesion Engnosre 2109 Wont Loop Sout Mouston, Texas 77027 Cecie Bale € Etude de a Conation CEBELCOR, $0 Av-F.D. Roosrel, Brees $ Copyright 1974 ‘ational Assocation of Corosion Ensiners Fst English Eaton 1966 seamen Pres Lid stcond Engh Editon 1974 Notional Annan of Corouion Engneers brary of Congress Catalog Card No, 6511670 PRINTED IN THE USA BY NATIONAL ASSOCIATION OF CORKOSION FNGINEERS 2400 Vest Loop South Houston, Toxae 77027 ATLAS OF ELECTROCHEMICAL EQUILIBRIA IN AQUEOUS SOLUTIONS )| | | CONTENTS List oF Corraunuzons Aonousreazive Cousen. oF Cetsicon CCosnusion ov Erupes FoNpawtesratss et Apbucamons CEFA Fonswozo by W. G. Burgers Puerace by R. Ponte Guossiey Novamox aso AnaResaTioNs 1. Inmooucros by P. Var Rysteberghe [Xsatochemica)thermod yaamies and kinetics 1, Menioo oF Estantisuine Pornerl-pH Equaraniun DIAGRANS by Mf. Powbate TL, Ust oF Poresrat-pH EquirmRion Discrass 1. Generales by M. roURBAR 2 General chemistry By 6, VANS! 3 Analytical chemistey 6, cantor 4 Corrosion by M nots 5. Eleetradeposition by 7» HoAR 6. Goology by RM. Gans IN, Estaausinavt asp [vreerReraniox oF Portstiat-pHt Eouaiaattnc DiaGkass H,0, 1,0; u Li Na, K, Rb, Be, Mg. Ca St, Ba, Ra BAL Se Y Lanthanices La, Ce, Pr, Nd, Pm, Sm, Eo, Gd, Th, Dy, Ho, Ee Tm, Yb, Le Actinides Ac, Th, Pa, U, Na, Pu, Am, Cm, Bk, Cr Th zr, HE VNG Ta 1. Ge, Me, HL Ma, Te Re 12 Fe,Co, Ni 15, Ru, Rh, PS, Os Be rr 15 18 Guin, Tl 17. C8, Ge.sa, Po Ie NP, As Sb Bi 19. O1S'Se Te Po, Hal 20 F.C,Be 1 YY, Tanees 1. Periodic classification of the elements 2 atemationa atomic weights 4 Order of srangemeat ofthe chemical sements in Chapter 1V ‘Aurion Inex Scare INoex es PageLIST OF CONTRIBUTORS ‘pessox, 1, Univesity of Grenoble, France. Beever, J. P, Univesity of Strasbourg, France “Boncers, W. G, Technical University, Delft, Netherlands. “CuaRLOT, G., Uaiesity of Paris, France. *Dstastay P.. University of Louisiana, Biton Rouse, La, US.A Drerosse, E, Belgian Centre of Corrosion Study (at present with the Sociéé des Laboratoire: Labaz, Brose. Belgium). be Zousew, N,, Beslan Centre of Corrosion Stody, Brussels, Belgium (at presens Harvard University Cambride, Mass., U.S.A.) “Gannets. R. M_ Northwestera University. Evanston, It. US.A. “Hoan, T, R Universiy of Cambridge, Great Britain “Iouas, F., “Les Pils Wonder” Company, Saint-Ouen, France *Kuyz. W.. Univenity of Saarbrieken. W. Germany. MaaacHint, M, University of Rome, Italy. “MoussanD, M, “Les Piles Wonder” Company, Saint-Ouen, France *porcuts, R. Mien Polytechnic, Tey Priva, A. LNwal Research Laboratory, Washington D.C, USA. Ponaats, M, Belgian Centre of Corrosion Study, Brussels, Belgium, Scavers, J, Bean Centre of Corrosion Study. Brussels, Belgium (at present with the Centre Etude de {Energie Nucléaire, Mol, Befgium) l *Scviwane, K., Unitesity of Dresden, Germany. “Vatenst, G, Univesity of Poitiers, France. evasteucennacte, C., Belgian Centre of Corrosion Study, Brussels. Belgium (at present with SERA Basel). “Vax Muvtoen J. Belgian Centre of Corrosion Study, Brussels, Belgium, vas: Rvssetoetone, P.. Stanford Universicy, Stanford. Calif. USA D sf Themmodyomic an Elta! Kieios “CTC. andor ofthe Cor Unoa af Tue and Applied Cheniary“LULPAC: 5 + Menten fs Intima Corsi nision of Bete of Tater — In memory of F. BC. SCHEFFER and in rite as.a testimony of grateACKNOWLEDGEMENTS Iris for mea pleasamt duty to express on belalf of Cebelcor and myself our sincere gratitude to the ontributors, the Union Miniére du Haut-Katanga, “Ui M.H.K.", the Instisut pour [Encouragement de la Recherche Scientifique dass "ndustrie et dans Agriculture, “LR.SLA.", and the Air Force Material Laboratory Research and Technology Division, U.S. Air Force Sysiem Command, whose collaboration and belp have assisted in the preparation of this Atlas, as well as to the members of the ‘Administctive Council of Cebeloor Special acknowledgement is made to Mr. Félix Leblanc. President of the Administrative Couneil fof Cebelcor and President of Université Libre de Bruxelles, to Mr. Jacques Errera ang io Me. Louis Baes, Honorary Professors at this University. Mr. Baes, who was formerly Vice-President of Cebeleor, followed with great interest the progress of this book, which he helped to inspire, up until his death ‘on 29 October 1961 (prior to its publication ia Freach). He will be remembered with gratitude. My thanks are also due to Miss Nina de Zoubov and Mr. Jean Van Muylder who, besides the important part they played in the preparation of this work, have shared the difficult task of collating and correcting the text and figures. M. Pournarx nee eee - “LSreemcenee “uae ca, oeacenery hse min mtg TS conn nic,Hegre eegach an ihn RT), Sie hcl oe Chmsnde Fe Bags NCD. = fees bau A er, estan tt agi tan Fc Sessa bee tiniest Se Mabe Boe (- *enMgthieninanors Shed teean ation tino edn Con ENR con) serait Petia Sera el ties Roe nm En St nrc an Stogtes 6, Peteum Ines ‘etesonace aay ‘inna OSE cn er Tee a ST) oo a Sa Ec esto er abt Boor re eon age de Lan «eS Hl 1 Meco i eae reborn 00 ee eer Tim abnate ge, ‘SlnacTeC5) Pena. “Ga Sindee (0530, Suge IE a te ‘rags Nal be Revce-Lamaca ek Spr can ca ennai igen ere ote emma at e St Tana Nae te Mp i Tah Inne Ser ep ob INE mbes “SMITZERLAND, a Ae fae (etd Sse ‘ian ipa ean Ui Sinatra Settee ty yucostav. Carn Olan po.FOREWORD Tue intaducton ite electrochemisry of potemtal-pH diagrams in the form originate by marks 4 ew era in te study ofelectochemealreitions occuring in an aqucows mum nea am Glecirode IY means of them it posible to predic