Corrosion Science, Vol. 3(1, No. 10, pp. 963-988, 199(I Printed in Great Britain.

(1(11()-938X/9() $3.00 + [).(X) Pergamon Press plc

THERMODYNAMICS AND CORROSION*t

MARCEL POURBAIX Belgian Center for Corrosion Study, C E B E L C O R , A v e n u e Paul Heger Grille 2, 1050 Brussels, Belgium

*This paper is the English text of a lecturc delivered by Dr Marcel Pourbaix at the International Symposium held in Brussels, 12-15 March 1989 on 'Corrosion Science and Engineering'. The Symposium was held to celebrate the forthcoming 85th Birthday of Dr Pourbaix which occurred on 16 September 1989. The Two-Volume Proceedings of this Symposium are available from C E B E L C O R . t An abridged version of this statement was given in a conference delivered on 13 March 1989, on the occasion of an Academic Session organized by the Universit6 Libre de Bruxelles (U.L.B.) during the "International Symposium on Corrosion Science and Engineering'. Manuscript received 28 January 1990. 963

PLATE1. Dr Pourbaix, photographed during the Symposium.

Thermodynamics and corrosion

965

Abstract--After having paid tribute to the pioneer works of Fritz Haber, Walther Nernst, Ulick Evans and Carl Wagner, the author mentions the joint activities of CITCE and CEBELCOR in electrochemistry and corrosion, with special reference to graphical methods in electrochemicalthermodynamics(electrode potential/pH and electrode potential/temperature diagrams) and in electrochemical kinetics (polarization curves in stirred solution). Examples of results obtained by these methods are givenconcerningcorrosion and some other fields related to electrochemistry. The author expresses the wish that further work be conducted in these areas, preferably by a group of electrochemists and other scientists who would accept to link their efforts in 'applied thermodynamicsand corrosion'accordingto a 'moral charter' similar to the one which led in 1949, in electrochemistry, to the creation of CITCE. INTRODUCTION DEAR FRIENDS, Thanks to all of you for being here this evening. I wish to express my feelings of special gratitude to those of you who came from the Netherlands: without the support which was lavished to me 50 years ago by Frans Eppo Cornelis Scheffer and by Willy G. Burgers, professors at the outstanding institution whose name was then 'Technische Hogeschool te Delft', the works which will be mentioned today could not have been achieved. And many thanks also to my American friends of the Electrochemical Society and of the Massachusetts Institute of Technology, M.I.T. who, after having so magnificently honoured me in 1984 in New Orleans and in Boston on the occasion of my 80th birthday, have suggested that we meet again today in Brussels on the occasion of my 85th. And my gratitude also to those, known or unknown, who have organized the present meeting which was for me a most pleasant surprise. And my congratulations for their pragmatism which led them to celebrate this 85th anniversary at a moment where my age is still only 84, which is a token of prudence. In this connection, I think that some of you will remember that Sir Winston Churchill, after a well-filled career, devoted an important part of his latter years to his hobby, painting, which he practised in a small village in the south of France, where he was at the time of his 80th birthday. This led the young mayor of this village to organize in his honour a manifestation of sympathy where he said to him: ' . . . and we also hope to celebrate with you your 100th anniversary', to which Churchill replied: ' . . . but, why not? You seem to be in good health'. But Churchill died at the age of 91 . . . I very much thank the Universit6 Libre de Bruxelles for having, in 1974, when it was considered that I should enjoy a relative retirement, left to C E B E L C O R the disposal of premises, which have allowed Antoine and his excellent team to pursue their task of goodwill. I express my very deep gratitude to those, very numerous, who allowed C E B E L C O R to start and to survive, and particularly to: - - George Velter, general director of Fabrimetal, who gave birth to it; Louis Baes, who was president of its executive board; Paul De Groote, Felix Leblanc, Jean Baugniet and Andr6 Jaumotte, who were successively altogether presidents of the boards of directors of both ULB and C E B E L C O R . As said in 1948 by Ulick Evans, 1 who was the father of the scientific study of metallic corrosion in the presence of aqueous solutions, the researchers who have wished to apply chemical thermodynamics to the study of these phenomena (which are essentially electrochemical, and not chemical) felt themselves on 'quicksands': the basis of their studies was real, but insufficient, and the researcher was sucked down without being able to progress--and, despite the classical works of Walther
-

966

M. POURBAIX

Nernst in Germany and G. N. Lewis in the U.S.A., one has for many years believed that thermodynamics could only be of little help in this area. It has been said that the often complex phenomena which occur in metallic corrosion do not follow the principles of thermodynamics. But, if thermodynamicians are sometimes wrong, thermodynamics itself is never wrong. Although the first applications of electrochemical thermodynamics may be found in the works of Fritz Haber (who mentioned insistently already in 18982 and in 18993 the importance of the concept of 'electrode potential') and of Walther Nernst who published shortly later his famous 'scale of dissolution tensions', one had to wait a long time before the value of this concept could be fully appreciated: this appreciation was thwarted by the existence of two opposite conventions concerning the sign of these electrode tensions (or potentials), which was, for the non 'noble' metals, as zinc for example, sometimes considered as negative ('east coast convention' in the U.S.A.) and sometimes considered as positive ('west coast convention'), and this until 1953, when the 'Stockholm convention' of I U P A C (International Union of Pure and Applied Chemistry) prescribed the sign 'minus' for the electrode potential of zinc. 3 In the meantime Georges Chaudron once said to me: 'Electrochemistry is not a science. I do not know two electrochemists who agree'.

THE AFFINITY. THE FIRST AND SECOND PRINCIPLES OF THERMODYNAMICS According to concepts introduced by Theophile De Donder, 6 the affinity A of a chemical reaction vM = 0 may be expressed by the relation A = Y, v/~ (where the/~ are the 'molar chemical potentials' of the reacting species M). The 1st principle of thermodynamics prescribes that the equilibrium condition of such a reaction, which corresponds to an affinity equal to zero, may be expressed by the relation v/~ = 0. The 2nd principle of thermodynamics, expressed by the De Donder's relation Axv >- 0 (which its author familiarly called 'Ave Maria') prescribes that the speed v of a chemical reaction is always, either zero, or of the same sign of its affinity. I have been concerned with the extrapolation of these concepts of De Donder to electrochemical reactions vM + n e - = 0 involving, besides chemical species M, free negative electrons e - . This has led me to consider that, according to the 1st principle of thermodynamics, there exists, for such reactions, an 'electrical equilibrium potential' Eo measured vs a given reversible reference electrode (for instance the standard hydrogen electrode SHE) whose value is given by the relation E0 = (Z vl~/23060n) V (SHE), where the molar chemical potentials/~ are expressed in calories. The affinity A of an electrochemical reaction may be expressed, in V, by the relation A = ( E - E o ) where ( E - E0) is the difference between the 'reaction potential' E and the 'equilibrium potential' Eo of the reaction, i.e. the 'overpotential' (or 'overvoltage') under which the reaction occurs. The 2nd principle of thermodynamics, expressed by the relation (E - Eo) xi >- 0 prescribes that the velocity of an electrochemical reaction (measured by the intensity of the 'reaction current' i) considered as positive in case of an oxidation and as negative in case of a reduction, is always, either zero, or of the same sign as its overpotential: if E > Eo, i -> 0, i.e. if the reaction potential E is greater (more positive) than the equilibrium potential Eo of a reaction, this reaction can occur only in the
-

