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38 CHAPTER IL ESTABLISHMENT OF THE DIAGRAMS » a Homogeneous reaction inthe gaseous phase cay 2+, oon Soe [Gvldbere and Wesge's hw of Aisoeation inthe gossour phase {nassaction Consequently for every chemical reaction EM =o, the equilirium condition at a temperature ‘Trean be expressed by the equation Homogereous reaction in aqueous solution. a) Bs lag(M) = tog k, ate sh i. the algebraic sum Ev log (M) of the logarithms of the fugacities, and activities (M) of the gaseous 4nd dissolved reacting substances is « constant which is the logarithm of en “equilibrium constent™” K The value of this equilibrium constant is connected withthe values of the standard chemical potentials 4 ofthe reacting substances and with the absolute temperature by the equation, H.0)— Hig, + OW loa, nore Te fru [Oswald's law of cecitalstic dissociation. Heterogeneous reactions—solidjsotution type: co Jog us) Tas - a When the temperature is t = 250°C, ie, T= 2981°K, as is considered throughout this Atlas, eee bites 2 2 < siti conditions (13) (i) and] become respectively / tps Coy jo BESTE eo eel er Mae + HO). FHASO aa) ¢ a) pees _ 20 Hiv0." Ho =p S00 + 137660 56690 ce sett Golubily in whish ” represents the standard chemirst potentiate at 29°C of the seautig substances M. Relation (20) [and relations (14) and (21) which are derived from it] is the gereral forma for chemical equitbria lor physicochemical ones) at 25°C Ths relation expresses that, when the equilibri sMeterogencous reaction —~gas/solution type (05,4 HaOy = HCO ps n state of a chemical or physicochemical change is obtained at a given temperature and pressure, the algebraic sum Evlog (M) of the logarithons of tne 60, Hlisco.~ Heo, Hino fupaciis and activities (M) of the gaseous and dissolved reacting substances is equal to 2 eenetone Lyre ream | log K. whose value depends only on the temperature and pressure, and can be calevated fhom relation =Hgoms of ston sbe0 eee (21) ifthe values of the standard chemical potentials u* ofall the reacting substances are known lorie ee So Gaye ee Saba, standard reference state, which is for condensed substances (solid or guid) the pure state for gaseous substances, the state having 2 fugacity (or “corrected” partial pressure) oft atm. Conversion from condensed phase (solid or lguid) to gaseous phase 10, = H,0,: {or dissolved substances, the state having an activity (or “corrected” molality) of 1 ¢-mol (or gion) ie Plier ghee oe nee per kilogram of solvent, Neb, — — Sag = — SE ee Given below are some examples ofthe ealeptation of the equilibriom constant, for the our types anaee of chemical reactions considered in paragraph 24, and also for the vaporization of water, based onthe following standard chemical potentiais 1. at 25 C:(*) Py,Q7 9°! ate. 0.0513 atm. = 23.7 mtg, (vapove pressure law, er ae : 1 Js important that we should be well aware of the fact that the different eguilibrum laws which 1.0 (racous) = 54535 FIOM) Islay = 115570 al ‘hese equations express are only particular cases of a single law of physico-chemical equilibrium FH, jzaseous) On Fe"> (dso) ~ 2x0 i ” ny alain law af ey = 0; tgecous) ea 8,0, fli) = 37886 7 HO liquid = 680 HAO; (solved) = 96250 7 , HE (linsolves) ° CO; (gaseous) = 94360 | FE Hissolv = 3598 H,CO, (issoled) = 145600” de (yEnc ve de ormavion anand appar sshoigue RTA of CEBELCOR. 19)0 CHAPTER It in which the constant K is known by diferent names, according to the nature of the change that is being studied: Guldbecg and Waage's constant (mass-action coastaa), Ostwald’ constant (distocation constant, ionic product of waten), solubility produc, solubility, Henry constant, vapouc pressure. The valle of eak of theze equilibrium constants Kis comected with the values of the stondard free enthelples {formation or standard chemical potentials) p* ofthe substances taking part inthe change, by the sane ‘elation, wicks ot 25°C: sou we oo 4 CENTRAL FORMULA FOR ELECTROCHEMICAL EQUILIBRIA (”) 4.2. GaLvame cents We hate defined an electrochemical reaction (or electrode reaction) as being a reaction involving both chemical substances M (neutral molecules and/or positively or negatively charged ions) and free electric charges for instance negative electrons e~ arising from a metal or other substance with meallic conduction) for example” Zn Such reactions can be brought about by the coupling of two electrodes st which take place respec tively absorption and liberation of electrons, for instance according to the reactions Bate aya =o, leading to the overall chemical reaction (ay Sie 24iiee “These galvanie cells may operate either without the external addition of electrical energy (in Which case the overall chemical reaction takes place in the direction suggested by its affinity), oF with the external addition of elecvicul energy {in which case the overall chemical reaction takes place in the opposite direction to that suggested by its affinity slone), Inthe first case, which is obtained in the discharge f batteries and accurnulators and in the spontaneous corrosion of metals, there is oxidation at the negative electrode of the cell and reduction at the positive electrodel"): in the second sase, Which is obiained in electcolysis and in the charging of accumulators, there is reduction at the negative electrode and oxidation at the positive electtode: in the two cases we call the electrode where thee is oxidation the anode, and the electrode where there is reduction the cathode. For example (Figs. 2 and 3), the synthesis of water in a hydrogen/oxyigen gas cell and the discharge cof a zingjcopper Daniel cell take place according to the following reactions: ~ se Eleetode oxidation) am In + taste + ve Electrode (eduction) f Overall reason Sgt gen 0) See be oh op. 54 10 Hse mee ne etode aacbed 1 the nepateterminal othe sl he to the postontominl ef she ol the postive lesa, ve cece andthe elie mate ESTABLI WENT OF THE DIAGRAMS. 41 Conversely, the electrolysis of water and the charging of a Daniell cell teke place as follows = ve Flectrode (reduction) 1 Electrode (oxidation) Gu Cerne aes Eaahe Overall reaction F tae A A He Oe APS zn Nan ww. () (@ Dsomposion of water (cetrobia: 2,0 = 28 +O, (0) Sjtnee otter (ga el) 38, +0, = 28,0, (o)Consion of oe with the evolution Si hycaqens 2a-+ at — Za" 48 b sth Fie 3 Daniel el 42, run ‘The electromotive force of such galvanic eels is the potential difference ¢; — 9; (°) or tension st the terminals of the cel) when the cell is “on open circuit"; and when the whole system isin electro- ‘chemical equilibrium, The value ofthis potential difference is connected with the value of the affinity Az of the overall chemical reaction (22) by the relation (2) Ce, win erent src the teal etc potato chia Hanalei ota made of eonon Fr ieaans ee othe to ode lhe ll The cledromatve les Ge heal washes Acai2 CHAPTER I cr, since os Ze ‘This difference of electric potentials or electric “tension”, is the equilibrium poteatal diffrence ‘ofthe galvanic cell, I'we express the electric potentials in volts and the chemical poten! equation (25) becomes sj im calories per mole, v8) Let us consider, for example, a Daniell cell in which the Zn** and Cu** ions are in the standard state (activities: 1 g-ion/l at 25°C), and for which the chemical potentials have the following values [according to Latimer) Equation (22) gives =H Za aie ‘The potential at the terminals ofthis Daniell cell in the equilibrium state is 1099 Vs the zine is the negative electrode, ic. the copper wire which is attached to itis negative with respect to the other terminal of the cell 43. ELECTRODE POTENTIAL, EQUILIBRIUM POTENTIAL OF AN ELECTROCHEMICAL REACTION With view to studying any electrochemical reaction Z#,M, + mye” = 0, et us considera galvanic cell ofa special type (Fig. 4) made up ofan elecirade 1 on which is taking place the reaction that we a rl Pi Reverses rence slectade let Flo 4 Mesurement of eletode potenti ‘ster and Lupine met) wwish to study, and 2 reversible reference electrode (hydrogen electrode, calomel electrode, silver chloride electrode) on which the stare of thermodynamic equilibrium of the electrochemical reference reaction is obtained. % must bs understood that this reference electrode is connected t0 # ‘on solution by ‘meaos of a siphon to avoid the existence ofa diffusion potential between the two solutions (for instance ESTABLISHMENT OF THE DIAGRAMS 3 ‘on of agar-agar jelly satureted with KCI and which, when an eketrc current flows inthe reaction n. emerges in this solution in the immediate neighbourhood of the metallic surface on whieh he cousin to he steed is raking place (Haber and Luggin’s siphon or Piontell’s siphom) The equation Sout Syactae sshich is deduced from equation (24) gives the value of the equilibrium potental difference of the cell formed by coupling the electrode studied and the reference electrode, ie. the value of the potential lnference when the whole of the system isin electrochemical equilibrium. Now the eeference electrode Jofintion, in estate of equilibrium, Equation (27) therefore expresses she equilibrium condition of ‘ecctochemical rection studied, Consequently a general electrochemical reaction » ie. EyM, + n,¢7 = 0, will be ina state of suiibeiom if the difference between the potential @ of the electrode on which this reaction is taking place and the potential Py of a given (") reversible reference electrode has a fixed value, aiven in ‘We shall eall the difference of potential thus measured between an electrode and a reversible ‘slerence electrode the “potential” of this electrode, or electrode potential E, and we shall call this stectrode potential the egulibrium potential of a reaction in the particular case when it corresponds to tke state of equilibrium of an electrochemical reaction taking place on this electrode. If we use the ssmbol Fo, to denote the equilibrium potential of a reaction r written in the form EM, + n,e" = 0, ccuation (28) can be written eb Tato Eve Ive use as 2 reference electrode the standard hydrogen electrode for which the chemical potentials of the constituents H (at pH =o] and H; (at 1 atm, pressure) are taken to be zero, the equilibriim cendlition (27) takes the simpler form Consequently, for any given electrochemical reaction taking place under fixed physico-chemical ‘eis (to which correspond fxed values of the ehernicul potentials, there exists a fixed value of ‘electrode potential at which the equilibrium state of the reaction is obtained If we consider a metal-solution system at the interface of which an electrochemical reaction can ‘etur for example zine in a zine sulphate solution, in which the reaction Zn = Zn*” + 2e" can take Plece; or platinum in solution of ferrous anc ferric ions, in which the reaction Fe** = Fe7"" + e= ‘28 take place; or any metal in a solution saturated with gaseous hydrogen, in which the reagtion Hy = 3H” + 2e” can take place, there exists a value of the electrode potential of the metal for which ‘he equilibrium state of the reaction is obtained. When the potential of the metal has this value, the fon canhot take place either in the oxidation direction or in the reduction direction: for example ‘san be neither corrosion nor electrodeposition of zine, neither oxidation of Terrous tons or tion of ferric ions, nether evolution nor oxidation of hydrogen, For any other value of the electrode {PHI 8understoos that this ference of ote i measured by Haber and Luguivs chod mealloned above i 9) Theelcice potentials in question here te those of chery Jens trea eg sper sucked oe eee oe“ CHAPTER 11 ESTABLISHMENT OF THE DIAGRAMS 45 potential, the stale of thermodynamic equilibrium will net be obtsined, and it is possible, fom the energetic point of view, for the reaction 10 take place, either in the exidation ditection {ifthe electrode potential is above the equilibrium potential ofthe ceaction), or in the reduction direction (if te elstrode potential is below this equilibrium potential, ‘As P. Van Rysselberghe has shown in his excellent Inraductlon to this Atlus, the equilibrium potential Ey of an electrochemical reaction is equal to the reduction affinity per unit charge, ie. the afinty of the chemical zeaction obtained by combining. in the reduction direction, the electrochemical reaction studied with the electrochemical reference reaction, which becomes at 25°C 5 Erste B01 Ev lag M1) — ah oon For exainple, in the case of the reaction Fe “+ 22° for which the standard equlivium 4p C7) poretal at 25°C, measured with respect to the standard hydrogen electrode is F!'