7 SIMPLIFIED PROCEDURE FOR CONSTRUCTING POURBAIX DIAGRAMS” E. D. Vermxx, Jn.’ Distinguished Service Professor Emeritus, Department of Materials Science and Engineering, University of Florida, Gainesville, Florida A. Introduction B, Thermodynamic backround . Consteuetion of diagrams D. Applications of Poubaix diagrams References A. INTRODUCTION For the behavior of metals in aqueous solutions, one of the ‘most important contributions to the corrosion literature has been the work of Pourbaix (1, 2] and his associates in the development of thermodynamic equilibrium diagrams E vs. pH), called Pourbaix diagrams. A vast amount of data may be presented simply and concisely in Pourbaix iagrams, When the advantages and limitations of such diagrams are understood, valuable inferences may be made regarding corrosion phenomena. The selection of conditions for cathodic and anodic protection is simplified, Candidates for consideration as inhibitor species may be selected with greater efficiency. Critical corrosion experiments may be designed with equal efficiency Corrosion processes involve both chemical and electro- chemical phenomena, In 1923, Evans [3] observed that, if two samples of iron connected by a galvanometer ate immersed in two solutions of potassium chloride separated * Adaped with permission fom J. of Fae, Modules Mater Ss, ng. 1,535 (0979); carent ile, J Maer. Hae, published by the Matera Edveation Council Copyright © Penasyvania State University Uhlig's Corresion Handbook, Third Elton, Bd by R. Winston Revie Copyright © 2011 Joba Wiley & Sons, ne by a porous membrane and if a stream of air is bubbled through one of these solutions, an electric current circulates between the aerated sample, which becomes the cathode, and the nonaerated sample, which becomes the anode and cor- rodes. On the other hand, if sample of iron and a sample of another metal (copper, zinc, or magnesium) are connected as above, a passage of electric current is also observed. Under these circumstances, iron becomes the anode and corrodes When connected to copper, whereas zine or magnesium become the anode and corrode providing protection to iron. ‘Thus, i is necessary to consider not only chemical thermo- dynamics but also electrochemical thermodynamics when considering corrosion reactions. ‘Chemical equilibria are defined as those that do not involve oxidation-reduction processes but do involve the law of mass action and the law of solubility product (involv- ing partial pressures or fugacities and concentrations or activities). By contrast, electrochemical reactions are defined as those in which free electric charges, or electrons, participate, B. THERMODYNAMIC BACKGROUND ‘The procedure for calculating Pourbaix diagrams is straight- forward and is amenable to computer calculation. On the other hand, certain assumptions are made that must be ‘bome in mind when applying the information available from Pourhaix diagrams in “real” situations, First is the assump- tion of equilibrium. Since Pourbaix diagrams are equilibrium diagrams, they give no information on the kinetics of the reactions considered. Kinetic information may be obtained experimentally by methods described elsewhere [4]. Italso is assumed that the reaction products are known and that the 994 SIMPLIFIED PROCEDURE FOR CONSTRUCTING POURBAIX DIAGRAMS free energy of formation of each solid and ionic species is mown for the conditions of temperature and pressure of interest. The pH of the solution is assumed to be known and ‘constant in the bulk as well as al the metal or reaction product surface, Temperature and pressure are considered 10 be constant and are usually assumed to be 298 K (25°C) and 1 atm, respectively. Poubaix diagrams may be calculated for other temperatures if thermodynamic data are available or ‘may be estimated [5]. Generally, the features of Pourbaix diagrams are not significantly altered by increased pressures since thermodynamic properties are relatively insensitive to pressure (as compared with temperature. The simple graphical methods described herein greatly facilitate the practical