on a thermodynamic bavi for given amen the eguilrim states of ll the posible reations between this element, is fons née solid and tpeeous compounds [a the presence of water, OF corse, aplication of ihe data conaiod i thete Shageams i ited by the rections which have been considered in establishing them as wll s bythe talues assumed forthe standard chemizal ptetials ofthe substances taking pact in there rections Jn eetan cues, for solid compounds thee chemical pontine may vary wih tbe perfection of th trysaline diate. Moreover, the diagram re based of the actives of fons, and not on hee eeal Conceivations, However, even wiih these resietios it evident that in a good many ess the dlagrams provide data which lead to important conclusions coetrning the possible reactions; these oneiusions are particularly important in the sty of corrosion in aqueous red Ti only through the indomitable energy and perseverance of Pourbaix and bis collboraiors that this Treatise, the Atlas of Eletcochnical Ellis, comprising data for 90 elements could bave been produce, ‘Thos: who are acquainted with the history ofthese diagrams know that it zos back to Pourbit's “doctorate thesis presenta the Techatal Universiy of Dall n 1945 withthe encouragement of iny late colleague, FE. C. Scelfer, However, thi thls was only a modest besnaing cmpored Hn the “complete” Ades. sinceely hope that ths dle wil had 4 wecome appropiate tothe Cho:mous amount of work that has heen necary to produce i W. G. Burcens PREFACE R, Poster THE publication of the Atlas of Electrochemical Equilibria is & most rewarding culmination of ull the «fforts of Dr. M, Pourbaix since the appearance in 1945 of his doctorate thesis, whigh was presented in Delft with the encouragement of the late Professor FF. C: Scheffer and of Professor W. G. Burgers, nd which was translated inca English in 1949 by J. N, Agar at the invitation of Dr. U. R. Evans Dr. Pourbeix, President-in-Charge of CITCE, has for many years been the driviny force of this srganization, within which the activity of the “PotentiaI-pH Diagrams” commission has been mast. intense and productive, counting also on the enlightened collaboration of its members. in particular Prof. Charlot, Prof. Delahay, Dr. Garrels, Dr. Hoar, Prof. Valensi and Prof Van Rysselberghe. ‘Through the efforis of Dr. Pouzbaix and his collaborators at CEBELCOR, ane with the generous ‘support of the Union Miviére du Haut Katangz, the Institut pour "Encouragement de la Recherche Scientifique dans I'Indostrie et dans Agriculture ([RSIA), arc CEBELCOR's Commission des Etudes Fondamentales et Applications CEFA, the gathering of data has made continval progress in volume und precision, thus enabling this atlas to be produced, Collected here in a condensed, logical and standardized form are the data which characterize the equilibrium conditions at 25°C of a very considerable number of processes. These processes involve water, hydrogen peroxide and go elements of the periodic system andl are in direct relationship with the eectrochemistry of aqueous solutions, both theoretical and applied: the extraction of metals, their finishing, corrosion and protection, analytical chemistry and other fields such as geology. whose con- nstion with electrochemistry 18 net often very apparent. Potential-pH{ equilibrium disgrams were originated for the theoretical predictio: reduction catalysis (according to & method devised by Michaelis) and of the conditions under which ‘vidation and reduction reactions are possible or impossible in the presence of aqucaus solutions tin & ‘Wanner related to the experimental work of Travers ond Thiesss). The method and technique used in esablishing them are the same as those used previously by their originator in work on the prediction ‘ofcatalysts im ges reactions: thus these potentia|-pH equilibrium diagrams result from the extrapolation te electrochemical sysiems involving an aqueous solution of work carried out on chemical systems involving a gaseous phase. Each of these two groups of work is based on the formulation ofthe equilibria. of aif the reactions possible in a given system as a function of tcp independent variables ithe other possible variables being considered to be parameters. These two independent variables are chosen in stch a way thatthe equilibrium formulue are linear (or practically linear): they are the logarithm of the ‘ony ¥en partial pressure log pg, and che reciprocal ofthe absolute temperature I/T in the case of chemical systems involving a gaseous phase, and the equilibrium electrode potential and the pH! of the solution ia the case of eectrochemical systems involving an aqueous solution. By this method the equillorivm cenditions ofall he reactions possible in a given system are represented on a plane diagram by families of straight lines. An investizator who constructs such diagcamts must have a certain appreciation bath of science and art: the science is necessary in plotting the lines (ie. above all in knowing the thermodynamic data) and the art in using the lines to create pictures which areas simple and useful as pessible, and which can, as U. R. Evans wrote in his Preface to the English translation of the Delf thesis, “Ul ng a vast amount of pertinent information in a small space The diagrams, which were originated for catalysis studies, have rapidly evolved towerds problems strochemistry of hetals, and corrosion in particular. The proguctiveness of the method caused of oxidation "PREFACE, thon 1 be