= ~ o44a, the redacion aft, relating to the reaction Fey's + Hayy->Fey + 2H (aking place under standard af whieh cendiions, is ~ 0-440 V: the oxidation affinity, relating to the reaction Fey, + 2H, >F enc, + Hayy E18 the equilibriom potential of the electcochemice! reaction; is + ogo. ) is the standard equilibrium potential of the reaction at 25°C, ie. its equilibrium potential for the particula: ease in which all the reacting substances ere in the standard state at 25°C: fugacity, 1 atm, for gaseous substances; activity, tg-molfl (or 1 g-ion/kg of water) for dissolved substances ‘The value of the standard equilibrium potential E can easily be ealeuleted from equation (37) if we know the standsrd chemical potentials u* of all the substances taking part in the reaction, Given below are some examples of standard equilibrium potentials and the corresponding equili: brium formulae, based on the following values of standard chemical potentials 1° (4). 44 FORMULATION OF ELECTROCHEMICAL EQUILIBRIA The equation, ew (which zives in magnitude and sign the vue of the equilibrium potential ofa given electochenica! Fet* (aad) =» yoa #0 asd) = 860 cl resction EyM + e~ =o) expresses in short the condition of thermodynamic equilforism of ths Bees ial = 258 5 Se escou) ea reaction, Indeed, the ainity A ofan electrochemical reaction can be expressed by the equation oe (Gisobes) o: oy ad the equation Sa ayi sb atotonl Homogeneous reaction in aqueous solution: oy eos aa 2380 ~ 20300 ano BE22 ork) on esion whichis equivalent to equation (29) expresses that the affinity ofthe electrochemical reaction is zero aN at the equilibrium, ‘Equation (33) enables us to compare the equilibrium condition for chemical reactions ane the equilibrium condition for electrochemical reactions? Solid/sotution reaction: Reaction equation EM Foy = Feit tac: Equilsrium consition Em =o Hohe csv a Giatoxa Bag 24 Ys ‘We see that in the same way that the equation of an electrechemieal resction differs from that of a = chemical one only by the presence of a term which indicates the presence of free electrons e, the Bae 9: tae Cee i Cre) al oleton Cnet) ‘equilibrium condition of an electrochemical action differs from that of a chemical one only by the presence of «term which expresses the energetic influence of these eleetcons in the form of an slectiode potential E, By manipulating equation (33) as we manipulated equation (8) relating to chemical equilibris, in paragraph 3, we obtain successively, by substituting fugacties end activities (M) and standard chemical potentials y/ an Gas/solution eaetion: BHD y= Ong Gay bbe Het She tHho 0. " age POT Ste Hao peoccuntate Fyn stant —o.ofoipll +o.01i8tozpg, (vl) (gas electrode tension) anna y, edox tons ; the above that (or “redox potentials"), the metal solution tensions aS (or “metal solution pot © gas electrode tensions (or “gas electcade potentials") are only ‘theee particular cases ofthe equilibrium tension of an electrochemical reaction.46 CHAPTER I 5. CONSIRUCTION OF POTENTIAL~pH{ EQUILIBRILSE DIAGRASIS(!2) In view of the above we shall now show how to proceed with the construction of potential pH. equilibrium diagrams. We shall consider, by way of an example, the particular case of the system iron-water at 25°C, which is treated in detail in Section 121 of Chapter IV, 5.1. STANDARD CHEMICAL POTENTIALS ‘We draw up a list of all the substances that we propose to consider and find out from chemical literature the values of the standard chemical potentials" ofall these substances, Except where indicated, these values have been taken [rom Latimer") We make a table of these values [in small calories) grouping separately the condensed substances (solid substances and liguid substances other than water), the solvent (water) and the dissolved substances, and the gaseous substances. Ia each of these groups we classify the derivatives of the clement considered in order of increasing oxidation number Z. “In the case of hydroxides'or other bydrated oxides, the chemical pocentials ate preferably calculated for the anhydrous oxide which would have the same stability"); when the same oxide exists in different forms {allotropic modifications, or differently hydrated oxides) we classify these forms in order of decreasing stability, ie. in order of increasing value of chemical potential calculated for ihe same chemical formula (which isthe anhydrous form here), and we label these forms by the indices a,b,c, Conceming the values accepted for the standard chemical potentials, we indicate their degree of accuracy by writing in italics the figures which cannot reasonably be considered exact, the last of the figures no in italics nevertheless being subject to caution. For example, here ate the values of the standard chemical potentials x* which we have taken in the case of iron! : : BH eh = = e fe f Fe boat - = FeO fle (FeCOM) = SRA — sone s Z ukew weer + + Feo, 312 ee : = +0 me, = Pert % 0 Feat tyes PeeOW,) 16 Feow : 2 Fecolny Sales a 5 : Poort) =11Leks 5.2, REACTIONS ‘We write the equations of the various reactions in which these substances can take part two by two in the manner shown in paragraph 2 above, ie. possibly introducing. apart from these 160 sub | stances A and B, water H,O, the H” ion, and the free eleciric charge €~ (1A sinilr acount ving ne the synm eoppr-naer, hu bmn plied ee technique #3) of CERELCOR. ros (] The chemi! poten ef is anhydroum side cated by miles Yo he as many es 38650 tH Bee ae hte? molecule NE ches Stat Born, = 115 Seal RONG To pg = 1s yO sBOpD = SB (IME Larne, The Osi So uf the Element ad ther Pa fn wot Sion. 2n ed, Prew NewYork. 19s Ress Reroute Themodiraae Deve. Uaiveaty af Cama 961 0 of eraruction ofthe pocenisipH eaulitiom dg relating vo te r= (Lecons at corein Aeerohinigne ( fiseue. pp oS. Rapper | al potential of the hydrated onde formals ofthe hydrated onde For J ESTABLISHMENT OF THE DIAGRAMS a ‘These reaction equations will therefore have the following general form: I= mit 0) to the physical state of the substances A and B, two forms Whpelhtnne < group these reactions as follows accord rnuieating, foreach reaction, the oxidation numbers Z of the element in each of thes «homogeneous reactions (two dissolved forms): by heterogeneous reactions involving two condensed substances (generally 1wo solid fore) & heterogeneous reactions involving one condensed substance (geuerally solid) and one dissolved substanee. ‘lien the system considered includes substances in the gascous state, we also consider all or some 1e groups of reactions below (group d will not be considered when there is only one substance in ous state) «heterogeneous reactions involving two gaseous substances; «, heterogeneous reactions involving one gsseous substance and one dissolved substance: {heterogeneous reactions involving one gaseous substance ané one condensed substance (generally solid) ln cach of these groups. we consider separately the chemical reactions. in which the forms A and B © ibe sume oxidation number Z and in which electrons ¢ do not appear (the coefficient af the tron is then equal to zero), and the electrochemical reactions in which the forms A and B have oxidation nambers. and in which electrons appear (the coefficient m is then not equal 102870) In each of these groups the chemical reactions are classified in order of ineveasing oxidation somber: the electeachemical reactions are classified in increasing oxidation number ofthe least oxidized ‘2. and following this successively in increasing oxidution number of each ofthe mere oxidized forme “Each reaction is given an iemtication number, with the intention thed we reject thase reactions ‘at later stage of the work, appear to present no practical interest. Thus we have below the reactions that we considered in the ease of iron|*) (4) Homegencous reactions (two dissolved forms) 1 Ress eall.om aurea ee 2 Fess SF Ihus reales ie Poole ua Fe(oMyye. i> 2 4, Re Fevee te For Om Veolee tte 4 Me Feiss pall ifle MeO seal : r Fe(OH) < eee No We, salhus Fear sane +50 eed #0 Fees! aihue fer +All We Footie S5ko= Foor S7- be Hl Fe(GI=aMG= Fear SAH + 5 be eidtion ) Behe sonvenion Gscused im preranh 2 this equation cua represen cpu 111 he equation Plow be chemical semble fm Het Wpe represent Soke shen the sym noel fe rorsen wate apd stance doled fn agueut stonCHAPTER tI (8) Heterogeneous reactions involving 1wo solid substances: nee FeO nally 9 ora Ht FejO, 6 4 5e— asl 1 FeO, coli £6 sree: FeiGi eal cee poner) 1, Fo,0, sill sae anes " FeO, all tae (©) Heterogeneous reactions involving one solid substance and one dissolved substance: oe 0 Fes = 0 wane Feo + 0 +a +3 90. gFes-> 4510= FeO, +61 a Sh aFeOi + MhO= FeO, +41 zi BaF e(OH FeO, + He0-+all+ ote Fe Fees sae = 3. Fe FeOs +3 ae ors3 | 3. Fe Fer wae passat Met 4 GIO FeO, Ne yo 5 ST GHReO: FWY = FeO, 4 alhOrae S305 FeO, = Fed, Sie Dae FoF ae Q aes 8 ae - 3. GH 5.3, EQUILIBRIUM CONDITIONS FOR THE REACTIONS ‘equilibrium condition, by applying the following For each of these reactions we evaluate t eauations, etahliched in paragraph Vand 44) for chemical reactions: for electrochemical reactions. and we write these equations in such 2 way as to make explicit the influence of pH, which occurs implicitly in the term Ev og (Mp. In the case of chemical reactions writtea i the form en GAL eH. = EB mls, in which B is the alkaline focm and A is the acd form of the element in question, the condition for equilibrium will be of the for 4 oy Bl tes keene iia piles (oy ‘This equation shows that the ratio of the fugacity (or activit;} ofthe alkaline form to the fugacity (or activity) of the acid form incresses linearly with the pH. tat ESTABLISHMENT OF THE DIAGRAMS “9 In the case of electrochemical recctions written in the form w 2NGeH.D + ne7= OB mils, sich A is the oxidized form and B the reduced form of the element in question, the condition for cquiltciars will be of the form a tye eg IU ag RE gg (AYE ) : bya Ey top (a and in the most common ease when & and the reaction is A + cH,O + me” = B+ mit" 90 yg (AD. ‘ pl + 229% gg (AD, o S12 ps 82 Nog GO {vis a5 well 10 note that the fugacity (or activity) of the oxidized form A occurs in the numerator of the term log (AB): the equilibrium tension Ey, increases when the percentage of tbe oxidized form “The equilibrium formulae for the twenty-nine reactions quoted in paragcaph 5.2 ean be found in paragraph 2 of section 12.1 of Chapter TV (p. 308) In the particular case of solid substances existing indifferent varieties having different free forma tion enthalpies (labeled in 5.1 by the indices a, b,c, ..) we label the eortesponding equilibrium con- stants and standard tensions with these seme indices [see, for example; equations (27) and (20) concera~ ing anhydrous Fe,0, and hydrated FeO, (or Fe(OH),)] Finally, if we put (A) = (B) in equilibrium relations of the type (ge) or (42) we obtain the following. equations which express the conditions of pH and electrode poteatial for which the activities (or the fugacities) of these two forms are equal(®), being valid for the case when the forms A and B of the clement in question are either both in the dissolved state or both in the gaseous state: Such equations, concerning the reactions between the dissolved forms of iron accorditg to reactions UMD are given under numbers I-11’ of paragraph 2 of section 12.1 of Chapter IV (p. 303). 