consideration of the various equilib- rium reactions involved. For chemical reactions, it is con- venient to make use of the Van't Hoff equation, which involves the equilibrium constent ac RT Ink = ~2,303 x 1.987 x 298log.K for electrochemical reactions, the procedures involve ‘manipulation ofthe Nernst equation, which can be written as 501 (ana) oa ot 1 COPE og Gwe ry where “= reduction potential paacine AG" = standard free energy change F = Faraday's constant ‘n= number of free electrons for the general reaction, PR + WHO — pP+hH* +ne Note that electrochemical reactions are written as oxidation reactions; thal is, electrons are on the right. Taking 40 = 1 and then 0.059144 Looseinl pH (7.2) ‘The standard free-energy change, AG*, for the reaction can be obtained readily from tabulated thermodynamic data ‘Therefore, the first term to the right of the equality sign in Eg, (7.2) is a constant. The second term also becomes constant when values of ap and ag are chosen in the normal ‘manner, In constructing Pourbaix diagrams, the concen- ration of the ionic species at the boundary between a solid substance and a dissolved substance is usually taken as a very low value. such as 10~®M. The sum of the frst two terms in Bq, (7.2) gives a constant equal to the value of the potential, ¢, at pH 0, The resulting expression is the equation of a straight line of slope equal to the coefficient of the pH term, —0.0591hin, and intercept equal to at pHO. Pourbaix diagrams are constructed from the three, and only three, types of straight-line relationships, which result from the analysis of the possible chemical and electrochem- ical equilibria in the system under consideration. Depending fon the reactants and products of the assumed reactio these straight lines will be either horizontal, vertical, or sloping: 1. A reaction involving a solid substance, 2 dissolved substance, and hydrogen ion in water without free clectrons gives a vertical straight line, that is, inde- pendent of potential (when n = 0, the slope ofthe line equals 20). Areaction involving a solid substance and a dissolved substance in water plus free electrons but without hydrogen ion gives a horizontal straight line, that is, independent of pH (when h = 0, the slope = 0). 3. A reaction involving a solid substance. a dissolved substance, free electrons, and hydrogen ion will give a straight line with a slope equal to —0.0591/in, After plotting the straight ines on potential versus pHT coordinates, the domain of the thermodynamic stability for each individual species is determined by requiring that all equations involving that species be satisfied simultaneously, Example 7.1. One solid substance, one dissolved sub- stance, and hydrogen ion in water without free elections 2Fe!* 4 31,0 = Fes0s + 6H" (73) Assuming the activities of HO and Fe,O, to be unity, the equilibrium constant may be expressed as (aus) x= (74) (ere log K = log(a:) ~ 2080) (75) = —6pH—2log(,9:)Referring to tabulated thermodynamic data and substituting in the Van’t Hoff equation, log K may be calculated: AG’ = —RTInK = ~ 2.303 « 1.987 x 298 log K Ag ; 108K = F505 x 1987 x OE (74) (1970) 1373 a) =143 Substituting in Eq. (7.5) and rearranging, we oblain a gen- eralized Pourbaix equation, log(ape:) = —0.72-3pH, (18) Tn the case where 10-6 (apes) then pH—1.76. ‘This gives a vertical line on the Pourbaix diagram. Example 7.2. One solid substance, one dissolved substance, and electrons, but without If" as a reactant or product: Fo—+Fe™* +26~ (9) K = age: (7.10) og K = log (aye-) ny ‘Using tabulated thermodynamic data, substitution in Bq, (7.2) gives 20,300 0.0591 ° = 3573.00 + > log(ames) (7.12) $= =0.440-+0.0295 og( are) which is a generalized Pourbaix equation In the case where gers = 107 then $= -0617V This gives a horizontal line on the Pourbaix diagram Example 7.3. One solid substance, one dissolved substance in water, plus free electrons, and hydrogen ion: 2Fe?! 4311,0 = FeO; +6H' +2¢ (7.13) CONSTRUCTION OF DIAGRAMS 95 ‘The equilibrium constant for this reaction may be expressed kK nd (24) and Woe = 6loglay) Plane) ag =< 6pl—21og(ages-) ‘ Substitution into Bg, (72) gives 6 GT Looe —2hoglane) = 0728-01773 pHH-00591 loglame:) (716) 1 generalized Pourbaix equation. In the case where pes. = 10-6 then § = 1.0826 0.1773 pt ‘This gives a sloping line on the Pourbaix diagram. C, CONSTRUCTION OF DIAGRAMS. ‘Table 7.1 lists the data for the iron-water diagram together With the various reactions and equilibrium formulas {1} Figure 7.1 shows a resulting Powbaix diagram considering that the only solid species are iron, FesOs, and Fe:0s Naturally, a number of eter assumptions could ave been made, However, this serves to illustrate the constuction of a diagram, Lines @ and ) designate the limits of thermo- dynamic stability of water at 298 K and | atm pressure, Above line (, water is uastable with regard to the evolution of oxygen, and below line @, water is unstable with respect to the evolution of hydrogen. The other dashed lines on the diagram comprise an “ionic species diagram.” For ionic species (dashed lines) tne coexistence lines represent the condition wherein the thermodynamic activity ofthe species on each side ofthat line is the same. For example, on line 6 the activities of Fe and Fe(OH), are equal. The triple pointinvolving kines 1,6, and7'is aninvarians point at which the activities of Fe” *, Fe(OH), * and HFeO, ae the same. ‘A line on the diagram represents @ univariant system, whereas a family of lines, each of which is related to a value of a parameter, represents a divariant or trivariant system depending on whether the parameter contains one component (Concentration) or two components (a term containing two concentrations). Heavy solid lines are used to separate solid species, wheres lighter weight solid lines are used to delineate the boundaries between a slid species and an ionic species.96 SIMPLIFIED PROCEDURE FOR CONSTRUCTING POURBAIX DIAGRAMS TABLE 7.1. Information, Reactions, and Equilibrium Formulas forthe Iron-Water System at 298K (25°C) and 1atm ‘A. Substances Considered and Substances not Considered Oxidation Not Number (Z) Considered Considered __p(cal) Name, Color Crystalline System Sond 0 Fe = 0 ‘alron, light gray, face-contered-cubie (Fo) substances 42 FeO hyd. — ~ 58,880 Ferrous hydroxide Fe(OH), white, shomb. 2 = FeO an, = Ferrous oxide, black, eubie FeO anh — — 242,400 ‘Magneit, black, cubic — FeOexH0 = Hydrated magnetite, green-black Fe,0y anh — (@)—177,100 — Haematite,xed-brows, thom, or cubie Fe,0, hyd, — ()— 161.930 Femic hydroxide Fe(OH), red-brown, fee Dissolved Fe = 20,300 Ferous ion, green substances HFeO,~ = = 90,627 Dihypoterite ion, ereen = eo? = Hypoferrite ion Fe = 2.530 Ferric ion, colorless FeoH?* = 55,910 Feri ion, coloress Fe(OH); = 306,200 Ferri ion, co = Fe0; = Ferrite ion = Feo! = Feryl ion = eos = Pesferite ion FeO: = Perferry ion 111,685 Ferrate ion, violet BB, Reactions and Equilibrium Formulas Two Dissolved Substances Relative Stability of the Dissolved Substances z= 42 1 Fe) :2H,0=HFeO; 43H 3 2 Fe 41,0 = FeoH* 4H" 3 FoH (OH),° +H 24s 4 Fe =e se ° (eon? s. Fe 410 =FeOH* 4H be By = 0.914 ~ 0,0591pH1 +.0.0591 log “OR ) 6 Fe? £2H,0 = Fe(OH), ' +2H* +e 1.191 ~0.1182 pH+-0.0591 log 1 HFeO;” +H” = Fe(OH),* +e Ey = ~ 0.675 +0.0591 pH +0.0591 log 16 2 45H! 440" (Feo) 8 HFeO;” +2H,0 = Feo, 45H! 4 de 1.001 — 0.0738 pH 40,0148 log S202). 2 : : (FeO, ) 46 (oe 9. Fel 441,0=Fe0e +8H* +36 Fy = 1.700 0.1580 pit +0.0197 log HES) 2 2 (Peoy 10. FcOH®* +3H,0 = FeOg~ = 7H" +30 Fy = 1.652 0.1379 pH +0.0197 log SOs) Fe(OH), +200 = Feo + 6H" 436 ) = 1359 0.182 pit + 0.0197 log (Reon) FeOe) Fon),CONSTRUCTION OF DIAGRAMS 97 TABLE 7.1 (Continued) Limits of the Domains of Relative Predominance of the Dissolved Substances Y Fe JRO; pH 1053, 2. Fe! /ReOW pH=243 3. FeOH?* /¥e(OH), pH=469 4. Bett JBe? F-07711 3. Fe jew? Fy=0914 ~ 00591 pit Fe?* /Re(OM),* By= L191 ~ 0.1182 pI 7 HFeO,~ /Fe(OH), =~ 0675 + 0.0591 pt 8. HFeO; /Fe0 F)=1.001 ~ 00738 pH 9 Fe /ReOg = 1.700 ~ 0.1580p# 1. FeOH /Feo,? y= 1.652 ~ 0.1379 pH u Fe(OH), (FeO? y= 1.599 — 0.1182 pt Two Solid Substances Limits of the Domains of Relative Stability of ron and lts Oxides and Hydvoxides 2. on 4 ¥e+H,0 —FeO+2H" +20 y= — 0.047 — 00591 pHt 1B. om 4267 3Fe + 480 = Fes0,+ 8H™ +86 y= ~0.085 ~ 000591 pit u. 0548 2Fe + 3110 = Fe,0; + 6H” +66 (@) Eo= ~0051 ~ 00591 ptt (0) B= —0.059 — 0.0591 pH 1s. +267 3FeO + HO = Fo,0, 42H! 426 Fy= 0.197 — 000591 pH 16. Doss 2FeO + HO = Fe.Os 4 2H* +26 (@) £o= = 0.057 ~ 00591 pt () Eo=0.271 ~ 00591 pH 426743 2304 + HO = 3Fe20; 2H? +26 (@) £=0.221 ~ 0.0591 pH () Bo =1.208 — 0.0591 pt ‘One Solid Substance and One Dissolved Substance Solubiley of Iron and Its Oxides and Hydroxides 18 Fe 10 = Fe0+ 200 log(Fe!*) = 13.20~ 2p ry FeO | Hh0 = HFe0,~ 1 log(He0)) = — 18.30 pl 3 2. 2Fe!* 4 310 = Fes0s +614 (@ log(te!~) = —0.72— ptt (0) log(Fe*) = 484 —3pit a 2FeOH?* +110 = Fe,0, +481" (@ log(FeOH*) = —3.15—2p1t (©) log(FeOMP*) = 2.41 —2pIt n. : We(OH)! = FeO, +0421" (@) log Fe(OH), ] = ~7.84~plt : one - (©) log Fe(OH). | = - 2.28 — pH 2. Fe= Ret +20 By = ~0.440-+ 0.0295 log(Fe"*) 24. 3 Fe4 210 = HPO; +311 +20 E) ~ 0493 ~ 0.088eplt +0.0295 log(ttFe0:~) +43 2s Fe= Fe +30 a= ~0037 + 00197 gle!) 42 4267 26 BFE | AHO = FesO, 81 4 26 F) = 0980 02364pI1 0 0886 og{Fe?*) 2. > SHFeO, +H! = FeO, +2H,0-+26 By = ~ 1.819 + 0.0295 ptt — 0.0886 tog(tIFe0:~) +48 2. Bet! 4 HHO = Fex0s +611" +26 (@) Fo = 0.728 —0.1773 pH 0.0591 log Fe?! ) (©) Bp = 1.057 0.1775pH1 0.0591 log(Fe**) 2. 24FO, = Fe0; +1026 (@) Ey = — 1139-00591 to(HFeO: ) (©) Bo = ~ 0.810 0.0591 log(HFe0;~) For reactions involving FeO, (0) indicates aabydous FeO, wheres 0) indieaes Fe(OH), Source: Exeeryed toe 1}98 SIMPLIFIED PROCEDURE FOR CONSTRUCTING POURBAIX DIAGRAMS “4 TEST FIGURE 7.1. Potential=pH equilibrium disgram forthe system iron-wter at 25°C (considering as solid substances only Fe, Fes0, and Fe,0;) [1], Reproduced with permission fom [1]. Copyright © Marcel Pourbaix, Example Problem. It is suggested that the reader construct the Pourbaix diagram for the Fe—H,0 system (considering the solid species Fe, Fe,O,, and Fe,05) at 298K and | atm pressure. Plot the diagram on graph paper using pH ranging from —2to +16 and the electrode potential from ~ 1.8 to +2.2 Voie. The equations for each coexistence already have ‘been calculated and are listed in Table 7.1, Itwill be necessary to define what ionic activity will be considered to represent “significant corrosion.” The establishment of what is consid- ered to be “corrosion” evolves into a determination as to the amount of metal dissolution which is permissible “for all practical purposes.” It often has been found convenient to consider the solubility of 10 ® g atoms of soluble ion perliter as representing “no corrosion for all practical purposes.” ‘On Figure 7.1, this assumption is represented by the lines marked — 6 (the logarithm of the activity) ‘The domain of the metal is found at the bottom of the diagram. For simplicity, it is suggested that the equilibrium involving the metal and its least highly oxidized ionic form is an easy equilibrium to start with. In this case, we are considering Eq, (7.23) in Table 7.1 involving iron and ferrous ion, In as much as no hydrogen ion is involved, itis apparent that this equilibrium coexistence involves a family of hor- izontal lines on potential versus pH coordinates the position ‘of which depends on the assumed value of thermodynamic activity chosen forthe ferrous ion. Ifyou choose 10” forthe ionic activity, you will oblain only one line. The question arises as to whether the domain of iron is above or below the line. Referring to the electrochemical equation, Fe oFeth 26 “thought experiment” i helpful in answering this question. If electrons were added, the reaction would be driven in the disection of iron; thus, the addition of electrons (and hence more negative potentials) favors iron rather than Fe?* Therefore, Fe is below the line and Fe?! above the line. ‘The next question is "How far along the pH axis does the horizontal Fe/Fe? ' equilibrium coexistence extend?” Ta the lft, the boundary is usually chosen arbitrarily by select ing the range of pH of interest. The limit for this line in the direction of higher pH depends on the activities ofthe ionic species and the restictions imposed by other equilibria, for example, line 13 in Fig. 7.1, whichis the coexistence between iron and FeO, 3Fe +4H,0—Fes0,+8H* +80 ‘This is alogical choice for next consideration, since Fe,O, is the solid species that involves oxide with the lowest level of oxidation of izon, Reaction 13 in Table 7.1 involves bothelectrons and hydrogen ion and will be a sloping line on the iagram, Another thought experiment will reveal on which side of line 13 ironis stable and on which side FeO, is stable Since this isa sloping line, there are two ways in which this Uecision can be made. Adding electrons will favor Fe; hence, Fe will be on the more negative side of the lin (.e., below the line). Addition of hydrogen ion (lower pH) also stabilizes the species iron. Thus, iron should be tothe leit of (or below) the line and Fe 0, to the right (or above). Simultancous solution of the equations for lines 23 and 13 will reveal the point of intersection and consequently the termination of dominance of the FelFe?™ coexistence. A similar calculation for reaction 26 in Table 7.1 between, Fe? and Fe,O, yields another line with a slope different from reaction 13: 3Fe?* | 40 > FeO | 8H 4 20 Adding either H™ or electrons to the right side pushes the reaction to the leit to restore equilibrium. This favors the TABLE 7.2, Corrosion and Noncorrosion of Iron at 298K" CONSTRUCTION OF DIAGRAMS 99) species on the left (Fe”*). By using the same procedures, itis observed that lines 23, 26, and 13 in Figure 7.1 intersect at an invariant point for a given activity of ferrous ion Line 20, the equilibrium between Fe’ and Fe;0s, re- presents a reaction in which there is no electron transfer, ‘Thus, by inspection of the equation, this coexistence will appear as a vertical line on the Pourbaix diagram. The decision of which species is on which side of the line can easily be made by assessing the effect of adding hydrogen jons and observing that this addition favors Fe*, Thus, Fe? is on the low-plT side of the line Tis suggested that the equilibrium coexistences be taken fone at a time progressing from the elemental state through the various oxidized states to establish the limits of each of the lines, It usually becomes complicated to draw all the lines and to remove those lines and portions of lines that are redundant or improper. ‘When the diagram is complete itis possible to test the predictions of the Pourbaix diagram you have just drawn. Table 7.2 reports a number of experiments conducted by Experiment’ Sample No, ‘Solution PH BMV) Stateof Meu” Gas a 1 1,0 disiled rm oases = 2 NaCl 1g 69-045 ¥ = 3 1,80, Ig 23-0351 ¥ Hy 4 NalisO, 1g 64 osmY, - 5 NaOH Iyt 2 +002 N = 6 K,C10, iy 8540235 = 7 + NaCl 1g 86 0.200 = 8 o2gn 67 =060 = 8 1g 71 +0900 = 10 oe 57 —0200 = u Ho: 308M. 34 40.720 2 Brussels city water 10 0.430 b B NaOH 4OgiL degassed 13.7 — 0.810 © 1“ City wateriron-copper 1s ass = 15 City wateriton-zine 15 0.690 ca 16 City water-iron-magnesium 15-0910 H 7 (City wateriron-platioum, 1s oes - ¢ vd City wateriron-copper 78-0385 = 15" City wateriron—zine 1 0.590 Hy Is Cay wateriton-magnesivm, 87 0495 H 1 ity wateriron-platinum Se = a 18 NaHCO, 0.1 Mf Pole 84 0.860 H 19 NaHCO, 0.1 M Pole + 84-0350, = 2» NaHCO, 0.1. Pole — Bd 0885 Hy 2 NaHCO, 0.1 M Pole 84 +1380 0; € n NaHCO, 0.1 M Pole — 840500 — 2 NaHCO, 0.1 M Pole 8441550 0; a NaHCO, 0.1 M Pole — 84 = 1.000 H 25 NaHCO, 0.1 M Pole + 84 +1550 Or “Experimenal conditions wed ott he predicions ofthe Pourbaixdagram forthe ro-wate syxem “soxerpe from M, Pouba, Lestres on Eletroctemical Corrosion, NACE, Houston, 1995p. 18 ‘abbreviations: Y = cotrsion; N100 Pourbaix in which iron electrodes were immersed in various solutions. The pH and the electrode potential were measured in each case, and the specimens were allowed to stand in beakers containing each of the indicated chemical environ- ‘ments. Now plot on the diagram the data from the experi- ‘ments numbered 1-25 in Table 7.2. For convenience, the sample numbers should be written beside each data point. ‘This will make it possible to compare the experimental results of Pourbaix with the predictions based on the Pourbaix diagram, Remember, the term “immunity” is reserved for noncorrosion and represents the case in which corrosion cannot ovcue for thermodynamic reasons. The term “corrosion” is reserved for areas of the diagram where an ionic species is the stable species thermodynamically. “Passivation” describes the portion of the diagram where a solid reaction product is formed. Presumably, ifthe solid reaction product is protective, corrosion will stop. Thus, the erm “passivation” might be said to apply to a region in the diagram where (thermodynamically) corrosion is possi- ble, butit does not occur, because of the formation ofa barrier coating. The diagram is not sufficient to decide whether a solid reaction product is also protective. This information can only be gained by performing an experiment, Compar- ison between the data points on your diagram with the information contained in Table 7.2 should reveal that in each case shown the Pourbaix diagram would have predicted correctly Whether of not corrosion would occur merely by knowing the electrode potential and the pH of the solution, o 16 oo 7 i q E fl a i r 2k [Maybaates| 0 % —t 1% 0 « 0, 16pH ‘Arsenies] [Batimaniotes FIGURE 7.2. Oxidizing corrosion inbibitors. The hatched regions indicate theoretical corrosion domains in the presence of 0.01 M solutions of inhibitor. Reproduced with permission feom [1] Copyright © Marcel Pourbaix.D, APPLICATIONS OF POURBAIX DIAGRAMS It is possible to predict conditions under which corro- sion, noncorrosion, and passivation are possible. It is also possible to make a number of other useful predic- tions. For example, the electrode potential for cathodic protection is represented by the equilibrium coexistence line between ferrous ion and iron in Figure 7.1. The domain of potential and pH in which anodic protection may be considered is represented by the passive region (either Fes0, or Fe,0s), but care should be exercised to avoid the domains where Fe’, Fe?*, or HFeO; are stable, Ifthe electrode potential falls in a corrosion regime (c.g. in the region where ferrous ion is stable), itis possible to stop corrosion by adding an oxidant that would bring the electrode potential into the region of stability for Fe,0, by raising the electrode potential, or by changing the pHT in the alkaline direction so as to move horizontally into the passive region, or by cathodic protection that has the effect of lowering the potential into the immunity region. It should be emphasized that the predictions made by using the Pourbaix diagram should be tested prior to actual use, since the formation of a reaction product film does not necessarily ‘mean that this film is protective. In addition, cathodic protection may result in hydrogen evolution atthe cathode, which could have an adverse effect on protective coatings ENCES 101 or might under some circumstances induce hydrogen embrittlement of certain metals. Its also possible to predict the types of ions that have promise as oxidizing corrosion inhibitors. Superposition of the chromium-water diagram over the iron-water diagram, for example, shows that the region of stability for Cr,0y coincides with a portion ofthe iron diagram wherein ferrous ion is the stable species. Consequently. inthe absence of an inhibitor, corrosion of iron would be anticipated in this domain of potential and pH, ‘The effect of adding chromates is to provide a means of forming a protective Cr,0, film that inhibits corrosion, Figure 7.2 suggests the influence of various oxidizing in- hibitors on the corrosion of iron [1]. These predictions should be tested before actual use, REFEREN! s 1, M, Pourbaix, Atlas of Electrochemical Equilibria in Aqueous Solutions, National Association of Corrosion Engineers (NACE), Houston, TX, and Centre Belge d'Etude de la Corro- sion (CEBELCOR), Brussels, 1974 2. M, Pourbaix, Lectures on Electrochemical Corrosion, Plenum, New York, 1973 3, UR, Evans, J Inst, Metals, 80, 263, 267 (1923). 4, B.D, Verink and M, Pourbaix, Corosion, 27(12), 495 (1971), 5, C.M Css and W, Cobble, , Am, Chem, Soc, 86,5394 1958),