applied all a weenis—rneks tod nantly, el aplicon have developed Lae eeig to oler branches of eecrochersry and related els eT eee em Weel caer recs Fe en toe aaa of euatney cage ork yal the cnet ae ute there rol ir en ernie paces retin element in qustion ara isnes in aqunis solution wale and Fee er CN fad react Sidropei aad cxfoesVoes ne peace] se aco a Ths meat valk he pects (ones and hydtontes, hydrides et) Te idea eh teaclon which chemialy posible theeis« “es entbalpy of reaction” (rotacd tp diftretnvon to ni velaon nthe degree of advancement of the reaction whore valet Co arate nang of te sem to rene and the dion of the enetion, Under aed re aE dando tis rs ena of earn ca be expressed asthe sta oa standard re enbaly Pa as ea pret papal condloescarecereicolasananrd retrace sate) mada Tnant co a at Ioan of he acter ef the subatances taking part Inthe ration, When the reaction is accompanied by the circulaiion of an electric current in 2 galvanic cell, the free enthalpy ae tian bar Uateeie charge gies ws the Tale of The quilt potential dference a the cea ae el or eectorma fore) which coresponds (0a sate of eullbrium the faction considered ‘An external source of electric current, such as that causing the circulation of "stray" currents in the bround, or thecutent supply of an skies bat, can imposeon a sstam the crealation ofa aa ietnien diecon and hence te roducton oft reaton ina given direction, subj oe CerGtiom (uhh i mca but not suffi) thatthe sours i apable of mantaiing a potest ittregy ste ein which exceeds he elisiom va, which then eld the “decomposiinn catape™ An leurchemial” presentation othe fee ens of action thus que nar fr Tautins proguond yan exersteurent cure It isconecned with evry aa ofthe phenomena Cotman ts casein wich eletrocherea rncors ae canned bythe eternal supply ef eet eure. ae tain ne sus af earochemfel reactor wlth jade eee even; spontaneous rrosen octses of te malic element a ofthe ler pe u series 1792 (ie. shortly after the discovery of galvanism) when Fabbroni clearly stated the hypothe: of the galvanic nature of corresion processes together with his chemical theory of galvanic phenomena, Shoughous the sad of Devy. Thenad and De Rive and up t tke moat eat ones, te elt SRonaneoes caronion presses take place ean these compared lo galvanic sytem Which donot Zeheng elec) wer wi the outsive nor or which the condions necessary forthe oceurre>z Sfrnodcatons oruffclen fo thet absencecan asin be represented an eel eleevochema iorm at ue consi galvanic couple in whith one ofthe to lestrodes isthe standard hydrogen clecode and Tor wach one ean represent the chemical mifsaton 98 bang the resultant of two Scmplementary poral exidaionseduction faction, taking place rxpectiey a each of the to Cresta: ith te parcipaon of electron inthe pases Raving meaic conduction, the ich. Spue coeticinn ofthe cletros aving qual shut and opponite sens fr the vo partial reactors The most conan contentions eoneeaingrelerence ste for ee thermodJnamic propertis af soseeus hydrogen athe hye fon in gusousyltion automata easel eu the contribution Stine seandardtpdogenelecuode inthe expresion fr the fre enthalpy of reaton. One can thes Sosterte vl ef hse enthalpy as being inrent To the acon takieg lace a he ote ele trode The potential diferences a he terminals of he guvanic couple are adopted, by defn, (Shas ofthe plemss or “eta potatal") of his elevrodewihcespeet the siandard hydrogen (3) sens of Such pote il ges the sete ofthe afitis” ofthe partial electrode ‘HW spond we spn of these flv esta potnin th coger oan Op AE seen Sieh, vss ens tg assed Euro Slog ihe noustonalthe wr of ny rece he sone shoe eulalen “lopiad by Oc Poor en aezordnce (oetnie conics oppsie) PREFACE ig reactions, referred to the reaction proceeding ut the standard hydrogen electrode as a conventional reference Tevel For the cell obtained by coupling any’ two electrodes, the equation of the overall reaction, the value of the free enthalpy of reaction and hence the value of the equilibrium potential cilference ean be deduced by simple algebraic addition of those corresponding to the calls formed by coupling exch of these two electrodes in turn with the reference electrode; the exactitude of the result depends on the possible “tiquid junction” contributions, In this way the study of redox reactions can be reduced to study of partial elecide reactions (or “electrochemical” reactions involving free electrons or electrons in phases having metalic conduction); the other reactions will be studied in the way which is classical for purely chemical reactions aot involving free electrons. ‘Tae equilibrium conditions can thus be represented in the general case of electrochemical reactions by a relation between the equilibrium potential, the standard free enthalpy of reaction (in the form of a standard equilibrium potential), and a linear combination of logarithms of activities In the particular ease of non-slectrochemical reactions the equilibrium conditions assume a simpler form as ‘quilibriom potential is involved; these conditions are then expressed by a relation between the standard free enthalpy of reaction (in the form of an equilibrium constant) and a linear combination of logarithms of activities, ‘With view to the graphical representation of the equilibrium conditions on a plane dis the choice ofthe relative electrode potential as one of the coordinates ieaposes itself in the more general case of reactions involving electrons: In view of the exceptional