34. CONSTRUCTION OF THE EQUILIBRIUM DIAGRANS Considering the electrode potential and the pH as independent variables and the logarithmic function ofthe conceatrations and/or pressures ofthe substances A and B as a parameter, we can now sroveed 10 establish potential-pH equilibrium diagrams on millimetre paper on which we bave pre- ously drawn the lines @ and b: (line «) (line 8) Bj. 0.000 — 0.0594 pH (salt) Kam 10a — a. pill (volt) ‘sich express respectively the reduction equilibrium of water according to the reaction Hy = 2H + 2e~ {and its oxidation equilibrium according to the reaction 21,0 =O, + gH* + 4e~ (@)at a hydrogen oF oxygen pressure of 1 atin [These single elatonsips an oly be applied when the formulate to wbsancts And B eee sme gos ofthe abstane under eonseration ce Fe" (Fe"™ Fresno ths to eet fox the spent Cer 8, 'NOreltoshipstae tobe mode by aig for si ks conten aon (foray the werent nef arms 'msolaion Grg05” + Cr”) cee tal restr Por ops) of the tw gastous Fras (Ny + NOD0 CHAPTER 1 ‘The drawing of lines expressing the conditions under which the concentrations (or activities) of the two dissolved substances are equal [equations (I'}(I') relating to iroa] enables us to represent in Fig. 1 (seotion 12.1 of Chapter IV) the domains of relate predominance of the dissolved forms in question: Fe"*, HFeO;, FeOH™*, Fe(OH)! and FeO, ~ ‘The dravsing of lines which express the equilibrium conditions for two solid substances [equations (12)-17)] enables us to represent the domains of relative stability of the solid substances in question Sucti a representation can be made, not only for stable equilibria (Fe/FeyO,/Fe,O,), but also for Unstable equilibria (Fe/Fe(OH),/Fe(OH)3) By superimposing these two diagrams, we ean easily pick out the conditions of potential and pH under which a given solid substance and a given dissolved substance can be simultaneously stable. By tiving a defince value (for instance zero) to the logarithmic term which, in the equilibrium equation for this solid substance and this dissolved substance [relations (18)-29]}, expresses the value of the concentration (or activity) of the dissolved substance (far instance 10° = 1 g-ion/l), we define a fine which represents the conditions under which the solubility of the solid substance considered, in the dissolved form considered, has this value. In this way itis easy to draw, step by step, a line which Fepresents the locus of the points of the diagram for which the solubility of the different solid substances in all che aliferen dissolved forms has the same value. It is often useful to establish such “equisolubility” lines for different solubility values (for example, 10°, 10°, so and 10~® gate, of the element con- sidered per kilogram of water('"). We thus obtain, after omitting those lines of parts of lines wich Dave no practical interest, figures such as Figs. 4 and 5 which are two electrochemical equilibrium iageams for the systems Fe-H,O: Fig. 4 represents only stable equilibria; Fig, 5 represent, with regard to Fe(OH}; and Fe(OH), unstable equilibria. It is as well to note that each of the lines indicating the solubility of the different condensed sub- stances in all the different dissolved forms changes direction abruptly at the places where the composi- tion of the system changes abrupily (for example in Fig. , when we pass [tom the domain of relative stability of Fe to the domain of relative stability of Fe,Og}; these lines change direction progressively When the composition of the system changes progressively, tbat is in the neighbourhood of the lines which separate the domains of relative predominance of the dissolved substances (for example Fe" and Fe*"*) The drawing of these curved portions of the equisolubility lines can be done by a graphical method that we have described elsewhere(?3, These equal solubility ines thefefore have sharp points at the limits of the domains of stability ofthe condensed substances, they have gradual curves near the limits of the domains of predominance of the dissolved substances. Such diagrams are valid only for solutions in the presence of which the metal or metalloid con- sidered can exist only in the forms that have been considered in establishing the diagram. When the solutions contain substances capable of forming soluble complexes with the metal or metalloid (for instance cyanides forming ferro- and ferricyaaides) or insoluble salts (for instance phosphates forming ferrous and ferric phosphates), itis necessary to modify the diagram by adding to it 2 representation of the stability conditions of these dissolved or solid substances. It is then necessary to establish dia- trams for systems which are not binary such as Fe—H,O, but ternary such as Fe—CN"—H,O of Fe—P0,-"-—H,0. (71 sal fc as rom the pant of of sipifstion. hes a olan sin he sme abies sees er lvgram a sie, Co Lens sur kero trong # Hacks Rapp tcaigee RT. 29 of CEBELCOR. 1956, pp. a2 nd 23. CHAPTER UL USE OF POTENTIAL~pH EQUILIBRIUM DIAGRAMSSECTION 1 GENERALITIES M. Pounaan ty re important preface that R. Plontelli has kindly written for this Avls, he has brought out the practical signifcance of potetial-pHT equilibrium diagrams and has pointed out the imitations which ‘ee must be aware of when using them. Inthe accounts which follow, the reader wil find some examples ofthe application ofthese diagrams tothe study of concrete problems of inorganic chemistry, analytical chemistry, corrosion, electtodeposition and geology. Elsewhere can be found some examples of thelr application to catalysis) and the study of batteries and accumulators) ‘We shall therefore be very brief here, and content ourselves with reviewing a few pai important fundamental idea. e We know well the tremendous scope given to chemistry by chemical thermadynamics; which isthe science ofthe application of energetis to chemistry ends based on the canst uf lena eyulibriam Chemical thermodynamics, whose fundamental basis was estabished around 1876 by J. Willard Gibb, and whose applications have greily developed since the beginning of this century, bas enabled us to Understand a Tange number of formerly mysterious chemical phenomena; it has allowed us to predict 2H,0 () and with reduction of ferric oxide according to the 1 4+ OH” + 20° = 2Fe"* + 3H,0 (28)(") If, for this same pH and potential the solution contains hydrogen peroxide, the later will tend 10 be reduced to water according to the reaction HO, + 2H" + 2¢792H,0 (2) (see Section 12, Chapter 1¥); ifthe solution coptains cupric ions, a cement of copper ean be formed by the ceduetion © p 2¢7 > Cu U5} (eee section 121, Chapter 1V); if t contains a chromate. a deposit of Cr,0, ccapabie of passivating the metal can be farmed by the reduction 2CrO,"~ + 10H* + 62" + C10, + '5H,0 (54) (ee section 10.1, Chapier 1} It must be understood that the electrode potentials and pH considered here are che characteristics of a meial/solution interface, and not of some other part of the metal oF solution, In the very freque ion FeO, ent Tenis pricy Pacman, Toei, Oa 948 [EVA dstaodsecpant of hie outs the scope of he gue des mutant @ pate) (Recut de Memes RM. § oF Ich and Te deannble ne Te cmportenet Secoe CEBELCOR. oe. “Tae reaion (2 Ei > 0 feu om the adaptation to electrochemical estons of De Donde’ ction Ar 2 © which sonnets the isin oP chescl geacn fed Bethe tig afte speed 11 iB the gh of ny (Ci'Fhe number acts ac hone der mh hee rentons fave Bem clsied i Chae TV in secon 12 fon, secign 12 or hyarosen posi section HAI fr copper ard section 101 fr chrom °s Law, considering this feaction current 19 be positive in the ease of § GENERALITIES 55 «ase in which the metal or solution isthe site of electric currents or chemical changes, it is necessary ‘> make sure that the:chemical composition assumed for the solution (and consequently its pH is of the fraction of the solution in direct contact with the metal, since this composition can differ zatly from the mesn composition ofthe solution; careful note must also be taken thatthe electrode potential ofthe metal is measured ia such a way as to avoid any effects of ohmic fll or diffusion poten sl for this pwrpose, iis best to use Haber and Lusgin’s capillary siphon method or Piontells method Finally, we cannot insist too much on the fact that the equilibriam diagrams discussed here can rly, by themselves, solve a very limited aumber of problems, as Piontelli has made clear in the final part of his preface. They are only tools at the disposal ofthe electrochemist ard they must always be used in conjunction with other means of investigation. Among these means, a particustly important iat is held by studies of electrochemical kinetis, which are based on the experimental determination © potential-current curves (for example by intensiostatic or potentiostatic methous) and which enable sw to establish the laws connecting the speed f of an electrochemictl reaction and its alnity EF) bright future can be predicted for groups of investigators who are competent at the sime time in ihermodynamics, kinetics, and physics and physical chemistry of metals,SECTION 2 GENERAL CHEMISTRY G. Vauenst 1. Introtution. 2, Redox couples. 3. Coexivence potential 4. Mixed covpes, 5. Graphical represetain 6. Disproportionation % Anphoteriztion. 8 Rotes of reactions which are thermodynamical posite. 