Thermodynamics and corrosion

967

direction of an oxidation, e.g. Fe --~ Fe 2 + 2 e - , or (H2) --~ 2H + 2 e - . A reduction is impossible. if E < E 0, i -< 0 i.e. if the reaction potential is lower (less positive, or more negative) than the equilibrium potential E0 of a reaction, this reaction can occur only in the direction of a reduction, e.g. Fe ~--Fe 2 + 2e , or (H2) ~---2H + + 2 e - . An oxidation is impossible. When, around 1936--1939, Theophile De Donder became aware of these formulae E0 = (E vp/23060n) and ( E - E o ) xi>-0 and knew that I had made some experiments which proved that these formulae were correct and useful, he jumped for joy (for, despite his 64 years, he had kept the enthusiasm of a child) and he exclaimed 'The good Lord is the simplest being in the universe!" . . . and I had the surprise of receiving, from the society 'La Chimie Mathdmatique' of which he was the director, a cheque for a thousand francs. De Donder expressed the wish that I should add to the text of the thesis which I was then preparing a 'Chapter VIII' which would create a still closer link between the formulae I had established and the formulae which were used by his school, but, despite prolonged effort, I could not succeed: our ways of thinking were too different, and the two parallel ways along which we were both walking towards similar goals could not merge. As has been mentioned by rector Paul Foriers 7 one had to wait the publication of Ilya Prigogine's thesis, in 1947, s for a full agreement between these two approaches of electrochemistry to be reached. In conclusion, if one wishes to study phenomena involving electrochemical reactions, it is rational: on the one hand, to determine, by calculation, the equilibrium conditions of all possible chemical and electrochemical reactions. This may be easily done with the formulae given in Table I if one knows the values of the standard chemical potentials /~0 of all reacting chemical species. - - on the other hand to determine experimentally, for every one of the electrochemical reactions r of practical interest, the influence of the 'reaction potential" E on the direction and intensity of the 'reaction current' it. This may be done by the determination of 'polarization curves' of type E = f(ir) under conditions where the reaction potential E and the equilibrium potentials Eo,,- are perfectly known. This generally implies that these experiments be performed in stirred solution and that the electrode potentials be measured vs a well known reversible reference electrode, using a junction-siphon of type Haber-Luggin or Piontelli emerging in the solution at immediate vicinity of the metallic surface on which the reactions to be studied are taking place (Fig. 1). When these two conditions are fulfilled, the polarization curves show, in fact, the relationship which exists between the velocities ir of the reactions r and their affinities ( E - Eo,r), which is a perfectly Cartesian way to study a phenomenon. According to the method of representation used at the bottom of Table 2, all polarization curves are rising from left to right and cut the ordinate axis at the point where the electrode potential is equal to the equilibrium potential Eoj. In the frequent case where several electrochemical reactions may occur simultaneously on a same interface metal/solution, the 'principle of superposition of partial tension-current curves' established in 1938 by Carl Wagner and Wilhelm Traud '~'~may powerfully lead to the perfect elucidation of the studied phenomena. Due to the frequent complexity of the electrochemical phenomena of corrosion
-

968 TABLE 1.

M. POURBAIX
CALCULATION OF THE EQUILIBRIUM CONDITIONS OF REACTIONS AS A FUNCTION OF THE STANDARD CHEMICAL POTENTIALS t/0 (CALORIES)

Chemical reactions

EvM=0 Ev, u = 0

where

P =po+ RTIn (M) = I'" + 4.5756TIog (M) (calorics per mole)

E vp + 4.5756TE v log (M) = 0 X v log (M)

=

log

where

log K -

4.5756T

(equilibrium constant)

for t = 25.0C (T=298.1 K):

E vlog (M) = logK

where

log K -

\~ vp 1364T

Electrochemical reactions E vM + h e - = 0

E = Eli + O"(X)OI984TS'nv log (M)

N" 0

(equilibrium potential)

whcrc

El', = ~ [ V ( S H E ) ]
LD UOUH

(standard equilibrium potential)

I
for t = 25.0C ( T = 298.1 K):
E, = Eo i, + 0.0591 E v log (M)
n

where

\" vpO E~j,- 23 060n

(and others) in which take part many substances involved in many reactions, it is often useful to make use of graphical methods. They represent the whole of the thermodynamic and/or kinetic data relating to these problems (for instance equilibrium diagrams and polarization curves set up as a function of an electrode potential). The study of these problems then is similar to a picture-game which is particularly simple for the players who are used to it.

Frans Eppo C, SCHEFFER

WiLLy GeraLd BURGERS

ULick Richardson EVANS

Th~ophiLe DE DANDER

Carl WAGNER

R,M. GARRELS

M.M. Roberto PIONTELLI,GobrieL VALENSI, Raymond DEFAY,Pierre VAN RYSSELBERGHE FLoyd BROWN

PLATE 2.

969

Thermodynamics and corrosion

971

Metat

~
f

Sotution HzO,Oz,H z Fe (OH) z Fe304 Fe203 HzOz

Reference electrode

FI6. 1. Electrode potential measurement.

THE THESES OF DELFT AND OF B R U S S E L S - - C I T C E AND CEBELCOR In 1945 two theses were defended in Delft and in Brussels related respectively to the electrochemical principles which have just been recalled (Delft) and to some of their applications to the study of corrosion (Brusselsl~r-13). And, several years later, in 1949 and in 1950, as proposed respectively by Willy G. Burgers and F61ix Leblanc, twin organisations, C I T C E (Comit6 International de T h e r m o d y n a m i q u e et de Cin6tique Electrochimiques',* whose name was changed in 1970 to I.S.E., 'International Society of Electrochemistry') and C E B E L C O R ('Centre Beige d ' E t u d e de la Corrosion') were created in Brussels for promoting, on the basis of these two theses, an international collaboration concerning researches relating respectively to some fundamental aspects of electrochemistry based on the m e a s u r e m e n t and the interpretation of electrode potentials ( C I T C E ) and to the fight against corrosion (CEBELCOR14-16). This collaboration, centered on a small group of enthusiastic friends acting with full 'fair play', led rapidly to very considerable progress in electrochemistry and in corrosion, and this altogether in the four areas of theory,

experiments, education and technology.

Plate 2 shows some of the distinguished workers who are referred to in this lecture. The lower left shows four m e m b e r s of C I T C E , meeting during a working session related to questions of electrochemical nomenclature: the late Pierre Van Rysselberghe (U.S.A.), R a y m o n d Delay (Belgium), Gabriel Valensi (France) and R o b e r t o Piontelli (Italy). The m e m b e r s of C I T C E , whose action has led to a real mutation concerning electrochemistry and some of its applications, were working according to a 'moral charter' which defined them as 'a group of searchers interested in the same problems, and collaborating in complete cordiality and frankness to the achievement of a given research p r o g r a m m e ' , 17 which was to be revised during annual meetings. *Here are the names of the 13 founding members of CITCE (x = deceased): Belgium: Carmen Boute, Andr6 Juliard, ~Jan Gillis,Marcel Pourbaix (secretary); France: Gaston Chariot, Gabriel Valensf~; Italy: Roberto PiontelliX; Netherlands: Willy G. BurgersX;Czechoslovakia:Jaroslav HeyrowskyX; U.K.: John O'M Bockris, Thomas P. HoarX: U.S.A.: Paul Delahay, Pierre Van Rysselberghex (president).