place occupied by H* ions among the species whose activities appear in the equilibrium celations to be considered hee, it was natural to choose & function of the activity of 4H ions as the second coordinate; the pH was ehosen in order to Tinearize the equilibrium relations, despite the dificuties inherent to the incividual thermodynamic properties of ionic species.) The linear combination of the logarithms of the activities of the species different from 7, whose ‘thermodynamic leva in the electrolytic medium i also variable, walle given the nature ofa "parameter" sshich is veriable from one curve to another in each family of equilibriam curves, For electrochemical reactions which do not involve bydrozen ions the loci of points representing ‘equilibrium conditions will be straight tines parallel to the pH axis; for “purely chemical” reactions involving hydrogen ions they will be straight lines parallel to the potential axis, When there is only ‘one species of variable thermodynamic level, the parameter, whieh is then proportional tothe logarithm ofthe activity of this species, characterizes the conditions of practical existence” of this species in the medium, iz. the domain of conditions under which the equilibrium can be realized in the presence of appreciable concentrations of the species, Let us consider ¢ system consisting of a metal in contset with solution ofits simple ions, these being the only ones which can exist; if the concenteation of these ions which is compatible with the equilibrium conditions is lower than a fairly low coaventional limit, ‘one can then speak of a state of thermodynamic inmnity of this metal. When the number of species of, variable thermodynamic level is io, the parameter, which incluces in general the ratio of their activities, gies these domains of relative predominance, which cun become practically total for ane to the es- clusion of the ocher. The diagrams thus give us a panoramic view of the “chemizal configurations” of our systems jodynamic basis. An examination of the properties of the potentie!-pH diagrams ‘eR tag Agee href ronnie convetion ian hg Oe ae eis ust aie RES POOR EE ee SME aa einen een Ley ace Se touching on the seni previge af mon soos which were: pede une! wilh aero acPaives hive pte re or the er ofthe me sonvcston, [Foe te purpowsenisged by Pon's digas o sy the perl fan terse wach lee ine senor _:etoustyerogen ct {aim buts mes nes adie One ca so postulate Na a Sieh haw mr Sesto yn sta ea copabe of haracrering the theroeynaia ee Fen th 2 te O#t "ions Sue ig te Sneaton eprom eatery wt er to shee Paripaton i 0 eines agua sali,a PREFACE suggests certain aspects which itis useful to know in order to apply them appropriately. It is evident that the electrochemical behaviour of a metalic phase, immersed in an electrolytic medium, depends ‘on the composition ofthe layer of solutioa which is in immediate contact with this phase. This corsposi- tion may difler considerably from the mean or intial composiion of the meviuim on account of the absolule and relative rates of the possible processes of electrolysis and matter transport (by migration, Giflusion and convection), This same observaiion is valid for the phases formed by the compounds of the metal, and -must be considered carefully in using the diagrams, When the metal forms soluble complex at stability with other substane ‘or ammonia), the equilibrium diagrams for the binary system metal-water mast be modified: one must ‘hen take into account the equilibrium conditions of these complexes for example by plotting equilibrium diagrams fora iernacy system. This may modify appreciably the domains of relative predominance of the distolved species and thc domains of thesmadynamic stability. In these cases one must therefore be very careful, particularly because aly when a dissolved species is greatly predominam, in the cise of dilute solutions at leas, can one assume, 2s has been done in this tii, thatthe activites are virtually the same as the molavites Use of the diagrams therefore renders necessary corrections of activities {or molatities); these corrections, which may be important for all the diagrams when one considers ‘concentrated solutions, may also be important when one envisages the use of binary diagrams for study- ary systems which inypive stable complexes, ‘Amongst the reactions considered in establishing the diagrams a special place is held by those \which involve @ metal or its ions and oxygen or the ions derived feom it, ane whick produce oxides or hydroxides, The equilibrium eonditions concerning these phases have @ fundamental interest, not only ‘when they ace the main subject of study bur also when ane considers the behaviour of the metal in electro chemical processes, such as those of corrosion. From this point of view the diagrams, in spite of their esseatialy thermodynamic nature, can give us information about one of the most important kinetic factors ia the electrochemical Eehaviour of metals. Indeed, in the case of electrochemical reactions, amongst the factors which can be named “resistances Lo reuetion”” and which, in spite of the aifinity available, determine the Kinetics of the reaction, a most important place is occupied by those which ‘depend on the formation of surface layers on the metallic phases. A fairly detailed study of these pheno meng has saggesed, quite recently, that one should distingwish between pussicution phenomena, cor responding to an increase of resistance to ionic exchange