9. Concise, 1. rerropuerion ‘The electrochemical diagram of an elemeat summarizes ia ain extremely condensed form the most salient features ofits solution chemistry. To cover such a vast domain necessarily requires a cerian complexity of the diggrams, the basic eatures of which may thus escape a first examination. is perhaps not superfiuous, therefore, before considering some concrete examples, to remind the reader of certain concepts introduced in the preceding articles, but at the same time relating them, more directly to chemical considerations 2. REDOX COUPLES Solution reactions, in particular those of inorganic chemistry, very olten involve a transier of clectrons e~ froma reducing agent R, to an oxidizing agent O,. The possibility of the reverse process under different conditions implies that R, is converted into # conjugate oxidizing agent O, while C, js converted into a conjugate reducing agent Ry. Thus the action of chlorine on ferrous salts cun te represented by the scheme: GENERAL CHEMISTRY ” In general, if the stoichiometric coefficients are chosen so that the reaction involves only one clectron (forthe sake of convenience), the free enthalpy of a so-called redox reaction: ely H:0, ) wien O is intro EY. This is due to the fact that in the final cullitrium state, AG = 0, be. Fy = Ey. Now x, > implies that E, > E'°™, but also implies that &y < 05 ie Ey < EP, Hence =e Since the order of addition of reagents to the system does not influence the equilibrium state otuined, the same relation E'*! < EY is evidently appropriate for predicting a significant reaction ‘hea one adds a reducing agent R, to a medium contaiting a certain oxidizing gent O; Ey> BM By, 4. Mexep courLes In most cases a complication arises: when the active element does not exist as & simple substance ic one or the other of is two forms R, O, (4s in the couples Fe?" |[Fe** and C1” |Cl,),the couple under* Consideration does not involve only an ability 10 transfer electrons, but can involve simultaneously the release or capture of other particles, The most important case is when the only elements linked to the active element are those of the aqueous solvent, iz, hydrogen and oxygen. Thus, the action of Potassium permanganate on ferrous salts in acid solution can be interpreted as a traasler of electrons anal B6 Bi here exit ron 3 = fi bt inode sino he peeing lve woul inya CHAPTER I, SECTION 2 on io manganese, accompanied by a capture of protons by the oxygen combined with it, while the reverse reaction can be interpreted as a transfer of electrons on to iron, accompanied by a relesse of protons by the solvent, which supplies the oxygen then necessary for the stabllity of che manganese aton deprived of electrons ne os ° ete Mn Ost BH at SFr a Mate §H0. bet to two J In most cases, therefore, we shall be considering hall-Feactions which can be represented >y * ait gHLO 2 Opt mH bam wo (of which the free enthalpy is (onesie Ti SG, AGP+ 2 3RT log the sctivity of the water being prectically unity. The reversible potential which can be associated with the souple fis here RT, (Oa AFR Introducing the symbol pH = —log(H*) o Bea — 2 an BE ng OD", i fc, (7° ifersfeorn (3) only in the term EE? ~ o0sgrmin pH, lineae in pH, which replaces the constant term E®. The precicion of redox reactions must therefore take into account the pt 0 {he media Ta general K varie throughout such reactions ules the macium vs sutably bared Lett suppose that this condition is fled: formula (7) (8) and (9, which are expresons forthe contstence potentials of R, and O, remain vai, provided that Es replaced by E” For the pancpal caves considered in 31, 32 and 3), we have the following coeisence potential 4.4. Oyand R, ip the aqueous phase: o 85 (ay og] — 2252 2. 0,8 pure substance at 1 atm. pressure; R, in the aqueous phase “ nm [ep 228 pog(ange— 282 a tog ts} — 280" pa 43. O;in the aqueous phase: R, a pure substance at 1 atm, pressure ene or [FP St tegca808 = 222 a ogc] — 2 oa For each pH, the calculation of Ee end Eby means ofthese formulae will once again enable vs toprediet the possibility (when E'*" < EP") ofa practically simiicant reaction between a relucing gaa! R, and an oxidizing agent 0; ‘ae hy are neptvg, toweser a8 the ct fe the couple NOH DO wae ahereg = sim © me Gee IVa) ym ant gre postive ar 20 in 18,02 for whh the hl eeacion ie $8 GENERAL CHEMISTRY 6 5. GRAPHICAL REPRESENTATION ad ef cartying out @ fresh calculation for each application, it is more convenient to make @ representation, once and for all, of the E{° values for each couple (R, ©). They depend on two sariables, C, and pH, and one ean therefore plot a family of iso-C, straight lines using E and pH as co-ordinates Jn general theze will be several such families of lines corresponding to a given element, since its ‘chemical properties generally involve the existence of various redox couples in which it takes past. For example, chlorine is the active element of the various couples: EEO, G4[C1O~ C1O-[C105, cIOz1 CIOs. 2105 Clos. ‘The eoleetion of families of io-C; lines for a given element, in terms of (E, pH) co-ordinates, consists the electrochemical equilibrium diagram for this element. Fora certain value of C, each (RO) line of such a diagram separates the plane ino two regions below it one has x, < 05, ie. the reduced form R, predominates; above it one has x, > 05. ie. the oxidized form predominates. Thus E, has a meaaing al each point of the plane: the straight lines E= A ~ BpH represent the particular values E/", which one need no longer éenote difereatly Jn order to predict the possibilty ofa reaction between en ovidizin agent O, and a reducing agent R., one can superimpose the corresponding two diagrams: after selecting the appropriate iso-C, lines, Hows tha. depending on whether the tine (R,,O3) lies above or below the ine (R,, O,) om the DEL scl considered, R can be oxidized, ors practically unoxidized. In the second cas it isthe reverse action between the oxidizing agent O, and the reducing agent Re ich becomes isi. The cae of two Hines intersecting ata point P (Fig. s by no means exceptional: it evcals {he marked influence of pH on the direction of certdn reactions. For example, the coexistence potential domain 0 (0: Rad [oersoctenonky joveaction orks e Sao pe Fiat, E csponding to the reference couple Ha|U*(E® = 0) at 1 atm. pressure. is Ey existence poteatitl coresponding to the couple MoO,(solid)|Mo’™ is Ey e711 ~ 02361 pH ~9039'logiMo*), whece (Mo?")repesents C2, Let us suppose that C, = 02, iz, [Mo Then Es = ocx — 0:2364 pH. In an acd solution, will hydrogen ata pressure of ratm reduce MoO, {0 dissed Mo?*? The condition necestary for thi is ~00591 pH, The aon —o.436ipH ction is possible at pH's belowe CHAPTER Ill, SECTION 2 whist at higher pH's, Mo}* can on the other and decompose water with the evolution of hydcogen and the precipitation of MoO,. These conclusions are apparent, without the necessity for calculation, (on looking at the electrochemical diagram for molybdenum {L¥. 10). We call altention here to the particular importance of wo couples which are involved in any aqueous system, due to the presence ofthe solvent: the couple H,|H* of which the coexistence potential is E, = ~o0sg1 pH. and the couple H,0|O,, of which the coexistence potential is E, = 1230 ~ (00591 pH. The straight lines (a) and (b) representing these couples are indicated in broken lines on all the diagrams in the Als. 6, piseeoroxioxanioy AA redox amphorer is a state X ofan element which is atthe same time the reducing agent Ry of a certain couple R,|O, and the oxidizing agent O,-of another couple R,| O;. Thus, the Fe'* ion iy en aamphoter, being the seducing agent of the couple Fe**|Fe!* and the oxidizing agent of the couple FelFe?*. To a given amphoter therefore correspond (at a fixed concentration) two coexistence lines E, = Ay — By oH: Ey = A; ~ B, pH. Now. in order for the amphoter to be stable, it must not be ible 4o react with itself according 1o the equation ‘ 2 1X4 gulls 0+ baker ml etm He Baa 10. 1s thus necessary that” HOOD Ee oe AL By pl > Ay Bypt the line representing its reducing function must lie above the line representing its oxi ‘The three predominance domains invclved age situated in the right-hand part of Fig. 2 FE] & “Theee cases may’ aise: | G4. The line E; lies below the line Ey over the whole range of pH considered, The umphoter is shen stable over the whole of this range. For example, the aqueous solvent is an amphoter since its inyolved in the 1wo couples H,0{0; fcouple 1) and Ha/Ht" (couple 2). represented by the to lines band fa} mentioned above: these (80 lines ate parallel and the fies lies above the second. which explains the great stability of water at al pHs 62 The line E, les above the line Ey over the whole range of pH. considered. The amphoter fic is known experimentally) is then always metastable, This isthe ease, for example, forthe oxygen containing compounds of stlphur. apart from those corresponding to sulphuric acid (HSO;, SOL) and dipersulphuri acid (5,037) a4 willbe scen in TV. 1p. The less oxyzerated compounds ove tact isolation solely 10 the manifestly slow rate at which they dlspreportionee, whieh is probably & com sequence of the ectivation energies nesesses) for breaking the covalent bonds. Ths, complete m ability eneountered only st-metal compounds. since eletrovatent bonds | GENERAL CHEMISTRY 6 ‘dominate in these compounds. Esch of them can be denoted on an electrochemical equilibrium ‘sogram, but such a possibility of existence is incompatible with reality for many non-metal compounds ifficulty can be avoided by disregarding certain very stable states (such as sulphates in the case ‘uiphue) for the purpose of certain narrowly defined practical applications, but this means that the ber of diugrams corresponding to a given non-metal must be increased, as has been done for ‘hlorine (IV. 20); these diagrams then correspond to different degrees of stability 6.3, The line E, cuts the line E; io 9 point P. In this ease, which is shown in Fig. 2, the state X is able only in the region of pH situated to that side of P on which E, lies nboxe E,. In the opposite i X must disappear by disproportionation. The extension Ey, E5 ofthe lines E,. E into this region not therefore appear to have any meaning: the only couple to be considered inthis region is R/O; jraing in a Way the metastable amphoter X. A new coexistence line E5, starting trom P. separates « Jomins Oy and Ry which have become contiguous. Reasoning step by step in this way, one under. nds why the predominance domains af most amphoters (but not those of the estreme states, i. those which are richest or poorest in electrons) appear on the diagrams as closed domains, Ther licnits in a torizontal direction are often due to the disappearance of a state simply on account of a variation jt pH, without there being oxidztion or reduction of the active element. The acid function of certain ydrogen-containing compounds involves an equilibrium between the protons released and the rest the molecule, Thus for dissolved hypochlorous acid: HCIO = C1O™ + H*. If, ata given tempera- ‘ure, & is the equilibrium constant for such « dissociation, and pk = —log , one hes fe va + log 3 ‘aren Now the ubove definition of coexistence requires a rertical boundary. of abscissa pl = ph ‘eparating the domains HCIO (om the ffi) and ClO (or dhe righ), Ia this example. pk = 149 at 25°C. ‘The generalization of this idea to other Schemes of proton release in the absence of redox reactions. ©2 On UF FIL AOL path reas no difficulties. The existence of triple points P not involving a vertical boundary, asin Pig. 2, implies however © possibility ofthe reversible disproportionation of an amphoter X on chace of pH of the medium. 5: all pH's at which X is stable, the point representing the equilibrium of its disptopertionation inio ©, and R; Ties infact inside ils predominance domain: it remains there iT one changes the pH in the sense which brings it nearer to the abscissa of P. The trajectary of the equilibriurn point always lies fetween the lines PE, and PE, und finishes up at the aripte point, If one continued to change the pH i the same sense, X would cease to be stable and would be converted into O, + Rz the active element ‘ould divide ise hetween these states in proportions of the sume order: the trajectory would then otinue in the immediate neighbourhood of PE,, the boundaty between the domains R,}O,. By of an example. we shall discuss « diagram showing metastable states of sulphur. This diagram,