972

M. POURBAIX

TABLE 2.

AFFINITY AND DIRECTION OF CHEMICAL AND ELECTROCHEMICAL REACTIONS: POLARIZATION CURVES

C h e m i c a l reactions Reaction E vM = 0

E l e c t r o c h e m i c a l reactions Y_.vM+nc=0

Fc + 2H + = Fc 2+ + (He)

Fc = Fc 2+ + 2c 2H + + 2c = (Ha) Fc+2H +=Fc >+(H2)

(c) (a)

Affinity Equilibrium

A = - Z VIA = 0

v/~

(calorics)

= n(E - E.)
E = E

(V)

Direction o f the reaction A v >1 0 ( E - Eo)i >1 0

if E > E 0. i/> 0

o
~o
Evotution of gaseous hydrogen

o x i d a t i o n or no rcaction

~
-0,24

g o s e o u s

Fc ~ Fc 2+ + 2 c (He)---* 2H + + 2c r c d u c t i o n is i m p o s s i b l c if E < Eo, i~< 0 r c d u c t i o n or no rcaction Fc *-- Fc 2+ + 2 c -

(c) (a)

(c) (a)

Etectrodeposition
of iron

/-7

(H2) *--2H + + 2 c -

--~ D i s s o L u t i o n -0.50

of iron

o x i d a t i o n is i m p o s s i b l c

Reaction currents
s_

Reductions

Oxidations

Fe :Fe~++ 2e- (c) (H)2: aM++ 2e- (a)

SOME

RESULTS

OF THE

ACTIVITY

OF CITCE

AND

CEBELCOR

H e r e are some results of the joined works of C I T C E and C E B E L C O R in the four areas (theoretical, experimental, educative and technical) which have just been mentioned.

Theoretical activitylS-2t The potential-pH diagrams at 25 C, and their applications to the protection against corrosion. A powerful support from the U N I O N M I N I E R E , from the I R S I A
(Institut de Recherches Scientifiques dans l'Industrie & l'Agriculture) and from the

U.S. Air Force led to the setting-up and to the publication by Robert Maxwell, in French and English, of an 'Atlas of Electrochemical Equilibria in Aqueous

Thermodynamics and corrosion

973

Solutions u9 which includes 'Potential-pH Equilibrium Diagrams' for all chemical elements in the presence of water, at the temperature of 25C. Here are some examples of these diagrams: Figure 2(a), which relates to pure water, shows that water is thermodynamically stable under a pressure of 1 atmosphere only in a well determined 'area', below which it may be reduced with evolution of hydrogen, and above which it may be oxidized with evolution of oxygen--Fig. 2(b) shows the acid, alkaline, oxidizing and reducing media. Figure 3, relating to iron in the presence of water shows notably, besides the lines (a) and (b) relating to water, the circumstances where thermodynamically stable metallic iron Fe, its solid oxides Fe30 4 (magnetite) and Fe203 (haematite), and its dissolved derivates Fe 2+ (ferrous), Fe 3+ (ferric) and F e O , H - (bihypoferrite) exist; from which may be easily deduced Fig. 4 which shows, according to some hypotheses, the theoretical areas of iron corrosion (where the metal may be dissolved), of immunity (where the metal is thermodynamically stable, and thus uncorrodible) and of passivation (where the metal may be covered by a more or less protective oxide film. Happily this theoretical diagram fits very well into the experimental facts. It has enabled us to explain strange facts, which were hitherto not understandable: the absence of iron corrosion in certain solutions of nitric acid (which raise the electrode potential of the metal in the 'passivation area' with coverage by an invisible oxide film); the conditions of success of the famous and then much debated 'Evans experiment' relating to the 'differential aeration of iron' (Fig. 5), according to which local aeration of an iron surface sometimes leads to corrosion of the non-aerated spots. From a technical point of view, such figures very much helped to set up perfectly safe criteria for the corrosion protection of the thousands of miles of buried pipelines used for the transport of oil and gas. The search for such a criterion had been the main reason for the creation, in the U.S.A., of the National Association of Corrosion Engineers. This rapid success came to us as an agreeable surprise, more than the first of the potential-pH diagrams, which related to copper, 22 had been set up, not for a
2 0 --16 12 08 0 4 __ 0 -04 Domoin of t h e thermodynomlc
rO 0

Oxyg . . . . . Luti. . . . d acid itica~ion

20 J6

OxidiiZmeda ing acidic

Oxidizing alKa i,lne rngKli0

-04 -f
Hydrogen evoLut:ion ond at kaL inizotion

~ ~
Reducing acidic me@io Reducing OLkotine medio

-08 -I 2

-08 12 f
-16

-16

~
--

-2
FiG. 2.

I
O

i
2

L
4

I
6

L
8

I
tO

i
12

I
14 16 -2

I
0

I
2

k
4

]
6

I
8

I
I0

I
12

I
14 16

pH

(a) Domain of thermodynamic stability of water under I atmosphere pressure; (b) Acid, alkaline, oxidizing and reducing media.

974
2.2

M. POURBAIX

1.8 1.6 1.4

o q
0

4ZO.

Fe042- 9

0.8 0.6 0.4-0.~'-b.I

"-..Fe(o~); " . .

~ ~..

_(~.
~
I

-0.2 --

- o., - ~ . ? ,
-0.6 ~ -0.8
-

H FeO2 Fe Q

- 1"2L -1.4 --I.6 --I.8

-2

-I

7 pH

I0 II

12

13

14

15 16

FIG. 3.

Equilibrium diagrams for the system iron-water, at 25C.

corrosion study, but for a study of catalysis. And this encouraged us very much to pursue the setting up of such diagrams as well as experimental studies related to their scientific and technological applications. Figure 6, 23 which was established as a result of the Washington Corrosion Dialogue' held in March 1966, helped the setting-up of methods of quality control of 'weathering steels' such as Corten and Mayari-R, as well as of recommendations intended to avoid disappointment in the industrial application of such steels. Alex Pirson, who was the first technical secretary of CEBELCOR has, with much talent and humor, popularized this iron diagram (Fig. 7).

2olQ t
16 08 ~ -12 -16 --

Immunity

l
-2 0

I
2

I
4

I
6 pH

I
8

I
I0

i
12

I
14 16

FIG. 4.

Theoretical conditions of corrosion, immunity and passivation of iron, at 25 .

Thermodynamics and corrosion

975

Ftow ofelectrons

Air or oxygen

,/3-

woy tap

~i~Porous
~ 1 1 1 I brrier
Potassium chloride solution-Metal

JJ

II

II ~

Metal

FIG. 5.

Production of a current by differential aeration (Evans experiment).