reactions between # metal and a solution due 10 theie separation by a surface layer, and states of passivity in which this resistance is suficient to reduce the rates of these rezctions below lints at which they are appreciable in spite of there being un affinity for the conversion of the metal into its eorrosian products The solid compounds (oxides, hydrovides, basic salts} formed by the various metals sith water represent the most common and important source of passivation of metals in an aqueous medium by a surface layer, Thus a knowledge of the conditions of thermodynamic stability ofthese oxides, hydroxides land basic salts can enable one to charaeterize the omuins of passivation predicted by thermodynamics. The passivation may eesult in a state of passivity, which may be local or complete, depending on the structurl properties of the phases involved. Indeed, in any branch of electochemistry, theoretical and applied investigations can be carried out thoroughly only if one takes into account three types of factars theemodynamic, kinstic and structural ones. It must be realized that thermodynamic studiss are in- sufficient. even in conjuetion with kinetic studies: structural studies are indispensable. This is the ease first of all because they give vs informacion on the deviation of the real phuses from the ideal ones considered by theoretical thermodynamics and kinetics; moreover, they alone enable us 10 anulyse, (0 control if possible. and sometimes to prediet the properties of our galvanic deposits or passivating layers, the selactivity of the attack processes. and all those properties which determine to a large extent the success of the vleetrocherieal processes of production, finishing and protection of metals. or the conse- ‘quences of corrosion phencmens, ‘iis the scale of lative potentials gives us the deeree of "thermo- dynamic nobility” of the vurious electrode processes, a knowledge of their “practical nobility” requires {such as cyanides ith respect 19 molacities PREFACE 6 that one sould alu take nto acount Kinet laws and the inne of sro actoton thee we Foy (ht mel whone ini exchanges 1° ln aqueous rid te sgid(oeal sheet he nave neds ting of "normal cletrschemizi behasioun. the betarbur i ascordaes wih thermodmamie predicons, balk when fey are attacked endcallyund when they ve depo catbdicaly eg. a refining or cet redeposion tah oF Ina dispucemen ream oem nestotin process For those metals wou tong exchanges wre slow, onthe olber hander cen very sow (nin Wath letrochemien! nena) tbe dvrgsne between the thermodymure nobly 100 the pee bl I sat Vea el seg Chea Ie 30 eT GR Per ee eee moe a thse Hoe ese of tet Sehavour un indopensale complemen oe ifomaton es 85 tn suum diagrams, Onc ofthe mes mprtamLinei features n many banchevaleleceaerty ithe infence ofthe anions selena contents of tc tal soon duble tyes a Sualjts of fon exchunges(acrdng 0 Saneus mechanisms. veh a compelive adhorpionat he Sara. ething constituents which bave in midi atin) ras desreyers of te sce ayers Or at agents which ean exploit vesk pins, or as strut factors metho Sposlion ve Isles actors in anode ta In all banches ofthe eleechemity ot et the spate pur tipation of anions, even indepenerly of uy complering ston and af heir aftenes ce te ens ‘civ ales, cam play am portant part, which mst eften be onsdor lo compl the inarnaton tha ore an cbila fom ne Gore [At present the poeril-pHagrims concern ‘nly pure raul and rennet thee i aso an snmp fo apply ther o sodium smulgams| tse fara ceanet tebe rive os foraton snr the betasiourofaloys, which oer dies om tut of te pure metus, wih eget acre rentianedatove Ii aly obvi thatthe eoresion behsiut ofa bron or of bes Ey comple rena ofthe ropes ofthe conituent mets and thi is rea more uso sailse een the other bund, krovlelge f te thermedsmamiepoperes ofthe pets feu othe retaleconstingan aly cin snstines enable so peu is pemteon odin oo acces clequllofan candtons ted Mc cond ion ay single or nuncarsomr eae ates creda each of which canbe considered f be te se ofa sre welldeiamned scion feos ihe sstems in which eorcion phenomena oxcur are very ois mulile erode tens ch ‘The cneeraons vith {fave Just deeuted help ut otcogaio tbe ie oth application of potenistepH equltium cigars to cnerete probleme icra theoreal o appleyeencn sr. oF of some oer nau uihin ie itis of uscragy othe weaabi neon de Foranjone sho might have dimed io ind the astern ren cagrms Io ay eon or octal probit exe pllon he aboteanalssyaayheve Crogan The thor of thi suas Riel as sated ton explldy the apion i ony ler unde ssanding fhe lms of hedaman hence onl and props ofthe cen ene es to appreciate great uty wich justfes the generous, pustonste and potable ere ef Pourtais and al thse who hne worked wih film to ree I aan whow metea Go cary toreGLOSSARY CORROSION: The reaction of metal with ts non-metallic environment that results inthe continuing destruct ofthe metal IMMUNITY: The stete of « metal in whieh corrasion is thermodynarically impossible ina particular envzcn- PASSIVITY: The sate of anetl in which corrosion in a particular environment is prevented by modicatns fis stace, for instance, by the formation of shin protective layer of oxi PASSIVATION: The proces leading to more ot les perfect pasty of mateil ‘Pusivation can be obtained by clectrochemcal means (fr iastance the anodic polarization of ion ina sotution of sodium bicarbonate) or by chemical means (or instance immersion of iron in fuming nities). CATHODIC PROTECTION: The