the: various couples involved are very close and it would thus be somewhat arbitrary to define a sesarate domain for each of the intermediate polysufphides. If, staring from the rentasuiphide, ie. from the domain 21-20-25), one continues co increase the pH, one areves finaly at tne vertex (20-257). where! GENERAL CHEMISTRY 65 the ultimate disproportionation of the polysulphide sulphur takes place, giving $,03- + HS, thus producing the minimum index y = 1; In actual fac, all the indices intermediate between § and 1 can sined by inereasing the initial proportion of alkali with respect to sulpbur, providing that one «ata soffciently high temperature, (d) Disproportionation of polysulphides by acidification, Under conditions in which the rate is sufficiently great, ie. a a fairly high temperature, the disproportionations {c) and (b) are reversed if lone Fe-2cidifes the solutions obtained. This is due so the fact that in the miatures of polysulphides and thiosulphate corresponding to such solutions, the representative point lies on line (20) and moves along it up to the vertex (19-21-20) on addition of acid; one can then move into the sulphur region, by means ofthe reaction of $,O3~ with S3~, the reverse af the disproportionation (b) considered above This is no longer true ifone starts with 2 polysulphide solution free from thiosulphate, which ean he prepared a indicated below: its representative point then lies inside the domain (21-20-25): it ' cowards the vertex (7-21-25) on acidification. At this vertex there occurs the disproportionation + H* = HS” +43; ine (7) s then followed as far asthe vertex (6~7~2), which lies on the vertical line corresponding to the ac couple H,S|HS"; hydrogen sulphide is then produced according to the uation HSI oS, Ic isin fact well kaowe thatthe acidification of polysulphide solutions, even at ordinary temper tures, liberates hydrogen sulphide, with the deposition of sulphur, The two suevessive reactions involved hase moreover been separated eiperimencally($) Nevertheless, at ordinary temperatures, the disproportionation of sviphur by alkalinization is a slow reantion, a8 s the reverse reaction, ie. the action of acids on disproportionated solutions. Under those conditions, a different diagram for the metastable states of sulphur, neglecting all oxygen-con- taining sulphur compounds(*) woulé give a better description of certain phenomena which can be Dbserved only at room temperature. On such an auxiliary diagram, the polysulphide domain is ‘naturally considerably enlarged. The representative point for alkaline colutions ef disproportionated sulphur no longer lies on a boundary and, at room temperature, acidification of such solutions has the same effect as if one were dealing with polysulphide solutions [ree from thiosulpbate, Nevertheless. the hae present would no longer be inert at low pH’s and would show its presence by the dis ‘onation (a), which produces additional sulphur +SO, below a pH of about 2 a 2. aurmorenzanon (ne may cl the reverse rection of dspropertonation an anphoeriarn, Returning 0 Fi. one may imagine tha, sta pH compatible wth Ie salty of ove eases te oidizng agent O, te eae wth he veduting agent Rte eeaton is ponble sce he ie PE, then es ste ne PE wl gve ie othe mphoit X Hence on en dave aul thet when to tates on er "HG of «given dona, they en es together to produce he slate proper otis Coma hs ah clertnton. Let fet now fo Fi 3 fo sore examples f Acton of hydrogen slp on suphurous el. The H,SO, and HaS domais, (12-1310) 18d, on either se ofthe domain, L8-1921-0) One can therefore have Beeston “ch docs in at constute the second phase of he pros for extracting sulphur fom Lacy ssc. Atroom temperatare is complicated by tne ormation fthonecompount wich weave need in ploing the mecasabe diagram n Fle () Dison ofsplur i ape soluins. The domains ofthe ditohed fons HSO;, $03 4 that of yale on eter se ofthe 8,0} domain. Sulphur can therfore teat wh phe st S4 ath,“ . CHAPTER 1. SECTION 2 solutions according to the equation + s.0F This i indeed one ofthe methods used for preparing lkali metal thosulphates {6} Disstcon of sulphur in sulphide soaions. On account ofthe smal second dissociation constant of hydrogen sulphide, a alka meta suphie dissolved in aqueous solution i converted largely ine hydrosulphide according to the equation : S210 = MS“ 01r i Nov the Sy. and HS” domains lie on either side of the $3~ domain (21-20-25); sulphur ean 4 therefore reoet with solution of sulphie (HS” + OF") according othe equation 484134 ON- 2 SH HLO. a This is a methed for preparing polysulphide soltions free from thiosulphate, and it can be used 4 even at room temperature, At this temperature itis not interfered with by the disproportionation of sulphur to give polysulphide + thiosulphate, which is stl very slow, as we have already seen, “ 8. RATES OF REACTIONS WHICH ARE THERNODYNAMICALLY POSSIBLE “The preceding paragraphs show how much care is required in making tse of the thermodynamic predictions embodied ,in the electrochemical equilibrium diagrams. For this reason they should be considered as a means of interpreting known expecimental facts rather than discovering new ones, ‘Thermodynamics cannot give information about the rates—which are often dliost zero—of reactions ‘which are compatible with the siate of a given medium. If this wére noi the case, many substances, such as sulphites, thiosulphaies, etc. would have remained unknown, In practice itis as if 2 double 4 barrier were associated with each redox co-existence line, at a certain distance above it (for the reducing function) and below it (for the oxidizing function). As explained-in IIL 1, such divergences may be characterized by overpotentials, which depend on eatalytic conditions. Their values (anodic or cathodic for reactions which can be brought about by electralyss, vary from case ( case. For example the senerally lov couples, whose co-existence potentials are represented by the lines (a) and (b) for water, are most often protected by overpotentials ofthe order of a volt. This means that gaseous oxygen does in fact oxidize only those reducing agents whose coexistence fine is more thar 1'V below line (8 Returning to Fig. 5, one can see that a stream of oxygen can oxidize a dissolved thiosulphate only with ifficuty to sulphite. On the other hand it can easly oxidize dissolved hydrogen sulphige to sulphus, and likewise it can easily oxidize an alkali metal hydrosulphide to pentasulphide at pll's between 8 and 19, oF to thiosulphate at pH’s above 10. This explains the well known difference between the ageing of a selution of ammonium hydrosulphide used for qualitative analysis, buffered at a pH of bout 9 on account of its nature, and that of a solution of potassium hydrosulphide, whose pH it 7 nearer 14. In the same way one can interpret another industtial process for the manisfacture of thio. sulphates, which consists of cisproportionating the sulphur first of all ia an alkaline solution, thes bringing its representative point on to the boundary (20) then passing a stream of air through the solution, thus bringing the representative point inside the domain (15-16-17-22-20) 9. conciusiox: The few exemples discussed sbove are sufficient to point out the usefulness of electrochemical iagrams asa means of linking up the respective features ofthe various compounds ofa given element ‘The systematic introduction of these diagrams into a tesl-hook of descriptive inorganic chemistry vould, in view oftheir tecourse to logical arguments, help to make it mare attractive th. xen enue | vion of spparently unrelated facts. This would also enable certain chapters to be conden ed, and would 4 thus compensate to some extent the alarming increase in subject inaiter to be taught.) 1)G.Watess. Bul Union Physins Primes 48. 930 6 GENERAL CHEMISTRY a Apart from their educational applications, electrochemical diagrams are of use in research, where an enable one to dispense with @ good deal of the preliminary caleulstion connected with .scevuning the thermodynamic possibility of anew retction, before tackling an experimental invest a, which would be completely fuile under conditions exciuded by the diagrams. But this is all that one can ask of these electrochemical diagrams. They do not enable. of to rrodict the Kinetics of «phenomenon, although this is the decisive factor forthe yield. A certain latitude mnust moreover be allowed with regard to the position of the domain boundaries: on the one hand. the replacement of activities by concentrations is only a rough approximation: oa the other hand, the erating influence ofa rise in temperature, whichis often taken advantage ofin practice, naturally Snodifies the boundaries valid at 25°C.SECTION 3 ANALYTICAL CHEMISTRY G. Ceartor systems, pH is one of the most important, and undoubtedly the easiest to control, The knowledge off ‘oxidation-reduction potentials, which enable us to predict the reactions for each plH, is elso one of primary concems of the analyst. Potentisl-pH diagrams present these properties in their most useful form. By comparing various diagrams itis possible to predict oxidation-reduction reactions; w predic the possibility of these cautions we sould say, because, unlike most other reactions, cxidation reduction reactions sometimes have very small zeaction rates, and the equilibria ean not therefore be attained. Now, for practical reasons, the analyst uses only fast reactions, In some eases the equi are reached so slowly that prediction of the reactions by means of equilibrium diagrams is of ne interest In other eases the diagrams are valuable for a first approximation, Finaly, in many cases they enabl ‘quantitative predictions to be made. In these cases the dingrains summarize « large number of p-opertis ‘and they do it ma manner which is more precise than previous methods, We ean quote some examples which are particulaely striking, especially a far as the understanding and teaching of chemical properties is concerned. For example, the potential-pH diagram ‘or maat ‘ganese: Mn (ID, Mn (I-11), Mn (11), Mn (LV), Ma (VD), Mn (VID, Starting from potential determinatio in skatine media and the solubility product of manganese (ID) hydroxide, the whole of the diagram ea be constructed. This diagram shows, better then calculations or descriptions the domsins of svistene of the varions chemical species the various substances that can be obtained, and the various reicton shat can be predicted for each pH, Making use of this diagram we can not only predict reactons, bu we can also see under what conditions they can be avoided. For instance, by comparing this diggrad ‘ith those of the halogens, we se that in a mixture of chloride and bromide, the bromide wll beoxis by the permanganate at pH = 3; the chloride can then be oxidized at pH! = 0. We ean predict tho substances which will reduce permanganate to Ma (Il) and also the smaller number of substances which will reduce it to manganese dioxide at pH = 0, and the very large number of substaness whic ‘will reduce it to Mn (II-IT), (Il) and (2V) in alkalie media, ete. ‘The diagram for cerium, for instance. shows us that salts of Ce (IV) are very powerful exdizingl agents at pH = 0, and