There exists, for every metal, a potential-pH diagram which is as specific to him as are, for everyone of us, our fingerprints and the lines in our hands. Figure 824 gives such theoretical 'corrosion-immunity-passivation diagrams' for 43 metals and metalloids. One sees from this figure that: Gold (no. 1), whose area of immunity completely covers the area of stability of water is the least corrodible of all metals. The frequent excellent resistance to corrosion of aluminium (no. 39) is due to the formation of a protective oxide film. In the case of exposure to the action of an atmosphere one has, however, to avoid any contact with substances which are acid (such as sulfuric soots) or alkaline (such as fresh cements). Aluminium frames should be kept with the same care as glass windows. Lead (no. 8) will be corroded by most soft waters, and this may, in case of water distribution through lead pipes, cause poisoning to the drinkers and death from 'saturnism'. Incidentally, according to Fig. 9, which shows the equilibria of the system Pb-SO2+-H2 O, in a lead battery containing sulphuric acid, the open circuit poten-

0.8 04~
Corrosion

~'~.~

Passwotion

-08

Immunity

G pH

I0

12

14

FIG. 6. Conditions of immunity, general corrosion and perfect passivation of iron in chloride-free solution; line I: in the absence of oxygen; lines 2: in the presence of oxygen.

976

M. POURBAIX

FIG. 7. Corrosion,immunityand passivation diagram of iron at 25C (by Alex Pirson). tials are respectively -0.31 V(SHE) for the negative electrode (in lead) and + 1.64 V(SHE) for the positive electrode (in lead covered with lead peroxide PbO2), which corresponds to an electromotive force of 1.95 V. When using the battery for starting a car, the representative points of the two electrodes move closer together: lead of the negative electrode dissolves by oxidation, and lead peroxide of the positive electrode dissolves by reduction. After starting the car, the dynamo induces a reversal of the current with recharging of the battery: redeposition of metallic lead with hydrogen evolution on the negative electrode, and reformation of PbO2 with evolution of oxygen on the positive electrode. As point 2 of Fig. 9 is situated above the 'oxygen line' (b), the PbO2 layer which covers the positive electrode is thermodynamically unstable when at zero current, and thus tends to dissolve with evolution of oxygen and diminution of the acidity according to the reactions. 52 and i.e. globally 2PbO2 + 8H + + 2e- --+ 2Pb 2+ + 4 H 2 0 2 H 2 0 - + (O2) + 4H + + 4e2PbO2 + 4H + --+ 02 + 2Pb 2+ + 2H20. (b)

Thermodynamics

and

corrosion

977

z
o
I GoLd O 7 I~ 2 ::~::::::::::::: . . . . . . . :l.::::::::::::::1::: ...... 0 ~

..::il~i~.::

";:i~i.:l:i:i:i:i:i:!:li:

:':'~ ........

...... ::::::::::::::::::::: 'o :::::::::::::::::::::::::::::::::::::::::

. . . . . . .

~:;i~::~:~:~,

12
2 I r i d i u m 14 3 PLQbnum
L4

pH

2 ......./.:::::
-I

20

o 13 Copper 14 I 7 14 0

I~" Technetlom 1 4

0 0

14 p~ 15 B~smuth 7 14

~2

E ~_~' ::::::::::::::::::::::::::::::::::
4 Rhodium 0

-2 RL~themdr~
0 Potlcldldm 4 pH 16 ~ n t l m o n y

N
i 7 Arsenic
0 7

14

18 Carbon

14

pH

"-:.::i:~:~:~?i

======================

-2

14"

14

pN

-2~'~"~'~
[ 9 Lead
0 7

~
0
-2

7 Mercury 7 I~

V I/ 1 / H / 1 / 1 /) '(
0 14 0 I I TeLi.Jrtum
0 7 b4 0

8 S~lver 7

9Osmium 7 14

/4I
L4

14 20 Rhenium
14 0

2i NrckeL 14 pH
7 .. 14 2

I;:I;:;::::~:::~:~::~:,:,:.:.;.I.:.:: z
E

.................. ::::::::::::::::::::::::: iiil

10 S e l e n i u m
9 0 7 14

12 Polonium
7 14 0

22 Cobalt
7 14

25 T h a L b u m
0 7 14"

24 Codm=um
0 7 i4

, E

............. ============================

e L E

!i~i].i~i:~:i:~ ':':':.':::'i~iiii

':'::::i:

t ":':::i:iiiii~i~ii~i:':~ "

2
I

2 5 I r o n 14

26 Tin

0 tzl H 2"7 M o l y b d e n u m p

-2
3 8 Zirconium TM 89 ALumimum 4 0 Hafnium pH

28 Tungsten

29Germomum

14 3 0 Endium

DR

/4

/4

pH

41 T i t a m u m

42 Beryllium

4 3 Mogneshurn

N
E ""':'::::i:iiiiii!i!i!i!~i!:::: i ~

........ bydi,,oL0t,on
Corrosion by gas,hootion ~ eQ&siv(~tcion by oxide or hydrox ide Layer ~l~lt~ivetion by hydroxide Layer Immunity

2 (~l, 14 31 Gallium

0 14 DH 33 Tantalum 34 Niobium

LA

14

35

Crlroml~m

5 6 Vanadium

52" Manganese

F I G . 8.

Theoretical corrosion, immunity and passivation domains of 43 metals and metalloids, ordercd according to their thermodynamic nobility.

978
Charge ~ ~ - , ,"~ , ~

M. P O U R B A 1 X

---_-_

Dischorge

_ ,,,

PbO2 ~,

".,

P~O~-

o -~

Pb2+
. ~

PbS04 PbO

"i'---Charge

ii
" - ~ " ~

I
0

I
I

I
2

I
3

I
4

I
5

I
6

I
7

I
8

I
9

I
l0

11 12

13 14 15

pH

FIG. 9.

Operating conditions o f a lead accumulator (with 1M H2SO4, p H 0.2).

This is the reason for the well known phenomenon of destruction of lead batteries out of service, when the PbO2 layer of the positive electrode is not regenerated by recharging on time, before it becomes too late. 25

The pitting corrosion of copper pipes for cold town water distribution. 26 In 1961, the 'International Copper Research Association', INCRA, asked CEBELCOR to try to elucidate some electrochemical aspects of the pitting corrosion which affected copper pipes for water distribution, and was then a severe problem in several countries, such as Belgium, Germany, Netherlands, U.K. and U.S.A., but not in France. Figure 10 shows a cross-section through a copper pit in Brussels drinking water. At the bottom of the pit white cuprous chloride CuC1 and a large quantity of red cuprous oxide Cu20 coexist: the pit is covered by a layer of green malachite CuCO3, Cu(OH)2 (and by a small quantity of calcium carbonate CaCO3). It is obvious that the solution existing in the cavity does not have the same composition as the bulk of the water, but is saturated altogether with CuCI, with Cu20 and with metallic copper Cu. Figure 11 shows the cavity after removal of the non-adherent Cu20. Figure 12 is the equilibrium diagrams of the ternary system Cu-C1-H20 for solutions 10 -2 M in C1- ions (355 mg C1- 1-1), which is approximately the chloride content of solutions saturated in cuprous chloride. The only point of this Fig. 12 where the three solid substances Cu, Cu20 and CuCI which coexist in the pit are simultaneously stable is the crossing point of the three lines no. 12, 51 and 55. This point, whose co-ordinates are E = +270 mV(SHE) and pH = 3.5 thus represents the conditions of thermodynamic equilibrium in the pit. As, under these pH conditions, the corrosion reaction of copper is reversible, it is easy to understand that any similar pit will grow or not grow according to the electrode potential of the metal inside the pit will be higher or lower than +270 mV(SHE). If, for any reason, the electrode potential inside the pit is higher than +270 mV(SHE), the copper will corrode there according to a reaction such as Cu ~ Cu 2+ + 2e-; if, on the contrary this potential is

Thermodynamics and corrosion

979
CuC03- Cu(OH)2(green)

(I O)

CuCO 3- Cu(OH)2 (~reen)

(I I )

u20 ~

Cu20

FIG. 10. Copper pit in Brussels water. Cross section showing the presence of red Cu20 and CuCI beneath a green mushroom of malachite. Flc,. 11. Copper pit in Brussels water. Cross section of the pit shown at Fig. 10 after removal of the loose deposit of Cu20.

lower than +270 m V ( S H E ) , copper will deposit there according to a reaction such as Cu 2+ + 2 e - ~ Cu, and the corrosion will be stifled. And this extremely simple criterion has allowed to avoid any corrosion of copper in cold drinking water. But, why did one not observe in France copper failures similar to those observed in other countries? Simply because, in these other countries, soft annealed copper tubes were generally used. The tubes were annealed in a reducing atmosphere which led to the superficial formation of carbon which increased the electrode potential of the metal above the critical value; this was not the practice in France where cold drawn hard tubes, not annealed, were preferred, which were free from superficial carbon. This criterion has also prevented any pitting corrosion of copper and of copper alloys in other cases, notably in the protection of condensers in copper alloys by addition of ferrous salts to sea water. 27-29 It has also allowed under the conditions
-2 -4

26 /'/"-~

'

-~

-,

-2~
I

1,8

0/

0.4

I CuO '

C u O ~2 . ~ I C ~ , ~ "

' "~

-04

--

-I.0

"

-14

I
- 1'82 0

I
2

I
4

I
6 pH

1
6

i
I0

I
t2

I
14 16

FIG. 12. Potential-pH equilibrium diagram for the three-component system Cu-C1-H20, for solutions containing 355 ppm CI- (10 2 g ion 1 l).

980

M. POURBAIX

which sculptures in gilded bronze resist or do not resist to the corrosive action of an atmosphere to be elucidated. 3'3t
Other applications o f potential-pH diagrams. The potential-pH diagrams which have just been presented are only a few examples among many, set up by many searchers, generally in the frame of the collaboration initiated in 1949 by CITCE, and this, not only in corrosion, but also in other areas, like the four last mentioned below which had not been originally foreseen: -----analytical chemistry general chemistry electrodeposition electrometallurgy batteries and fuel cells

Gaston Chariot, France; Gabriel Valensi, France; Thomas P. Hoar, England; Paul Duby, U.S.A. Jean Brenet, France.

In this area of batteries and fuel cells, a synthesis-statement about the thermodynamic and kinetic aspects of the electrode reactions would be particularly welcome. Geology: Robert M. Garrels, U . S . A . 32"33 who pioneered the thermodynamic study of sedimentary deposits and established such diagrams for the Colorado minerals of uranium and vanadium, and stayed in 1963 at U.L.B., where he was appointed Dr. Honoris Causa. His decease, which occurred on 8 March 1988, has sadly affected his many friends. Flotation: William T. Denholm, Australia 34 who, pioneer of the electrochemical study of flotation, applied such diagrams, with great success, to the treatment of sulfide minerals. Agriculture: F. N. Ponnamperuma, Philippines 35-37 who, when visiting me around 1975, told me that these diagrams (mainly those related to iron and to manganese) had helped the 'Rice Research Institute R.R.I.' to double the yield of rice fields in south-east Asia (optimal conditions about pH 6.6 and E +0.03 to 0.14 V(SHE)). Ecology: Mitsuo Kurachi, Japan who, searching for a remedy to very severe damages (illness known as itai'-itai', and contamination of rice fields) provoked in Kamioka by effluents of the Mitsui Mining and Smelting Cy containing a too high amount of cadmium, set up, with the help of such diagrams, a treatment which decreased the cadmium content of these effluents below 1 ppb. Moving now to medicine and coming back to corrosion, Fig. 13 shows the behaviour of iron and of stainless steels in the presence of chloride containing solutions, somewhat similar to sea water and to the fluids which impregnate the human body. These diagrams have been set up for a study about the behaviour of surgical implants, z4 The hatched areas show the conditions to be avoided, where these implants may corrode with dissolution of alloying elements which may be very damaging for the health. The triangular hatched regions which appear in the lower left part of the diagrams relating to stainless steels may be particularly dangerous, for they correspond to localized corrosions occurring inside interstices which have become acid (for instance under a screw) and which, as shown by the experience of F. L. Laque (Fig. 14) may allow a rubber band to shear a plate of stainless steel. One of the consequences of the diagrams and experiences shown in Figs 13 and 14 is that, in the case of young persons, who still have a long life expectation, it is

Thermodynamics and corrosion

981

~.

:Lectropotished and . " o ~ " ~ . ~ emeri polished ~

~f

L~ C

= FII

I Protection

-I

))
0 2 4 6 pH 8 I0 12 14 0

I0

12

14

pH

IElectropotished :no pitting

~(~
E L e c t r o p ~ , ~ Emeri p o t i s h e d ~ ~ Protection

&

rotectlon

-Itc ) 1
0 2

[
4

1
6 pH

[
8

I
I0

L
12 14

I (d) l
0 2

I
4

L
6 pH

[
8

I
I0

I
12 14

FIG. 13. Experimental areas of general corrosion, immunity, pitting, imperfcct and perfect passivity of iron and steels in the presence of solutions 10-1 molar in chloride (3.5 g CI I 1), at 25C; (a) iron and unalloyed carbon steels; (b) AIS! 410 chromium steel (draft); (c) AIS1304 nickel-chromc steel (draft); (d) AIS1316 molybdenum-nickel-chrome steel (draft).

Chromium

steeL

C h r o m i u m - nicl~eL steel AiSi 304

C h r o m i u m - nickel molybdenum steel AiSi :516

AiSi 430

FI3. 14.

The 1NCO rubber band test for crevice corrosion (after F. Laque et al. and J. P. De Greve).

982

M. POURBAIX

generally advisable to remove the implants after healing of the fracture. In the case of elderly people, older than 85 years for example, for whom the life expectation is obviously shorter, one may spare a second operation and leave the implant where it
is.

Figure 15, relating to titanium, shows that the risk of corrosion which has just been mentioned for stainless steels does not appear for this metal.

The diagrams of electrochemical equilibria for high temperatures. Before closing the chapter relating to equilibrium diagrams, I should remind that such diagrams, often extremely useful and promising, have been set up by many researchers, for aqueous solutions at high temperatures, for molten salts, and for systems involving a gaseous phase. Some of these works will be mentioned later. Equilibria in the presence of aqueous solutions. 21,39,50 Long range work undertaken in the U.S.A. by C. M. Criss and J. W. Cobble 14as well as by H. C. Helgeson, D. H. Kirkham and E. L. S c h o c k 42, concerning the determination of thermodynamic data for substances dissolved in water at high temperatures, have allowed many researchers to set up, without or with use of computers, potential-pH equilibrium diagrams for high temperatures, up to 300C. Equilibria in the presence of molten salts. 43 Diagrams of electrochemical equilibria relating to molten salts have been set up for carbonates (R. Buvet, M. D. Ingram, C. J. Janz, M. Pourbaix), for chlorides (C. Edeleanu, R. Littlewood), for hydroxydes (B. Tremillon), for nitrates (A. J. Arvia, A. Cont6, M. D. Ingrain, S. L. Marchiano, N. Ramasubramian, R. A. Rapp), for silicates (R. Littlewood), for sulfates (R. W. Geist, C. O. Park, A. Rahmel, R. A. Rapp). Equilibria in the presence of a gaseous phase.44-46 Figure 16 shows an example of an equilibrium diagram relating to the oxygen-iron system drawn as a function of an electrode potential and temperature, set up in the frame of a very vast project aimed at the achievement of a series of Atlases of Chemical and Electrochemical Equilibria

I
O 2

I
4

I
(5 pH

I
8

I
IO

I ~
12 14

Fm. 15.

Areas of general corrosion and passivation of titanium at 25C (draft).

Thermodynamics

and corrosion

983

-I0 0 IO 20 30 40 50 60

sotso~,
k i

=~t

to,=p o 2 = ~ i "
q . ~ ~ -- FGzO -5

'~ K FI

+I

O.36~ .---____ ~

_____.~_

~~ - ~

c~

90 Io0

--~ -{0
"

?/

/~ Im~B/~Fel-xO"
';

D iID Cj i

IlO - d _ 5 120
130 140 150 160
170

180 __ 190 _ 2O0

Fe -2 0 lOg DFe=-E "5

~'
-3

-2

s~o

logo
50o

,s~o
TOK

2o~o
15oo ToC

2500

3000

3500

~ooo

zooo

z5oo

3000

F1G. 16,

Potential-temperatureequilibriumdiagramfor the oxygen-ironsystem.

in the Presence of a Gaseous Phase for oxides, hydrides, carbides, chlorides, fluorides, sulphides and nitrides of all chemical elements, from 0 to 6000 K. It should be well understood that all the diagrams of electrochemical equilbria which have just been mentioned should be used only with greatest care, mainly because they are calculated on the basis of thermodynamic data which may be incomplete or erroneous, particularly when they relate to aqueous ions at high temperature or to non stoichiometric solid substances. It is thus essential that the exactness and the practical validity of these diagrams be verified and specified by experimental researches which would, if feasible, include the measurement and the intrepretation of values of electrode potentials. Experimental and educative actities CEBELCOR's team has striven to develop on every occasion experimental techniques based on the measurement and the interpretation of values of electrode potentials. This has led to rapid methods for the appreciation of the corrosion velocity, notably concerning the particularly complex phenomena of localized corrosion, 4v as well as of atmospheric corrosion. 4s This is specially true for methods based on the setting up of polarization curves in stirred solutions 49'5 which have allowed perfectly reproducible and interpretable kinetic information to be obtained very quickly, for the first time. As a result of the 'Washington Corrosion Dialogue' organized in 1966 by the National Bureau Standards (N.B.S.) for coupling fundamental and applied corrosion research, the 'Advanced Research Projects Agency (A.R.P.A.)' entrusted to CEBELCOR an important mission of research and education towards some universities and industrial firms of the U.S.A. Thanks to support afforded by ARPA

984

M. POURBAIX

(B. Floyd Brown) and to marks of interest expressed by the 'Carnegie Institute of Technology', Pittsburgh (Harry Paxton) and by the 'University of Florida', Gainesville (Frederick N. Rhines, Albert G. Guy, Ellis D. Verink . . . . ), a very intense and successful activity was developed, which led to the creation of a 'Center for Applied Thermodynamics and Corrosion '5~ whose task was to promote Belgian-American collaboration in the specialization fields of C E B E L C O R and the 'Corrosion Service' of U.L.B. in Brussels (Applied Thermodynamics and Electrochemistry) and the University of Florida in Gainesville (physical metallurgy). This activity included courses, conferences, 'corrosion weeks', 52 research relating to the behaviour of alloys under marine exposure, 53 as well as student theses relating to the setting up of 'experimental potential-pH diagrams' for alloys: copper-nickel (Ph. Parrish, 54 K. D. Efird, 55 T. S. Lee 56 and J. M. BowersS7); copper-zinc (W. C. FortSS); ironchromium (R. L. Cusmano 59 and K. K. Starr6). Two of the fairest 'fleurons' of this Belgian-American collaboration, which was pursued in specially close and agreeable liaison with the 'Naval Research laboratory (N.R.L.)' were the development of the concept of 'occluded corrosion cell (O.C.C.)' in localized corrosion (with Jean Van Muylder and Lucio Sathler 61'62) and the famous work of B. Floyd Brown on the electrochemistry of stress corrosion cracking. 63'64
Technical activity 65-68

In the technical area C E B E L C O R strived to conduct in a parallel direction fundamental and applied research with the study of technical problems confronting the industry. When observing natural phenomena with open eyes and a reference electrode at hand, the C E B E L C O R team and its many friends were able to develop their capability of extrapolation and of prediction, and to apply it to industrial practice.. We were sometimes considered as sorcerers, good or bad depending whether or not the remedies we recommended came into line with the immediate interests of the parties concerned. Early in 1962, shortly after the death of Louis Baes, the President of the Board of C E B E L C O R , who had for many years magnanimously protected our fragile institution, an opposition arose against our electrochemical doctrine, by mistake and on the occasion of one of our best researches. Then started a period of decline when C E B E L C O R lost three-quarters of its team. It had to rebuild its destroyed team after a period of instability and damaging opposition. After one year of strenuous efforts C E B E L C O R recovered its status as a recognized Corrosion Center, when, in June 1963, during the Brussels Congress of the European Federation of Corrosion on 'Methods of Testing and Control of Corrosion', the validity of our electrochemical methods was finally officially acknowledged. From then on, corrosion research work underwent a fundamental change and most of the corrosion problems became more easily solved, with the exception of some particularly severe cases of localized corrosion (i.e. stress corrosion cracking) which occur in numerous industries. 47 As Mars G. Fontana stated in his Campbell memorial lecture, 69 as in his 1963 lecture at the 2nd congress of the International Corrosion Council 7 which one should read again: 'There is an overwhelming need for education about the plague of corrosion. The very great majorities of premature failures occurring today are caused by phenomena already well known, and such

Thermodynamics and corrosion

985

failures may be avoided'. Regarding the problems which are not yet solved, I think that their solution lies within the range of the researches where electrochemists and other scientists would accept to link their efforts in 'applied thermodynamics and corrosion' according to a moral charter similar to the one which united in electrochemistry the founding members of CITCE. I wish such an action should be achieved. Let me quote Oscar Arias who said: 'Man could never have achieved what is possible had he not sometimes attempted what is impossible', and is the secret of happiness not revealed by the young fox to the 'Petit Prince' of Saint Exupery: 'One sees well only with the heart. The essential is invisible to the eyes'. Thanks and courage to Antoine, to Rende, to Suzanne, to Jacques, to Ivan, to Philippe. And my thanks also to Richard De Kriek who very kindly edited this text. Marcel Pourbaix
REFERENCES 1. U. R. EVANS, An Introduction to Metallic Corrosion, pp. VII, XX. Arnold, London (1948). 2. F. HABER, Ubcr Stufenweisc Reduction des Nitrobenzols mit begrenztem Kathoden-potentia[. Z. Elektrochemie 4, 506 (1898). 3. F. HABER, Z. Phys. Chemic 32, 193,270 (19(/I)). 4. W. NERNST, Z. Phys. Chemic4, 129 (1889). 5. J. A. CHR~STIANSENand M. POURBAIX,Convention concerning thc sign of electromotive forces and electrode potentials, C.R. 18e Conference Union lnternationale de Chirnie Pure et Appliqu(e, Stockholm (1953), 84-85 (1954). 6. TH. DE OONDER, L'Affinit( (r~Sdaction nouvellc par Pierre Van Ryssclberghc), pp. 23 and 97. Gauthier Villars, Paris (1936). 7. P. FORtERS, Allocution, S(ance d'Hommage (~ ll),a Prigogine, prix Nobel de Chimie, Bulletin ULB et UAE3, no. 4, p. 25 (mars 1978). 8. I. PRIC, OGINE, Etude thermodynamique des PhOnomg'nes irr(versibles, pp. 32-43. ThOse Bruxclles 1945-Desoer, Li~Sge(19471. 9. C. WAONERand W. TRAUD, Ueber die Deutung yon Korrosionvorg~ingcn durch Ueberlagerung yon Tcilstromspannungs Kurven. Z. Elektrochemie 44,391 (1938), 1(1. M. POURBAIX,ThOs6 Delft 1945, (a) Therrnodynamique des solutions Aqueuses Dilu(es, Repr?sentation graphique du ROle du pH et du Potentiel. Rdimpression CEBELCOR (avec PrcSface de F.E.C. Scheffer et Foreword de U. R, Evans), CEBELCOR (1963); (b) Thermodynamics of Dilute Aqueous Solutions with applications to Electrochemistry and Corrosion, Translated from the French by J. N. Agar. Edward Arnold, London (1949). 11. M. POURBAIX,Applications de la Thermodynamique fi l'Electrochimie. C.R. Colloque de Thermodynamique, Bruxelles (janvier 1948), pp. 125-136. Ed. Union lnternationale de Physique Pure ct Appliqudc, Paris (19481. 12. M. POURBA~X,Corrosionpassivit(etpassivation dufer, lnfluencedupHetdupotential, those Bruxcllcs 1945 (extrait). MOmoires Soc. Roy. Belge Ing~nieurs et lndustriels no. 1 (mars 1951). 13. M. POURBMX, ThOses ct Textes inddits. Rapports Techniques CEBELCOR 115, RT. 181 ~ 184 (1970). 14. M. POURBA~X,Le CITCE et le CEBELCOR. Le rnouvernent scientifique en Belgique VI, 476-48 I. Ed. FddOration Beige des Socidtds Scientifiques (1961). 15. M. POURBmX, Le Centre Beige d'Etude de la Corrosion CEBELCOR. Recucils dc Mdmoircs 'Corrosion et Protection des MattSriaux' (Tome 1, pp. 5-10). Soc. Roy. Belgc lngdnicurs lndustriels (no. 3) (1952). 16. M. POURBAlX,The birth of CITCE. Electrochimica Acta 16, 173-175 (1971). 17. Cornptes rendus des R~unions de CITCE; (1) 2~ rdunion (Milan, 1950) Ed. Tamburini, Milan ( 1951): (2) 36 rdunion (Berne, 1951) Ed. Manfredi, Milan (1952); (3) 66 rdunion (Royaumont et Poitiers, 1954) Ed. Butterworth, London (1955); (4) 7~ rOunion (Lindau, 1955) Ed. Butterworth, London

986

M. POURBAIX (1956); (5) 8~ r6union (Madrid, 1956) Ed. Butterworth, London (1957); (6) 9~ r6union (Paris, 1957) Ed. Butterworth, London (1958). M. POURBA1X,Leqons en corrosion Electrochimique, 2~ Edition. CEBELCOR (1975). M. POURBAIXet al. (a) Atlas d'Equilibres Electrochimiques ~ 25C, Ed. Gauthier-Villars et CEBELCOR (1963); (b) Atlas of Electrochemical Equilibria in Aqueous Solutions (translated from the French by James Franklin). Pergamon Press & CEBELCOR (1966). Reimpression by NACE & CEBELCOR. Diagrams of Chemical and Electrochemical Equilibria. Their Setting-up and Applications. Proc. NA TO Advanced Research Workshop, Brussels (2-5 September 1981), Ed. MARCELPOUBBAlXand ANTOINE POURBAIX.Rapports Techniques CEBELCOR 142,263 (1982). Equilibrium Diagrams-Localized Corrosion, Proc. Int. Symp. ElectrochemicalSociety, New Orleans, 7-12 October 1984), Ed. ROBERTD. F~ANKENTHALand J. KRUGEk; Electrochem. Soc. Proc. volume 84-9 (1984). M. POURBAIX,Thermodynamique et corrosion. M~taux et Corrosion 14, 189-193 (1938). M. POURBAIXand A. POURBAlX,Les 'Aciers patinables', (weathering steels) et la Corrosion dans la construction. Rapports Techniques CEBELCOR 107, RT, 147 (1968). M. POURBAIX,Electrochemical Corrosion of metallic Biomaterials, Proc. conference Biointeractions 84, London (4-6 January 1984); (a) Biomaterials 5, 122-134 (1984); (b) Rapports Techniques CEBELCOR 147, RT. 272 (1984). P. DELAHAV,M. POURBAIX,P. VAN RYSSELBE~GHE,Diagramme Potential-pH du Plomb. Comportement Electrochimique du Plomb-Accumulateur h plomb. Loc. cit. 17.1, pp. 15-28 (1951). M. POURBAIX, Some applications of potential-pH diagrams to the study of localized corrosion. J. Electrochem. Soc. 123, 23c-36c (1976). J. LEGRANO,Note sur la Protection des Condenseurs en Alliage cuivreux par addition de sels ferreux dans I'eau de mer en circulation. Rapports Techniques CEBELCOR 143, RT. 264.4 (1982). I. CROUZEa"and A. POURBAtX,A criterion for protection of copper-alloys against pitting corrosion in sea water and brackish water. Rapports Techniques CEBELCOR 155, RT. 293 (1988). J. STUBBEand J. BRIQUET, Assessment of Fe S04 dosing of a heat exchanger. Rapports Techniques CEBELCOR 155, RT. 294 (1988). Corrosion and Metal Artifacts--A Dialogue between Conservators and Archeologists and Corrosion Scientists. Gaithersburg, Maryland (17-18 March 1976). NBS Special Publication 479 (1977). M. POURBAIX,Electrochemical corrosion and reduction. Loc. cir. 30, pp. 1-16 (1977). R. M. GARRELS, Mineral equilibria at low Temperature and Pressure. Harper, New York (1960). R. M. GARRELS, Applications of equilibrium diagrams to geology. Loc. cir. 20, section 3.3, pp. 247258 (1982). W. T. DENHOLM, Applications and limitations of equilibrium diagrams in flotation. Loc. cit. 20, section 3.4, pp. 259-874 (1982). F. N. PONNAMPERUMA, Physicochemical Properties of Submerged Soils in relation to Fertility. International Rice Research Institute--IRRI Research Paper Series no. 5 (February 1977). F, N. PONNAMPERUMA,E. M. TIANCO and T. Lue, Redox equilibria in flooded soils: I. The iron hydroxide systems. Soil Science ! 03, 375-381 (1966). F. N. PONNAMPERUMA,T. A. LOY and E. M. T1ANCO, Redox equilibria in flooded soils: II. The manganese oxide systems. Soil Science 108, 48-57 (1969). M. KURACm, Utility of potential-pH equilbrium diagrams for the treatment of waste water at Kamioka mine and refinery. Rapports techniques CEBELCOR 132, RT. 241 (1977). J. VAN MUYLOER, High temperature potential-pH diagrams. Loc. cit. 20, section 1.1, pp. 11-58 (1982). C, M. CHEN, K. ARAL and G. J. THEUS, Computer calculated Potential-pH Diagrams to 300C, Volume 1: Executive Summary, Volume H: Handbook of Diagrams, Volume IH: Users Guide for Computer Program POT-pH-TEMP. Electric Power Research Institute EPRI. NP 3137 (1983). J. W. COBBLE,Measurement and estimation of the thermodynamic properties of aqueous systems at high temperature. Loc. cit. 20, section 2.1, pp. 119-136 (1982). E. L. SCHOCKand M. C. HEGELSON, Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures. Correlation algorithms for ionic species and equation of state predictions to 5 kb and 1000C. Geochim. Cosmochim. Acta 52, 2009-2036 (1988). M. D. INGRAM,Electrochemical equilibrium diagrams in the presence of molten salts. Loc. cit. 20, section 1.3, pp. 91-100 (1982).

18. 19.

20.

21.

22. 23. 24.

25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40.

41. 42.

43.

Thermodynamics and corresion

987

44. M. POURBAIX,XI-ZHEN YANG, HE-MING ZHANG and ZHONG-CHENG ZHANG, some oxidation equilibria: towards the setting-up of atlases of chemical and electrochemical equilibria in the presence of a gaseous phase. Corros. Sci. 26, 873-917 (1986). 45. M. POURBAIX, Thermochemical diagrams: some applications to the study of high temperature corrosion. Mater. Sci. Engng 87,303-317 (1987). 46. M. POURBAIXand H. ZHANG, Equilibrium diagrams of systems O-S, O-Al, O-Cr, O-Fe, O-S-AI, O S-Cr and O-S-Fe. Towards a thermodynamic predetermination of the circumstances of dry corrosion of metals. Werkst. Korros. 39, 504-511 (1988). 47. M. POURBA1X,(a) Analyse des probl~mes pos6 par la corrosion localisde. Etude dc leur impact industriel et propositions d'action. Rapports Techniques CEBELCOR 152, RT. 287 (1986); (b) Analysis of current problems caused by localized corrosion. Study of their industrial impact and proposals for action. Rapports Techniques CEBELCOR 152a. RT. 287a (1986); (c) Analyse der durch die 6rtliche Korrosion verursachtcn Probleme. Untersuchung ihrer wirtschaftlichen Aus wirkungen und L6sungsvorschl~igc. Rapports Techniques CEBELCOR 152b, RT. 287b (1986). 48. M. POURBAIXand A. POURBAIX,Recent progress in atmospheric corrosion testing, Corrosion 45, 7183 (1989). 49. M. POURBA[X, Sur l'Interpr6tation thcrmodynamiquc de courbes dc polarisation. Rapports Techniques CEBELCOR 1, RT. 1 (1952). 50. M. POURBMX,The utility of thermodynamic interpretation of polarization curves. J. electrochem. Soc. 101,217-221c (1954). 51. F. N. RmNES and M. POURBAIX,Cr,Sation du "Centre de Thermodynamiquc App[iqu6c ct Corrosion'. Creation of thc 'Center for Applied Thcrodynamics and Corrosion'. Rapports Techniques CEBEL('OR 117, RT. 192 (1971). 52. Proc. of the 2nd Corrosion Week of the "Center ]or Applied Thermodynamics and Corrosion', Gainesvillc, Florida (24-28 March 1974). Rapport Techniques CEBELCOR 126, RT. 229 (1975). 53. E. D. VERINK and M. POURBA)X, Use o1 potentiokinetic methods at successively increasing and decreasing electrode potentials in developing alloys for saline exposure. Rapports Techniques CEBELCOR 117, RT. I91 (1971). 54. PH. A. PARR[SH, Use of experimentally determined Pourbaix Diagrams to elucidate the role of iron in the passive behavior of copper-rich alloys containing nickel. Gainesville, MSc Thesis (June 1970). 55. K. D. ENRD, Crevice Corrosion of a copper-nickel alloy and its relationship to the experimental Pourbaix diagram. Gainesville, MSc Thesis (December 1971)). 56. T. S. LEE, The use of experimentally determined potential-pH diagrams to elucidate the influence of solute additions on the passive behavior of binary copper-nickel alloys with and without chloride. Gainesville, MSc Thesis (August 1972). 57. J. M. BOWERS, Crevice Corrosion of a 70-30 chromium modified cupronickel and its relationship to the experimental Pourbaix diagram. Gaincsville, MSc Thcsis (June 1973). 58. W. C. FORT, Study of the dczincification of 70-311 brass using Pourbaix diagrams. Gaincsvillc, High honors Project (12 March 1971). 59. R. L. CUSAMANO,The cstablishment of a three-dimensional (potential-pH-composition) diagram for binary Fc-Cr alloys in O.I. molar chloride solutions. Gaincsville, MSc Thesis (March 1971). 60. K. K. STARR, The significance of the 'protection potential' for Fe-Cr alloys at room temperature. Gainesville, Ph.D. Disssertation (March 1973). 61. k. SATHLERand J. VAN MUVLDER,Sur la nature chimique ct 61ectrochimique des solutions ~ l'intdricur des cellules dc Corrosion occluscs. Rapports Techniques CEBELCOR 126, RT. 224 (1975). 62. L. SArHLER, Contribution h l'Etudc du Comportement 61ectrochimiquc du fer en pr6sence de solutions de chlorurc ferrcux, en liaison avec la corrosion Iocalis6e, Th6se Bruxelles (1978). 63. Belgian-American Symposium, Brussels (3-4 September 1969). Abstracts of the Papers, Rapports Techniques CEBELCOR 112, RT. 168 (1970). 64. B. F. BROWN, The role of the occluded corrosion cell in strcss-corrosion cracking of high strength steels. Rapports" Techniques CEBELCOR 112, RT. 17(1(1970). 65. 10t?Anniversaire de la Fondation du CEBELCOR et 12~'rdunion du CITCE, Bruxelles (24-30 Avril 1961). Rapports Techniques CEBELCOR 82, RT. 97 (1962). 66. M. POURBAJX,Application de l'Electrochimie ~ la Science de la Corrosion et en pratique. Application of electrochemistry in Corrosion science and in practice. Rapports Techniques CEBELCOR 120, RT. 205 (1972). 67. 25( Anniversaire de la Fondation du CEBELCOR, S~anee acad~mique et s(minaire 'Applications

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techniques de la science ~lectrochimique ~ la protection contre la corrosion', Bruxelles (12-14 Avril 1976), Rapports Techniques CEBELCOR 129, RT. 234 (1976). 68. A. JAUMOTrE,Apropos de l'oeuvre de Marcel Pourbaix, Rapports Techniques CEBELCOR 148, pp. 193-203 (1984). 69. M. G. FONTANA,Perspective on corrosion of materials (1970 Campbell Memorial Lecture). Metall. Trans. 1, 3251-3266 (1970). 70. M. G. FONTANA,Corrosion engineering and corrosion science. Corrosion 19, 199t-204t (1963).