establshracat of a siate of immunity by catbocie polarization, Le. by making the eleccc potential ofthe electrode (or electrode tesion) more negaliv Aer the completion of the preset Tras Uh has Been observed() that ping of tines steels (and of other passvable metals and alloys) de to clotdes mey ofice be avoided by a cathodic irestment under conditions which do net lead to immu, bat ead to peretpassiviey “Taking tis fet into account, cathodic protection may be defiaed more generally es the etablishment of sete of inmunty or of perfect psscaion by cathe polation sate ofeathodie provetion ean be obtained by the use ofan em applied though an exernal source or by means ofa galvanic anode (ish as tbe or mugsesium forthe Protection of iron or see) INHIBITOR: A substance capable in the form of small additions to reactive mum, of stopping or of sowing oon a shemical or an cletrochanea reucdon ata meal surfice. When ths resction woul rest in cosoxin ‘he iar sella a epyvoson iibior ELECTRODE POTENTIAL (or tension): The difereneeE = 9, ~ g, between the elctrie potential, ofatermizal tea ofa metallic electrode dipping in electrolyte solution and the elect potertal ofthe terminal ead of reversible teleeneeslestode in contact wi this solution, this diference of potential being corrected om soul of the potential diference ot the liquid jurcton which may exist between these two elctodes. The fv lsds are wide of the same meth copper fr insane. In general the eletode tensions or potetials E Soi tecepresed in vols with respect 10 the tandard hydrogen clectrcée, ie. an electrode of painted platinum. tn which an eqllonum fs estabished between gaseous hydrogen under a pressure oft atm, aad an equeois salution of pH = 0 ()Set CEBELCORS Rappone Testigues & F 4,128 980, ee Coron Selene 3. £3959 963 i NOTATION AND ABBREVJATIONS a - [dere etn fe ante [et team = aa pe) 9 legen Rhy ' tie a doiyéio a piri gain Snhyee yd os logit 1 ace to x dents ola Mla et gamenolee per ive fim erp Maynor a chelate eee beyond etc (‘aga of pasos sbnancy, or atviy ee Serniente ts doled sbsnce Mi one =A ialmpee ene ee geaveneo rest = nan oa auormed TiGema) aie tn Sone oneal toate E Shot potent (oreo tension) | mV” ml 5 Spittal ore eqs |p hence ek i Standard emi posal 5 seanardvle of (taeda cqutbrum | f° Sana chemi pot at °C oy fA icoamgee et stay ive of at 25 (andar | fm rm or micron) lism poral 35° x oval Le | gamagealeat per ive Smt Strosne fos Soller coc! of heletrone™ feces faceceatad ele one : oe [Soh Siders orton Ee peste penne fit paetaiper Dee pee ona period fom amon |Get Genter rapa a Fampe fee then. Shomboheti or teary) fold femmekenl peice Sib seeds : ior : sod it ental of formaion . She t Standard etal of fomston q nto of fain ‘ Sesst enn sthemnn aac |} Samar etropy af formation 7 ago! {= Std etry of main td bpd [ieee te neceme ae todton, —Rpone ‘sith Solty i lesb ooeat teeters t mer oe tlm & faction cuenta the equitom (x |W Be change en) la rdaloo number In ll tables formulae and diagrams which appese in Chapter 1V of dhe present Ai, the physeal site of substanass considered wil be indicated as follows : M solid substances, Mt gaseous 20 2M guid subeanees, yi dislved 94 sous siuonshCHAPTER I INTRODUCTIONINTRODUCTION REMARKS ON ELECTROCHEMICAL THERMODYNAMICS AND KINETICS Prenat Vax RysseLneroHe Stanjond Univers, Calfornis, U.S.A, ‘Tue excellent Preface by Professor R. Piontlli provides a perfect basis for this Introduction which can thus be reduced to a few remasks concerning certsin fundamental points, all the details of the ealewletion and of the construction of the tension~pH diagrams being presented by M. Pourbaix in the following chapters § We shall begin by examining the meaning of the very name givén to the diagrams in the present book, Let us vsuall ta, for many years, thelr name has been both in French and in English, “potential PH diagrams”. Comnission No. 2 of the International Committee for Electcochemical Thermo- dynamics and Kinetics (CITCE), “Electrochemical Nomenclature and Definitions”, has presented in yearly reports since 19s1 a critical study of electrochemical concepts and has mage a number of recommendations concerning the exact significance of various terms currently used and. in some eases it has found uselul to insist on the adoption ‘of new terms or of new and more precise definitions of old terms. In pacticular, Commission No, 2 of CITCE has presented in recent reports 8 systematic treatment of the various tensions~electrochemical, electric, ehemical—which should be considered in the fundamental theory of electrochemical equilibria and of irreversible electrochemical Phenomena. Up to now this vocabulary of tensions has received general approval among French: speaking electrochemists and, with the very precise translation tension — Spanmung, that of theit German-speaking colleagues. The situation seems to be the same in most of the other languages, but 4s far as English is concerned, certain resistances have been encountered, and some of these have been rather strong. On the other hand, eacouragement has been fortheoming fom some quarters in the United States, and statements of adoption of the new terme have been made, in Austelia for instance, Before entering into a brief discussion of the question it is advisable to note that the word “potential” bas been used in thermodynamics, physics, etc, in so many diflerent senses that the appella- tion “potential-pH diagram” appears to be really too vague, particularly in view of the fact that the Potentials here involved are actually combinations of differences of inner electric potentials of the various phases or linear combinations of chemical potentials reduced to the unit of charge. The cbjection can, of course, immediately be made that the word “tension” has also been used in many lffereat senses, but, wien one has to distinguish between inner, outer and surface potentials; chemical Potentials, electrochemical potentials; oxidation, reductioa and redex potentials; thermodynamic Potentials, ete, the three very precisely defined types of tensions, whic are wiways differences or linearCHAPTER combinations (reduced to the unit of considerable amount of claity Inthe general mame ~“tension-pH diagrams” the word tension is used without adjective. We shall ‘immediately see that it can be understood as refering to equilibrium electric tensions, but ako, and, ‘we submit chiefly so ceduetion chemical tensions, which ave ako called in the CITCE reports reduction afiities per unit of charge and correspond to one of the possible types of the quantities which'ate ratber currently called “electromotive forces As far as pH is concerned, the diagrams presented inthis Atlus use itn the well-known operational sense. Commission No. 2 of CITCE hat been examining for some time the possibility of establishing a rational definition of pH, but we shall not enter here into these theorctieal considerations In order to define the various tensions as briefly and clearly as possible, let us firs! examine the typical example of the Daniel! cell, which we shall represent by the following diagram: urge) of the corresponding potentials. certainly introduce BAGH Un rea {oTlowed by an external ciseuit 1° — 1 “The inner electric potentials ofthe various phases ace represented by o.g?,... Theelecri tension U of the ee. considered from left 10 right in the direction of the numbering of the phases, 0 Usitoer, Whether a current passes through the cell (U is then an irreversible electric tension) or not (U is then the rewersibe electric tension, if one leaves out of consideration the electric tension @! — 9! of the liguid junction between solutions 2 and 3, ether by neslecting it or by estimating it numerically and subtracting it from the total electric tension). The terminals 1 and I’ being chemically identical, we may write oF e v whore #1 = pf represent the chemical potential of the electron in copper aid F represents the Faraday, Messuring instruments, potrtometers and voltmeters slays pve ut diferences of eine potentials between chemically identical phases which shoul then always be associated tothe phase of the eletochemis’s galvanic and ebtrolytic cll In general the copper wise: ual as conection will belong to the electrochemical systems under std Inicoducing the eletrochemical potentials ” wwe have w ‘where in the denominator of the secosd term on the lef-hand side, the charge —F is that transported by £ mote of clectcons passing from 1" to 1 through an external conductor. The difference of electro- chemical potentials in the numerator is equal to the electrochemical afnity of the process 8 <0) > 4Fe*"* + 40H”, and these feric ions react with the hy- 4roxp! ions according to the reaction 4Fe™** + 120H” > 4Fe(OH), | to form a brown deposit of fee hydroxide; in less aerated regions the action of oxygen leads to the separation not of eric hydroxide, but of magnetite FesO,, In general these oxides are deposited in the form of rust at a 2K Ove Electrolytic dsoeation ofiguid water UWyOm > Boast Ogg, Precipitation of erroushydeoxige 440M) FEC Dissolution of gaseous COs Ont Oy Coveosion of ion with evolution of hydrogen Pear alley, + ‘Oxidation of ferrous ions by permanganate i 8Magyt Sees ‘These reactions can be written in the general form a FMM EM Mes VM WE in which the “stoichiometric coefficients” ¥, ¥4,.-. and vf, vf... are positive numbers, By bcinging all the terms to one side of the equation, we can write the reaction equation (1) in a shortened form in which the stoichiometric coeficients v have the same numerical values asin (1) but bear either « + (or & ~ sign; as sign convention we say that the coeffciensv are postive for the reacting substances M oo the right-hand side of the reaction equation (1), and negative for the reacting substances on the left-hand side For example, the following reaction written in form (1) NaOpe sles SEet > Mets H,0-4 Sree willbe weitten in Form (2) Marna {1,0 + 5Fennr— Nn Or— BH 5 Fer BBy writing the reaction in form (t) of form (2) we do not assume that we know the direction in ‘hich the reaction is really proceeding. Depending on the circumstances, reaction (1) can take place from left o right, using up certain quantities of substances M’ to produce substances M", or conversely from right 10 left, producing substances M’ at the expense of substances M", When the reaction takes place fron left to right we say in general that it takes place in the positive direction; when it takes place From right to left, we say in general that itretrogresss, or takes place in the negative direction, In short, by choosing the direction in which to write a resetion, we do not assert that it will proceed i this direction; we merely choose the direction which will be taken as positive; when a reaction takes, place from let to right, we say moreover, that it takes place in the direction in which it is written,CHAPTER 1 ‘The rule forthe signs of the stoichiometric coefficients in the reaction equation (2) can be stated very simply as follows: when reaction (i) takes place in the direction in which it is written, the cone stituents which appear have postive stoichiometric eveffcenis in (a) and those which disappeas have negative swichiometre coeltcicnts. 2.3. FLECIROCHEMICAL REACTIONS Me shall define an electrochemical rection (or electrode reaction) as being a reaction iavolving, besides molecles and ions, negative electrons e~ arising from a metal or other substance by metals Conduction Such reactions will be oxidutions if they proceed in the direction corresponding to the Tberation f electrons; they will be reductions if they proceed in the direction corresponding to the absorption of elec:rons. Some exmples of electrochemical reactions are eduction efhyirogen ions to gassous hycrozen Reduction of sasous oxygen to hydroryl ions aN ae > Hg Orgy Ath Opt 62 + 40itpyy Reduction of permanganate to manganous ions Wn rags + BMG) Se eA 4:0 (Oxidation fron to Ferrous ions Fog Peggy eae Oxidation ferrous jons to fete ions reer ‘These reactions san be written in the general form ° yon aes See co (Eacnecal 4. MET00 OF WRETING THE REACTIONS 11s well known that, jr every chennicul reaction involving, among other substances, gases and/or dissolved substances, there exists an eguibrn constant whose'calue or a Gen temperature and torel ressure isa vertain function of the pata! presseres(r the Jagaites) ofthe gaseous reacting substances and ofthe cncentrarions (or the activites of the dissolved reacting substances, Some examples of toch equilibrium constants are dissociation in the gaseous phase (Guldberg and Waage’s constant, mass action constant) 2M Og 2th gt Oe fe dissociation in solution (Ostwald’s constant, dissociation constant. ionic product of water): WOn= Hager Oly, ‘ou 4issolution of sparingly soluble solid subscances (solubility produ) FeO, AN Osgo4 HD y= AIT AS Daons ‘issolution of gascous substances (Oy hy = ICO ESTABLISHMENT OF THE DIAGRAMS 35 1k is possible to show(*) that, for every electrachiemical reaction involving gases and/or dissolved stances. there also exists an equilibrium constant whose value, for a given temperature and toral re isa function, not only ofthe partial pressures (or Fugacities) ofthe gaseous reacting substances st of the concentrations [or activities) ofthe dissolved reacting substances, but ako ofa diference of slctric potential (or electrode tension Consequently. if in order to establish equilibrium diagrams as a function of pH and electrode potential, we concern ourselves with investigating the influence of the pH and the electrode poteutil on the equilibrium characteristics ofthe different reactions that we are interested in, i is as well to write these reactions in a certain specified manner which makes clearly apparent in the reaction equation «any Hons and electric charges e~ that may take part in the reaction, For this purpose we shall in general use the following convention for writing che reactions: for Lt, ‘in which his theapeciic molar enthalpy ofthis conatitent an si its specific molar entropy. unde the conditions of meum, pressure, temperature and concentration experienced bythe consttoent For the chen action 2M © 0 we cin write, oa the basi of equations (3) an (7) © Ske pe thTeet or, representing the summation Esx by the notation AX: ) —AnaG+an—Tas, jn which G repesents the tree enthalpy G =H — TS: we point out, however, that although the X corresponding to x = 11 is being represented moze and more widely by the symbol G. itis sill often repcesented by he symbol F used by G. N. Lewis and his colleborators Equation (g}ean be written in particular for rengents and reaction products considered sepastely ih the pare state and under the same conditions of temperature and pressure. For example, if we con- sider the reaction Ueart20nm Hn starting from the substences H, and Os in the gastous sate representing the formation of liguid H wwe have Dy Mg BPO (9 Se toe cL v8 ESTABLISHMENT OF THE DIAGRAMS u ‘A very widely adopted convention consists of assigning the value zero to the chemical potentials of elements in their normal moleculat state at 25°C and 1 atm. pressure, If H, and O, are both con- at Fatm. pressure we have therefore, ac Ou which shows that the free enthalpy of formation of liquid H,O starting fcom its elements at 25°C and ‘atm. isthe same as the chemical potential of liquid H1;O, 8 substance which is then in its standard slate In view ofthis, and taking into account equation (5) the condition for thermodynamic equilibrium of @ chemical reaction, ie. the condition which expresses that the affnity of such a reaction is zero, can be written or, substi an Byte RT Eva i into ths equation the values of the chemical potentials shown in equation (6), cr further, by replacing the ideal gas constant R by its numerical value, and chahging feom Napierian logarithms to decimal iogarithms: @) eat (and T Sy ng (WL that is Which ean be wetten ow [Emaan ow ce o [Now the formulation ‘of a rezction equation is equivalent to the usual formulation my) SMe My stp. The stoichiometric coeficieats v of the formulation (2) are usually considered as being positive forthe substances M" on the right-hand side of the usual formulation; they are considered as being negative for the substances M’ on the left-hand side. Equation (13) can therefore be expressed in the form enya nas nef FTN {naa bas we to poi Cu aie Frio 15 fhe ae othe eau outa K sea koe nef head any of san heey fe son he ptr cs nl he ing