that salts of Ce (Il), on the other hand, are very powerful reducing agents it slightly acid media, “ Redaction by metals, titration of oxidizing o- reducing ageats using oxidetion-reduction indiceto separations, ete, can be predicted and perfected by means ofthese diagrams a ANALYTICAL CHEMISTRY ° ‘These properties are no less important for the electrochemical reactions used in analysis. Electoo- chemicel reactions can be dealt with in a manner analogous to chemical oxidation-reduction reactions, ‘Toe koowledge of equilibrium potentials as a function of the pH js the basic piece of information in tne ease of so-called rapid electrochemical reactions (oxidations and reductions iavolving certain metal, the antimony electrode, the hydroquinone electrode, etc). In other cases kinetic factors must be iat troduced, but, asin the case of chemical reactions, the knowledge of the equilibrium potcntil for each pH is stil often a good enough first approximation to predict or distinguish between a certain number of possibilities. Electrochemical reactions are, of course, the basis of numerous electrochemical methods used in analysis: potentiometric, amperomettic, coulomettic methods, separation by electrolysis, ele ‘To conclude: the knowledge of potential-pH equilibrium diagrams provides an important i= nt for analytical chemistry, which very often involves chemical or electrochemical reactions ia Ic seems likely that this systematic method will be used more and more widely in the fature. BIBLIOGRAPHY . Ceantor, Sur sation des diograrmes potoniel-pH en chinie analyrigue: Penayseguaitatie et les réctons # soltion, Mason, Pais, 1957; Methuen, London, 1954; Aguila. Madrid, 1954; Kijortsu Sruppon, Tokyo ost .SECTION 4 CORROSION M. Pouasane ‘Theorticlcorosion, mus and passivation contions Resisance of meal t pure water Metals which can be pessicted nd atta. (oxide corrosion ihbiors. Degree of nobis of ects Theenentsnonie robe and inmarity Prectea! nobly. mounts end passe. 6, Expevimentalappeetions. 11 Note on thesieneance an retical implicants the poenil-pH eletvockemical euro dagrans. eeveree Ler us assume. asa first approximatioa, that a metal is eorrodible in the presence ofan aqueous solution intially containing none of this mesa} according as the quantity of this metal whi thermodynemicails by the solution i lower of higher than a very smisll quantity whi argument, we shel! set arbitrarily at 10-* gat. 1; this eontent corresponds 10 066» iron, copper and zine; it ecrresponds to Co} me for aluminium and to o7 mg‘ for lead [this hype thesis iv a1 all correct, the lines on the potential-pH equilibrium diagrams which Gorrespond 19 4 solubility of 10°" geat wt of metal per live Gie-the ~* euui-solubility lines) mal between the damain where corresios is posible (corrosion domain! and # domain where 4 clear distince ‘CORROSION a ayossible (non-cortosion domain). In the nor-corrosion domain, two regions {or groups of regions) = vistiaguisted: in one of these regions, the slid stable form is the metal itself {domain of inmunty, ‘oie proteston) in which case, although pretenting « genuine metal surface, the metal is quite sncorodible because the corrosion reaction is energetically impossible: inthe olher region (or regions the solid stable form is not the metal but an oxide, a hydroxide, a hydride or a sult (passiration domain} the metal then tends to become egated with this oxide, hydroxide, hyGride or salt which cun, according tthe circumstances, form on the metal either a non-porous film practically preventing all direct contact fetween the metal {Self and the solution fin which case protection agains: corrosion is perfect. of a rrerous deposit which only partially prevents contact between the metal and the solution (in which case reotection is only imperfect). Understood in this way, passivation thus does not necessarily imply the ‘se of corrosion. Experience shows that, in the ease of non-chlorinated solutions at east, whe oxide vs are generally perfect protectors for numerous metals, among whieh are aluminium. chroraium, oom and tn, In some relatively rare cases, a degradation of the metal may come about through the action. not of dissolution, but of gasification accompanied by the formation of a volatile hydride or oxide. If as'a rough guide, ve assume that metal corrosion can take place inthis way ifthe partial equilibrium pressure of the hydride or the oxide is equivalent to atleast 10°* atm. the lines of the potenti pH equilibrivm slingrams which correspond 0 a hydride or oxide pressure equivalent to 10” atm, will enable vs to wahlish a domain of corrosion by gasification 1 soes without saying that the concentration (10~® g-at.wty/l) and pressure (10* atm) values adopted here forthe definition of the corrosion thresholds are arbitrary and that, in practice, there are ‘good reasons for mocifying these critical values. With this reservation, however, this theory can be fegarded as exact as far as protection by immunity (or eathodie protection) is concerned As for protection by passivation, on the other hand, this theory is rather an over-simplifcation; although, thanks to U. R. Evans, the part played by oxides in protection by passivation received formal suretion in (927, this Fole is not proved in all cases of passivation; for example, absorption phenomena sin play @ predominant part, On the other hand, there is a great scarcity of sufficiently precise data "ing the composition and the thermodynamic properties of protective oxide films. and such data ss. tedispensible for an exact knowledge of their stability conditions. However this may be, in spite vf ese imperfections which it is well to take into account. the conclusions provided by the theerstcal ‘corrosion, immunity and passivation” diagrams frequently coincide appreciably, quantitatively speaking, with the facts. For lurcher details, the reader is referred to the exposés which will be made in Chapter 1V. We Point pasticularly to thees such cases of agreement concerning cespectively the resistance of metals to Pore water, metals whieh ean be activated and passivated and oxidizing inhibitors of corrosion. We "out 10 use these diagrams forthe purpose of building up an overall picture ofthe degree of nobility ‘and of some non-metallic elements 2. RESISTANCE OF METALS TO PURE WATER (See Fig. 1) Generally speaking, the metals showing perfect resistance to pure water at a temperature in the Felon of 25°C will be those having an equilibrium diagram on’ which the perpendicular from pH = 7 ‘tosses only the immunity or passivation domains (outside all corrosion domains) at potentials between ‘id 440-7 V, which are possible only in the normal conditions of use for construction metals. With some reservations which will be pointed out later, and apart from the six metals in the Fatinsm group, the following thirteen metals fall into this category: berylliam, aluminium. gallium, ‘rium. tin, silver, gold, titanium, zircozium, hefnium, niobium, taniaium and chromium. 5 for those of the above-mentioned metals for which a corvosion possibilty exists at very low stecicode potentials (i titanium), it will be particularly important to avoid all reducing action andCORROSION 2 CHAPTER In. SECTION 4 to.see that the surface has a good polish. As for chromium and silver, and also possibly gold and titanium, metals for which a corrosion possibility exists at high electrode potential, slight dissolution will be! observed in the presence ofa highly oxidizing action 3. METALS WHICK CAN BE PASSIVATED AND ACTIVATED (See Fig 2) Generally speaking, the metals which can be passivated by oxidation and activated by reduction fzose which have a higher oxide less soluble than a lower oxide and will thus presenta triangular cosion domain; the lower the apes ofthis triangle in the diagram, the easier it will be to passivate the (Tse aoe baa ahaa meee? @ 1% (Fania on ete Fria 2. Pastve and ative set (shove. ‘etal by oxidation. This applies o the following metals, in descending order of passivability: titanium, chromium, tin, iron, manganese, lea, silver, nickel and cobalt(!) For the three ist metals (titanium, chromium and tin) the passivation domain of which, for ensive pH range, is situated partly below the stability domain of water, passivation wil be very ea OTe treatm) igor Fic. 5 Meal resistant to pure wae, The ttc’ eons ndiate Leoreta comonoe domains. adel peat 1 te more easly passivated tan ide Leos grams lead us to vet oe Chagie WN, “Toe aowhotchd eons ite toot immu a passin demas exons 125 flekel) a 12? (cobald)4 CHAPTER IL SECTION 4 will occur, more often than no, spontaneously, even in the absence of an oxidizing agent. Tron pas- sivation wil equite an osiicng ation whic, being weak for pH values between 9 and 13, wil have be relatively strong for other pH values. Passivation of the five other metals by the formation of anf oxide layer will only be possible by means of a very strong oxidizing action (c.g. an anodization such # fs tha which serves as the bass for charging lead batteries) t must howeve, be understood th, in spite ofthe dificulty of passivation, silver generally has a good corrosion resistance owing to the size Of is immunity domain, and tha, for reasons which have as yel been ony insufficiently clarified, nickel {and perhaps coal too} can often be passivated at tower potentials than Fig, 2 leads us to anti pate ‘Conversely, passivated titanium, chromium and tin can only be acivated with relative dificuky they generally remain passive after the oxidizing action, which would possibly have brought about p Hioiioas hag Gaeava cation (6c fi ce fia for pe valle ialoeen gaua'ry Anes toe other pH values. The other five metals (manganese lead silver, nickel and cobsli) wil be very easily sctivated, it being nevertheless understood that whereas activation wil alnays bring about corrosion Of manganese (a BY no means noble metal the immunity domain of which exists only at vey lo electrode potentials) activation ofthe other four metals wil only cause corrosion if there subsists a certain oxidizing action of variable intensity according to the metal (maintaining the electrode potential of the metal within ite corrosion domi). 4 4, oxiDiziNG CORROSION iNnIatroRs (See Fig. 3) The high suscepibilty of iron to corrosion is mainly de to the existence, in the left-hand region of the part of Fig. 2 (No, 4) relating to this metal, ofa large triangular domain of corrosion. In the ease of | solutions in presence of which the passivating ion oxide acts as an elfetve protector (which generally implies the absence of ehlrid}, corrosion can be avoided by the Intraducion into she solution of an inhibitor having an oxidizing effet suficient to enable the electrode potential ofall the points on the surface ofthe ion to be high inthe passivation domain of the meta. Protection vill be particulaey {| effetive if, forthe potential and pH condition corresponding to the “corrosion domains” ofthe ion, the oxidizing inhibitor can be reduzed together wit formation ofa solid: in becoming deposited onthe | “weak points” ofthe iron sariace, this solid wil improve the protective eet ofthe passvating oxige film This will thus enable us to obtain some data on the posible effecivenes ofan oxidizing inhibitor | by superimposing on the theoretical “corrosion, immunity and passivation” diagram for iron the potentiat-pH equilibrium diagram wich shows the stably conditions of the solids which can be formed by redustion ofthis inhibitor. This bas been done with Fig. 3, where consideration has been taken of oot M solutions of the nine following oxidizing substances! hyperosmate, pertechnetates, mates, molsbdates,tungstates, vanadate, slenates, arsenates and antimonates, 'A thick bine indicates the potentials below which the inhibitor can be reduced; the shaded sections sepresent those part ofthe corrosion domains of iron for shich the products of the seduction of the ‘oxidizing egent are not solids, {f, as 8 fret approximation, we assume that the reduction reactions of the oxidizing agent are reversible and thatthe solids formed in this reduction constitute a protective coating on the iron, the shaded sections in Fig. 3 show the theoretical conditions of corrosion, the rnon-shaded areas representing the theoretical areas of non (OH) (aed solution), pH> 330 or {H*) < (OH) falaline solutions, ‘The vertical line pH = 7 drawn in Fig. 4 therefore separates a domain in which there is @ pre- sminance of H* ions over OH” ions (acid solutions) rom a domain in which thee is @ predominance WOH” ions over H ions (alkaline solutions). Another consideration is that water and its constituents can be reduced with the evelution. of ‘nchoyen, or oxidized wiih the evolution of oxygen, according to the reactions 2H" 4 267 =H, (reduction) and 21,0 Og + all” + 4e~ (oxidation. ” =ilibrium conditions of these reactions at 25°C are respectively Ey = 0000 — 00591 pH — 01295 og Ay (14) Ey = 1228-00591 pH + 06167 logy, (13) Win the same way that we have put pH =~ logitt=) se put og pa, and 10— 108 Pow ‘he 140 equilibrium reactions (14) and (15) can be written respectively E,= 0400 ~ 00591 pH +00295 2H, (14) E,= 1228 ~ 00581 pH — 00147 70. (15) Now, in the same avay that water can dissociate into H™ and OH ions according to the reaction H.0 = H* + OHM and is considered neutral feom the aidity/alkalinity point of view if H") = [OH ), act the ines (and (8) ae practically valid fo sets in which te fee ebay of formation of the wate Pes eau a he re nth of frmaton of pure wae. that i 366g ca at 14 For mo egeeunsolsbone, Sigs Blow is sue: ns eae on sere the aby the water wikh i shown by an slots a eke eae ‘arin Fig "Tha inciea fo sully of waer shan cen sbtasces are dined nk shows be a aioe NORE ction of the tempeetre. by an ekvation ofthe oti font Jeoanered with vaduton of he vepourpessute] ® 4 dereon ofthe fering poi tae ot [3] pp t2. and),108 CHAPTER IV. SECTION LL ‘water can decompose into gaseous hydrogen and oxygen according to the reaction 2H,0 = 2H, +O and may be considered neutral from the oxidation/seduction point of view if py, = 2Po, isi Jog pa, 108 Poy +108? = 108 Aa + 030, ie HH = 10 — 030. we combine this equation with the equations (000) — vosp1 pet + 00095 mH, (24) 228 — 09501 pH 904710, (5) we obtain, as the condition for the neutrality of water from the oxidation/reduction point of view 10 = 2786. g Ey = 0813-00591 pH of H=2S6 or By combining these relations with the relation pH = 7-00 which expresses the neutrality of a aqueous sofation from the acidity/akalinity point of view, we obtain the following characteristics fora the condition of absolute neutrality of @ dilute aqueous solution, at 25°C: 3 pH=700, i=2756 10=2785 By= 404 V. However, although the concept of neutrality from the acilty/alkalinity point of view has a great practical interest, the concept of neutrality frome the oxidationjreduction point of view is of principal academic interest. rH, which is widely used in biological chemistry, is connected with pH and elect potential E (calculated in volts with respect to the standard hydrogen electrode) by the following relation gp valid for 25°C: f= S94 29H OF ‘The neutrality characteristics thet we have just defined enable a potential-pH diagram to divided into the following four regions, shown in Fig. 4: top left: oxidizing acid media bottom left: reducing acid media; botcom right: reducing alkaline media; top right: oxidizing alkaline media 3.4. DECOMPOSITION OF WATER. FORMATION OF HYDROGEN, OXYGEN, OZONE AND HYDROGEN PEROXIDE In the portion of Fig. 6 below line (a), relating to the equilirium of the reaction Hz = 2H" + 2¢ (14) for a hydrogen pressure of 1 aim, itisthermodynamically possible to reduce water with the evolutiod of diatomic gaseous hydrogen at atmospheric pressure. This can be done using an electrolytic cath or'by the section of sufficiently powerful reducing agents, such a5 metals with low electrode potent (iron, zine, magnesium, sodium, etc) For electrode potentials below those indicated by lines (3) and (49, negative hydrogen ions H. cin theoretically be formed; at very low potentials, below those indicated by the family of lines (13h itis theoretically possible for monatomic gaseous hydrogen to be evolved with an appreciable part pressure, the equilibrium proportion of H, with respect to H,, calculated from equation (9), remaining extremely small, however (ofthe order of 107"). In the portion of Fig. 6 above line (b), relating to the equilibrium of the reaction 24,0 = 0} + 4H” + 427 (15) for an oxygen pressure of 1 ate, itis thermodynamically possible to oxidize wat sith the evolution of diatomic gassous oxygen at atmospheric pressure. This ean be done by means of an electrolytic anode or by the action of suliiently powerful oxidizing agents (permanganate, fuoriniggd ae). WATER 1083 or electrode potentials above those indicated by the family of lines (16) its theoretically possible sve itomie gaseous oxygen (oz0r2) tobe evolved with an appreciable patil pressure the equiibriom. Gefen of Os with respect to Os, calculated (fom equation (11), remaining very smal, however Uf: order af 10" to 10%) At potentials above those indicated by the family of ins (5-6), the \osion of gas may be accompanied by the formation o! hydrogen peroxide and its fon HO; “et.us consider, as an example, the action of fuorine on water. As will he shown in section 201, concening fuoring, the stable form of fluorine for potestials corresponding to the fares of lines {ish (19) and (5-6) of Fig 6 ace hyéroBuorie acid HF and fuoride ion F™, with » possibility ofthe formation of gaseous fluorine monoxide FO at high potentials Gaseous fuorine tends therefore, inthe presence of water, onthe one han, torn into duociae monoxide and hydrofluoric acd according Fenian > Fe and FL+HL0 > Fee 2H rae overall reaction 2p IhO > Fy aF-+ allt and, on the other hand, to be reduced according to the reaction Fea 3 ar. ‘Combining this last reaction withthe three oxidations 21.0 +O» BO > 0 alesse 5, Olle be (18) and 21,0 > HyOyraHrm2e- 3), this eduction of Ruorine to fuoride gives rise to the following three sumultaneous ceactions + aFra ene (Cormaion of hydrofuorc acid and oxyae, ormaion of hydrofuosc acid and ozone, + (oration of bydroftuorc aid and hyéropea petowide) ¥oraH0 > ,0,2aF— all As a result of this, the action of fvorine on water can give tise to the simultaneous formation of Mucrine monoxide, hydrofluoric acid, ozonized oxygen and hydrogen peroxide Some other considerations relating to the reduction and oxidation of water will be discussed lute, when xe study hydrogen peroxide (section 1.2), hydrogen (section 2) and oxygen (section 19.) 4, BIBLIOGRAPHY UD. Povnaare, Thermodaniqu’dr solutions agueuet dldes (These, Delf 1945: Béranges. Pars end Lie, (549). 3ed Eaton, Cebeeor 1965, CP. Devaay, M. Poursa and P. Vani Rvssexnencte, Comportement éietrochinique de Voxsséne, ae Frau ‘ocypéae et der radius OH et HO, (CR. 2* Réunion du CITCE, Misa, 1950) : U3) NC Focnanx, Leyort ule eorrosian electochinique (2 fascule) (Reppor technique RT-36, of CEBELCOR, 6) NC Pocnaare, Levon suo corrosion Hectrochimique(3*fscicule) (Rapport technique RT. 49, of CEBELCOR, bgSECTION 12 C HYDROGEN PEROXIDE(') M. Pouraalx and N. of Zousov SUMMARY Substances considered ond substances not considered Reactions and equlibriam formal. 2, Two dissolved substances. 2a, Relative stability of water, hydrogen peroxide and the HOF ion 212, Limit ofthe domsins of lative predominance of H,03 and HOS ( 22, One dissolved substance ané one gaseous subsiance. Relative stability of oxygen. hydrogen peraxide and the HOS ion. uli siagram and is icerpretaion 3, Establishment of the diagram, 4. Formation of hydrogen peroide ‘Onidizing and reducing properties; decomposition of hydrogen peroxide 3, Action of hydrogen poroxce on iron 4 Bibliography see abo [ILE DB} ane £8) 106 (Eas: fom dhe Rappon CEFAR.2 of ve Commision des Etudes Fondaneaales et Appieaoas of CEBELCOA HYDROGEN PEROXIDE ro 1. SUBSTANCES CONSIDERED AND SUBSTANCES NOT CONMDERED(?) emidet—_Natconntene ve Mame Luguid wbstance yD <0 Water bissohed substances H+ = © Hydrogen oa on = 31995 Hydroxide ion 3,0 : = 8147 Hydrogen peroxide i é S551 Hydrogen perorge ton : on 3530 Hydeoy! = BO, 509 Hydrogen pero] e 95 18000 Hiyperoxie on Ccawous substances Oy = 0 Natural oxype0 z o 19000 Ozone “These free enthalpy values are all due to W. M. Latimer, 2, REACTIONS AND EQUILIBRIUM FORMULAE 21.180 DISOLVED suastANces(*) 21 Relative stability of water hydrogen peroxide and the HO ton (an) Lo HO wor + He toed 1.08 pl 2 ako Hy Oseatiee ae Eee ETE 0,050 pl + 0.098 los (8,03) BHO SMOs SSS ae Eyam 2 19— 0.0886 pt + 0.0205 log (1003), ‘nit of che domains of relative predominance of H,0; and HO = s168 Hognos ‘ONE DISSOLVED SUBSTANCE AND ONE GASEOUS SUBSTANCE Relarive stability of oxygen, hydrogen peroxide and the HOF fon ee beral PO, 0, walimsae~ Hoe D.6R—0.0501 ptt + 0.0288 Dose OE 40; Hear = 0.58 — 0.0205 pHf + 0.0208 ng 3. EQUILIBRIUM DIAGRAM AND ITS INTERPRETATION Sh BSTABLISHVENT OF THE DIAGRAM “The electrochemical equilibrium diagram 1 was constructed by means of equilibriam formulae 1-5. This diagram comprises two families of lines, relating respectively to certain fixed values of the centration of hydrogen peroxide in the forms HO; and HO (2 and 3) and to certain fixed values ae = "HO, + Hos “ne "oo The eink OW and HO. which are nt consred Ne. ie dusussd in a previous my (1 ine folloning equations we hse, with 2 nen fo siplation, taken water vo be thesbet108 CHAPTER IV. SECTION 12 HYDROGEN PEROXIDE 109 (Fig. 3), and, on the other hand, domains in which hydrogen peroxide can be reduced to (Fig. 2) oF oxidized to oxygen (Fig. 3) Beiow the family of lines (2-3) (Fig. 2) hydrogen peroxide {an oxidizing agent with the formation of water; for instance it oxidizes ferrous ions to ferric 10 the reactions 3.2. FORMATION OF HYDROGEN PEROXIDE and reducing properties; decomposition of hydrogen peroxide It is well known that hydrogen peroxide can be prepared by the low temperature clectrolyg of sulphuric ai solutions using a atinum anode; is also formed in small quantes, when ct eee ‘etal (an, alominium) corrode in aqueous sclation an is eee soizgses67senueeuse, veal mation ThOsraiea¥e > ak eae E aozessmewszozsssunucs e 2 A HH qe eark separa loin of hydrogen Eyes By Bee Pa 16 areca. sieeen of rele bg 8 ie 12 ” region ofthe oxidation 412 ~~ a nphoge pare gon ie ~~ oaks eccin dena! acter’ 408 2p of eduction Ce 1 os} BB tnen Seca renter ————9 Of SS E os “6. ‘agin of formation of ‘hydrogen peroxide by oo os raiclen ose” a4 oz ° aa 6 -02 PORES SET EE et -08 "2. Feat of drogen per by eon Fe. 3 Frente dope prey thereon Sem rege a ag tare An “08 Above che fai of lines (5) (Fg. 3) hydrogen peroside can act as reducing agent with the femation of oxygen; for instance it reduces permanganate to manganous ions avcording to the ne SHO, > sO.tniteeie ch aod tienes! Sashes 80 14 18 , issrose perorde thus appears unsable and reducible to water below the family of ines (2-3) é Fae fig aki appears unsable and oxidicable to oxygen above the family of lines (45) Fi. 3) I these SEs ‘eo fans of lines are plotted on a simple diagram (Fig. its found that these two domains of l sssabilty have a common area, in which hydrogen peroxide is doubly unstable and can decompose ‘Pe 1, Potenia pH egultnm diagram ofthe aysem hydrogen peroicesates a 25°C Seiwnieh aad aivge eauay Ee aaee Inte frst case, the hyérogen peroxide isformed by the oxidation of water according tothe react HOpeateae > 210 © 2H,0~ 11,0, + 241” + 2e~ (2) cectrode potentials corresponding to the portion of Fig. «abo and thy S Ouastnese {he family of fnes (2-3) tn the second case, itis formed by the eduction of oxygen dissolved in overal eaction BHO, > allsO- Or. 2, according to the reaction Q, + afl” + 27 + H,O, (4) at electrode potentials correspondigd sola to the portion of Fig. 1 below the amily of lines (4-5) As showa in Figs. 2 and 3, these two families of lines enable us to represent, on the one had ‘domains in which hydrogen peroxide can be formed by the oxidation of water (Fig. 2) or by the reducti ‘he domain of double instability, and only in this domain, hydrogen peroxide can decompose sina into water and oxygen. Consequently, if a sdtiion of pecoxide is in conttet witha metalic sutite ‘rode potential is situated in this domain of double instability, the hydrogen peroxide can decompose10 CHAPTER IV. SECTION 12 spontaneously into water and oxygea according to the reaction 2H,0; ~ 2, + Ox, HP hydrogen peroxide decomposes spontaneously into water and oxygen on a metallic surface, this surface must necessarily exert an elecicode potential whose posiion on the diagram is situat jn the domain of double instability. We have here an example of the electrochemical catalysis of chemical reaction. (On the other hand, in the presence of metallic surfaces wh not included in this domain of double instability, the decomposition of hydrogen peroxide into wa nd oxygen is impossible: the hydrogen peroxide will cither be practically stable; or else it will reduced to water (below this domain) or oxidized to oxygen (above this domain) condition is represented by 8 poi 2oezs6enreewzoz2s sane 2 rz 16) 6 2 2 aa os al os o 0 Lod “04 Loa -0.8 +3 nmunity ie -r0 “18 SOT ESTE EO TSS Se Te eh Fra § Conrosion and paivatonofeca by hyo ca pownde, Reduction and decoration ef Fydeopen peony ion ‘9 oon te pose ofa soaton of 0. a 03g). cersion}. Stren iste presence of soliton of HO, of 3B (pusivatton), Fic. 4 Decompostios of hydogenperoide to 13.3. ACTION OF HYDROGEN PEROXIDE ON RON We have verified two of these facts in the particular case of the action of hydrogen peroxi| solutions om iron ([2]. [3]}: some piano-wires were put into two glass flasks containing respective a relatively dilute solution of hydrogen peroxide (0-3 g/l) and a relatively concentrated solution bydrogen peroxide (30 1) di ‘After e few hours the plf ofthe solution and the eleetrode potential of the iron were measure and the state of the metal surface was noted. The conditions of pH and potential cbisined were mark fon Fig 5,a potential-pH diagram representing, on the one hand, the theoretical conditions of instal and double instability of hydrogen peroxide solutions, and, on the other hand, the theoretical condit ‘of corrosion, immunity and passivation of iron. ‘We see in Fig. § that, forthe relatively difute solution of hydrogen perokide, the point represeat the condition of the iron (E = —0200V; pH = $7) is situated in the domain of corrosion of if ‘and in the domain of reduction of drogen peroxide; therefore corrosion of che metal without evolst of gas takes place according to the reactions: Fe > Festwae and) Ossatteae > alo eH O,n 3H Fees aii. ‘overall rexetion HYDROGEN PEROXIDE ut For the relatively concentrated solution of hydrogen peroxide, the point representing the condition fon (E = +0720 V; pH = 3+) isin the domain of passivation of icon and in the domain of ability of hydrogen peroxide; therefore passivation of the iron occurs without corrosion ly by the formation of @ protective film of Fe,0;), and evolution of gaseous oxygen is noticed the surace of the metal, resulting from the decomposition of hydrogen peroxide according to the “ustion 21,0, +2H,0 + Oy, Moreover, iis noticed, after some time, and as a result ofthis decom sosition which causes a reduction in the-concentration of hydrogen peroxide to below the critical rnenttation nevessary to ensuse passivation of the metal, that the electrode potential of the iron cases abruptly ané takes up a position, as in the previous case, in the domain of corrosion of iron tnd in tke domain of reduction of hydrogen peroxide. The evolution af oxygen is seen to stop, passiva 1ses and the metal begins to corrode 4, pIBLIOGRAPHY 1 P, Drtasiay, M. Pounaanc and P. Van Rvsseiasnon, Comportemant élecrachimigue de Foxypire, de Peau snypéne et des rudicaus OH et HO, (CR. 2* Réunion éu CITCE, Milan, (950) 2] M.Pounaact, Applications de diagrammes potenil-pi relatifs au fer et & Peau oxy inde. Experiences de dma: rain (Rapport technique RT.2 of CESELCOR, 1954). AUPoceaare, Lesons sar la corrsiondlecrochimigne (1 fisieule) (Rapport technique RT.7 of CEBELCOR, SF Piven, Legon sr la corrosion eecrochimigue (3 asicule) (Rapport technique RT.49 of CEBELCOR,SECTION 2 HYDROGEN() M. Poursanx and N. de Zovov SUMMARY 1. Substances considered and substance mot considered 2 Reactons and eqlibrium formule. 24, Two dissolved substances. 2.14, Relative silly ofthe ons H*, OFF" and. 21a. Limits of the domains of relative predominance of the fons H 22, Two gaseous substances 2ant. Relative stebilty of Hy apd 3.22. Limit ofthe domais of lative predominance of Hy and Hy 2.3 One alszoived substance an one uacuus sulsiance. Solubility of hydrogen, OW” and H Equtltbrium diagram and is interpretation il Essablisment of the diagram. 3 3 Formation and stabilty of diatomic gastous hydrogen. Hydrogen over‘otentia Exchange currents 13, Hydrogen electrodes forthe measurement of pH. 34, Realization of powerfl electrochemical reductions 3.5. Corrsion of metals with the evolution of hydrogen 535, Diffsion of drogen int ion sad pickling emtritement 237. Conditions forthe formation of monatorce gaseous hydcogen, 4. Bibliography (Adapt vesop ofthe Rapport wcbsigue RT-59 of CEBELCOR (ul 1958, fal ofthe llowiog arguments have aeay to pubis (12) HYDROGEN 1, SUASTANCES CONSIDERED AND SUBSTANCE NOT CONSIDERED Orton Coarse ocemitend el) guid substance * Ho 2 800 Disord substances “1 He = ai sao ¢ = 520 ©), + a 0 . on = a1 Gascosesubatanoes ° u S 4807 ‘ 4, - ° 2, REACTIONS AND EQUILIBRIUM FORMULAE. 21. TNO DISSOLVED SUBSTANCES 2, Relative stability ofthe ons HY, OH and = I + on Yeg(OHI-) = 14.00 + pil Heseg0 = OU ae nem 212 Limits of the domains of relative predominance of the ims H", OH™ and Hl” rayon pit 7.09 fey Baa ts i-/08 Eya— 0.711 — 0.0001 ptt TWO GAsHOUS SUBSTANCES Relative sability of Hy and Hy ‘ Rem seee 8 22, Limit ofthe domains of relative predominance of Hand Hs Bain 2.105 — 9.0801 ptt 3 ONE DISSOLVED SUBSTANCE AND ONE GASEOUS SUBSTANCE Solubity of hydrogen Ry 2.16 = 0.0505 pat 0.0301 ce Tm 0.000-—0,0511 yt —9.0395 Mins Hh, sae "Nal calculated tom the solubility of bydfogen in water at 25°C 1r-S4cnil fot py, = Usem 2.211 0.025 og us Water Hydride fon ‘Natusl hydrogen Hydrogen jon Hydronic fon Atomic hydrogen ‘Natural hydrogen Pu, 2.106 = 0.0301 pit +0.0501Tog =H ( Pu, Pa,ue CHAPTER IV. SECTION 2 HYDROGEN. us 3, EQUILIBRIUM DIAGRAM AND TTS INTERPRETATION. HOAMATION AND STABILITY OF DIATOMIC GASHOUS HYDROGEN DDiatomic gaseous hydrogen can theoretically be formed at etmospheric pressure by the reduction cf water at potentials below those indicated in Fig. 1 by line (a), which refers to the equilibrium of faaction (6) in the particular ease when py, = tatm These conditions of potential can be obtained Giher electrochemicaly (using appropriate cathodes), or chemically (using corrodible metals or other ‘ducing substances) iiydrogen overpotenials, Exchange currents. As is well known, the egree of ireversiblity of the 3.t. ESTABLISHMENT OF THE DIAGRAM. Using formulae (1}(7) we have constructed the electrochemical equilibrium diagram Fig. 1. On it we bave represented the conditions of stability ofthe gases H,, and H., as defined by equationggg (6) and (6) and also the domains of relative predominance of the ions H’, OH” and H™, as defi by equations (V3). wo Ole oss 6 7s oe WU Be tydrogen evolution rection 2H" 422” > H,, which can be represented by the “overpotental” of et ce ele ee 7 8 ‘Ho reaction, varios greatly with the nature and condition of the metal surface (or the surface of another 18 bs is “tance with eestronic conduction) on Which the reaction oecurs | o bis As en example, some values of “hydrogen overpotentials” ate given below. These values were jut forward by Thiel and Hammersehmidt in 1923, for twenty-two elements in the presence of a 1M Dilution of H,S0,, at 25°C; the current densities to which these overpotentials correspond were not indicated by the investigators The elements are given an “order number” which classifies them in order increasing hydrogen everpotential (Table D, iz q Tame | Hiydrogenoverpotenils in the presence of 1M H,SO, (alter Thiel and Hammerschunit (1) Ln om va DARBY I Abecssssoneee OV Bo Pte BOWMAN NA nang teat O38 tw. os How 3 Ts 0x0 1 Oe 6.0095 #2. Mo. 2. 0 2 ose : op i ew Stn ose i son 1 si Ms oar TA o.0168 1. Sh, z ee eon i eG) Shown in Fig. 2 are the values, according to various investigators (Petcherskaia and Stender (1), jeuson [2], Kabel [3] and Jofa [13]) of che hydrogen overpotentials 7 of twenty-three metals and metalloids, for various current densities, in the presence of a1 M solution of H,SO,, ic. the solution considered by Thiel and Hammerschmidt, at 25°C[‘}. We have not made a critical examination of the Salues given in Fig. 2, which is therefore given without prejudice; however, we point out that Tafel's 4b Jog f, which seems to be valid generally for a given surface state, does not apply to 2s given for Te and Bi. nor to some of the values for Pb; these deviations are probably due to of hydrides. For those cases in which the results of these determinations arc in approximate agreement Thlel’s law, we have determined, by linear extrapolation to an overpetential of zero, the logarithm ‘exchange current” fog ig =<, i. the reaction current when the electrode potential of the "etal is equal to the equilibrium potential of the reaction H, = 2H” + 20°. Now the value of the ‘change current can be considered as being an absolute measure of the degree of irreversibility of this tion on the given electrode. The table below shows, on the one hand, the values of the exchange ced from Fig. 2 for nineteen metals in the presence of 1M H,SO4) and, on the other of exchange currents given by Kortiim and Bockris [5] (i the presence of various solutions and HCl, e+ to 1 M). The metals considered have been classified approximaiely in decreasing Zoe se 5s 67 6 SON ROM IS orm of graphie The overpotenta ate by lf for Hg are lor 2605 M solution of H,S0. a 20°C. Fic. Poteaal pH euivinn dagram fo he system hydrogen-watt, 23°C: