Potential-pH Diagram of Lead and its Applications to the

Study of Lead Corrosion and to the Lead Storage Battery '

PAUL DELAHAY
Louisiana State University, Baton Rouge, Louisiana

MARCEL POURBAIX
University of Brussels, Brussels, Belgium

AND
PIERRE VAN RYSSELBERGHE

University of Oregon, Eugene, Oregon

ABSTRACT
.The reactions and equilibrium equations of the system lead-water are given in detail
and are used in the construction of the potential-pH diagram of lead. Some important
features of the diagram are discussed, in particular the solubilities of oxides and hydrox-
ides and some of the important oxidation reduction reactions. A modified form of the
potential-pH diagram of lead showing corrosion, passivity, and passivation domains
is presented. The addition of passivation domains due to the presence of carbon dioxide
and carbonates are determined. A modified potential-pH diagram taking into account
the presence of sulfate in solution is also presented. Important features of the behavior
of lead storage batteries are studied on the basis of this modified diagram.

The construction of potential-pH diagrams for the is calculated by the following formula
various elements has been previously discussed (1, 2, ~-. -- A o __
E xAF~x y FR~ zAF~:o 0.0591 m p H
3) and diagrams for iron, copper, chromium, and ni-
23,070n n
trogen have been presented. A particularly inter- (ii)
esting and important case is t h a t of lead which is + 0.0591 log a~)x
discussed in the present paper. Applications of po- n Red

tential-pH diagrams in the study of the corrosion of
lead and in the analysis of the behavior of lead
storage batteries are also presented.
C O N S T R U C T I O N OF T H E P O T E N T I A L - p H
DIAGRAM
in which z~F~ are the standard free energies of for-
m ation of the reactants in calories and a the activities
of the reactants. Formula I I is valid for a tempera-
ture of 25~
The equilibrium constant K for the reaction
pA +mH + = qB+zH20 (III)

ITS USE IN THE INTERPRETATION OF is calculated by the following formula

E L E C T R O C H E M I C A L P R O P E R T I E S OF
log K pAF~ - qAF ~ -- zAF~2o (IV)
LEAD AND LEAD COMPOUNDS 2.3RT
THERMODYNAMIC FORMULAS in which 2.3 R T = 1363 calories at 25~ When A is
a hydroxide and B the corresponding cation the ac-
Since the theory of potential-pH diagram has been
tivity of ion B is calculated b y formula
discussed elsewhere (1, 2, 3) we shall only present a
short discussion of the thermodynamic formula ap- 1 p/~F] - q/~F ~
. - zZ~F~o z pH (V)
log aB . . . .
plied in the construction of a potential-pH diagram. q 1363 p
The potential E corresponding to the equilibrium
STANDARD FREE ENERGIES OF FORMATION
x Ox + m H + + he- = y Red + z H20 (I) All standard free energies have been obtained from
Latimer's book (4) except for the following cases.
1 Manuscript received March 6, 1950. This paper pre-
pared for delivery before the Buffalo Meeting, October ll The free energy of the PbO,~- - ion has been calcu-
to 13, 1950. lated on the basis of the value E ~ = 0.300 volt given
57

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 58 JOURNAL OF THE ELECTROCHEMICAL SOCIETY February 1951

b y G l a s s t o n e (5) for t h e s t a n d a r d p o t e n t i a l of t h e (7) PbOT ~- 2 H + + 2e- = P b + 2H20

reaction E = 0.248 - 0.0591 p H
P b O 3 - - + 2H~O -t- 2 e - = H P b O c + 3 O H - (8) Pb3t)4 + 2H;O + 2 H ~ + 2e- = 3 P b ( O H ) 2
which leads to - 6 6 , 3 3 9 cal for this free e n e r g y of E = 1.101 - 0.0591 p H
formation. (9) Pb304 + 2 H + § 2e- = 3 P b O r + H20
T h e free energies of P b O , Pb3()4, a n d PbO2 h a v e E = 1.076 - 0.0591 p H
been r e c a l c u l a t e d f r o m t h e d a t a of A n d r e w s a n d (10) PbO.., + 2 t I + + 2e- = P b ( O H ) 2
B r o w n (6) a n d of S p e n c e r a n d M o t e (7) b y c h a n g i n g E = 1.113 - 0.0591 p H
f r o m - 5 6 , 5 6 0 to - 5 6 , 6 9 0 cal t h e free e n e r g y of (11) PbO2 + 2 H + + 2e = P b O r + It.20
w a t e r . T h e following values were used in our calcula- E = 1.107 - 0.0591 p H
t i o n s : A F ~ = -- 45,230 cal for P b O , AF ~ = -- 142,730 (12) 3 P b O 2 + 4 H + + 4c = P b ~ O 4 + 2H20
cal for Pb304, a n d AF ~ = --50,860 cal for PbO2. E = 1.122 - 0.0591 p H
T h e free e n e r g y - 1 9 2 , 5 3 2 cal of PbSO4 has been
c a l c u l a t e d on t h e basis of L a t i m e r ' s vMuc (4), C. Helerogcneous Reactions Involving One Solid
- 0 . 3 5 6 3 v o l t for t h e s t a n d a r d p o t e n t i a l of t h e re- Without oxidation
action (13) P b ( O H ) 2 + 2 t t + = P b ++ + 2H20
PbSO4 + 2 e - = Pb + SO~-- log at,b++ = 12.46 -- 2.00 p H
EQUILIBRIUM EQUATIONS
(14) HPbO2- + H + = Pb(OH)2
log am,,,o2- = - 1 5 . 6 8 + 1.00 p H
E q u i l i b r i u m e q u a t i o n s h a v e been c a l c u l a t e d b y (15) P b O r + 2 H + = P b + H20
a p p l i c a t i o n of f o r m u l a s I to V as follows log apb*+ = 12.67 - 2.00 p H
For Water (16) H P b O 2 - + H + = P b O r + H20
log a , pbo2- = --15.49 + 1.00 p H
(a) 2 H + + 2e- = H~ (17) PbO2 + 4 H + = l)b +4 + 2H20
E = - 0 . 0 5 9 1 p i t - 0.0295 log Pn2 log at,~,+~ = - 7 . 1 0 - 4.00 p H
(b) O ~ + 4 H + - b 4e = 2H~O (18) P b O ~ - - + 2 H + = PbO2 + H20
E = 1.229 - 0.0591 p H -t- 0.0148 log Po~ log a~,bo~-- = --30.24 + 2.00 p H
For Lead and Its Compot~nds tVith oxidation
A. Homogeneous Reactions (19) P b ++ + 2c- = P b
Without oxidation E = - 0 . 1 2 6 + 0.0295 log apb ++
(20) H P b O 2 - + 3 H + + 2e- = P b + 2H20
(1) HPbO~- + 3 H + = P b ++ + 2H~O
E = 0.706 - 0.0886 p H + 0.0295 log a,~Pbo2--
(21) I)bO3 - - + 4 H + + 2e- = P b ( ( ) H ) 2 + H20
log a n ~ o 7 _ - 2 8 . 1 7 + 3.00 p H
a Pl~+ + E = 2.007 - 0.1182 p H + 0.0295 log apbO3----
(22) PbO3--+4H ++2e- = PbO,+2H~O
(2) P b O T - "4- 6 H + = P b +~ + 3H20
E = 2.001 - 0.1182 p H + 0.0295 log aFbo~- -
(23) Pb~O4+8H ++2c- = 3Pb +++4H20
log arbo7 _ 23.13 -4- 6.00 p H
a Pb+ 4 E = 2.200 - 0.2364 p H - 0.0886 log arb ++
With oxidation (24) 1)})304+ 2H20 + 2e- = 3 H P b 0 2 - + H +
E = - 0 . 2 9 7 + 0.0295 p H - 0.0886 log aHp~o~-
(3) P b +4 + 2 e - = Pb ++ (25) 3PbO3--+ 10H ++4e- = P b 3 0 4 + 5H20
E = 1.691 + 0.0295 log ae,,~+ E = 2.463 - 0.1477 p H + 0.0443 log apbo~- -
a~b+ + (26) PbO2+4H ++2e- = Pb +++2H~O
(4) P b O 3 - - + 6 H + + 2 e - = P b ++ + 3H20 E = 1.482 - 0.1182 p H - 0.0295 log aph ++
(27) PbO2 + H § + 2e- = H P b O 2 -
E = 2.375 - 0.1773 p H + 0.0295 log a r b o 3 - - E = 0.649 - 0.0295 p H - 0.0295 log aH,bO,--
(~ Pb+ +

(5) P b O ~ - + 3 H + + 2 e - = H P b O ~ + H~O DESCRIPTION OF THE POTENTIAL-pH

DIAGRAM OF LEAD
E = 1.543 - 0.0886 p H + 0.0295 log apbo~- -
aH PbO~ Fig. 1 has been e s t a b l i s h e d on t h e basis of f o r m u l a s
(a) a n d (b), a n d (1) to (27) given a b o v e . I t gives a
B. Heterogeneous Reactions Involving Two Solids
f a i r l y c o m p l e t e p i c t u r e of t h e v a r i o u s t h e r m o d y -
With oxidation
n a m i c e q u i l i b r i a of t h e s y s t e m P b - H 2 0 a t 25~ F o r
(6) P b ( O H ) ~ + 2 H + + 2e- = P b + 2H20 t h e s a k e of s i m p l i c i t y t h e d o m a i n of s t a b i l i t y of
E -- 0.242 -- 0.0591 p H P b ( O H ) 2 , which is slightly l a r g e r t h a n t h a t of red

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 Vol. 98, No. 2
PbO has not been represented. The domain of Pb_~Oa
whose equilibrium properties are insufficiently known
is not represented. When one ion is involved in a
reaction, the equilibrium condition'is represented for
values of the activity of this ion equal to 1, 10-'-',
10-4, and 10-6. When two ions are involved in a
reaction, the equilibrium condition is represented for
a ratio of their activities equal to 1.
The domains of predominance of lead and its vari-
ous derivatives, i.e., ions, oxides, and hydroxides,
can be interpreted as follows. Line 19 for example
represents the equilibrium between Pb ++ ion and
metallic lead. A point located below line 19 ( - 6 ) cot-
0.6
- -- | 1 I l
-I 0 I 2 5 4 5 6 7 8 9
F1G. 1. Potential-pH diagram of lead. The area between
lines a ~nd b corresponds to thermodynamic stability of
water. Thin lines represent equilibrium conditions between
a solid phase and an ion at activities 1, 10-~, 10-4, 10-s.
Heavy lines represent equilibrium conditions between two
solid phases. Dotted lines represent equilibrium conditions
between two ions for a ratio of activities of these ions equal
to unity. In this and subsequent figures circled figures and
letters refer to the corresponding equations in the text.
responds to a Pb ++ activity smaller than 10-s while a
point located above 19 (0) corresponds to a Pb ++
activity larger than 1. Therefore, the domain below
line 19 ( - 6 ) essentially corresponds to the stability
of metallic lead since the equilibrium activity of
Pb ++ ion is smaller than 10-6. Similarly the domain
above line 19 (0) corresponds to the stability of Pb +*
ion.
The following domains of predominance are shown
in Fig. 1.
Pb: below lines 19, 7, 20.
PbO (also approximately Pb(OH)s) : limited by lines
7, 9, 15.
PbO~: limited by lines 12, 17, 18, 26. 27.
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POTENTIAL-pH DIAGRAM OF LEAD 59
Pb3Ot: limited by lines 9, 23, 24, 12.
Pb++: limited by lines 3, 15, 19, 23, 26.
Pb+4: limited by lines 3, 17.
HPbOo.-: limited by lines 5, 16, 20, 24, 27.
PbO3- -: limited by lines 5, I8.
Fig. 1 shows, among other things, that metallic
lead, usually stable in presence of aqueous solutions
free of oxidants, can be dissolved in oxidizing acid
solutions with the resulting formation of divalent
plumbous ions Pb ++. A very strong oxidizing action
may transform these Pb ++ ions directly into the
brown tetravalent lead peroxide PbO~_which is insolu-
ble in neutral or moderately acid solutions, slightly
soluble in strongly acid solutions with the resulting
formation of plumbic ions Pb +4, and very soluble in
strongly alkaline solutions with the resulting forma-
tion of plumbate ions Pb03--.
~ ',~)?
! t
I 0.6
J
A
§
0
~ [ HPI~2- J
-4
,o --b
-6
6 8 IO 12 14
I0 II 12 13 14 15
fH
Fx(;. 2. Solubility of lead oxide and lead hydroxide as a
function of pH.
Lead hydroxide Pb(OH)2 and the oxide PbO ex-
hibit a minimum of solubility at pH = 9.4 at which
the concentration is 10 5.s gram ion per liter or 0.33
mg of lead per liter in the ease of red PbO, and
10 6.0 gram ion per liter or 0.21 mg of lead per liter
in the ease of Pb(OH)2. This is shown in Fig. 2 which
has been constructed by plotting the logarithm of the
total lead activity (aeu+§ -F anFbo~-) against pH.
Both PbO and Pb(OH)2 dissolve in acid solutions
with formation of Pb +§ ion and in alkaline solutions
with formation of biplumbite ion HPbO~- and, to a
lesser extent, plumbite Pb02--. The latter ion has
not been represented on the diagram because of the
lack of precise thermodynamic data.
The oxidation of PbO, of Pb(OH)~, and of alkaline
solutions of Pb ++ can lead to Pb304, to PbO2, and to
solutions of tetravalent lead under the form of plum-
bate PbO3- -. In very alkaline media Pb~Oa can also
be formed. This oxide has not been represented on
the diagram.
 60 JOURNAL OF THE ELECTROCHEMICAL SOCIETY
The dissolution of Pb203 in alkaline solutions ac-
cording to the reaction
Pb203 + 3OH- = HPbO2- + Pb03-- + H20
which has been studied by Glasstone (4) leads to
solutions containing equal amounts of the ions
HPbO2- and PbO3-- whose equilibrium character-
istics are represented by line 5. The oxide PbO2 and
plumbate solutions are stable in presence of alkaline
solutions free of reducing agents because of the fact
that, at pH values higher than 7, lines 26 and 27 are
below line b which corresponds to the oxidation of
water to oxygen. In presence of acid solutions PbO~
is thermodynamically unstable under atmospheric
pressure since, for such solutions, the 20 lines-are
under line b; PbO,. then tends to reduce into plum-
bous ions Pb ++, water being decomposed with libera-
-I 0 I 2 3 4 5 6 7 8 9
t. IVATION
a. 0.2
0 0
- 02.
-ii
it PASSIVITY
-I 0 I 2 3 4 5 6 7 8 9
Fro. 3. Corrosion, passivity, and p a s s i v a t i o n of lead as
deduced from Fig. 1.
tion of oxygen. The latter reaction, however, in-
volves a large overvoltage and this circumstance
favors the stability of plumbic salts.
Fig. 1 also shows that lead can generally be used as
an electrolytic anode at pH values between 0 and 12,
in which case it covers itself with PbO~.
Metallic lead is thermodynamically stable in pres-
ence of neutral or alkaline solutions free of oxidants
since, in such solutions, a portion of the domain of
stability of lead is above line a. In acid solutions
under atmospheric pressure lead generally tends to
decompose water with evolution of hydrogen, in
which case its potential exhibits a value between
those of line a and those of the line of the 19 group
which corresponds to the lead concentration of the
solution. This decomposition of water by lead is,
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February 1951
however, usually very slow on account of the high
overvoltage of hydrogen on lead (8).
APPLICATION OF THE DIAGRAM TO THE
STUDY OF THE CORROSION OF LEAD
In the present section of this paper, as well as in
the next one, equilibrium diagrams are used in the
study of phenomena which in practice may be sub-
ject to irreversible conditions. Nevertheless consid-
erations based upon equilibrium theory are useful,
indeed fundamental, since they give us the limits
wtthin which these corrosion phenomena can take
place.
CORROSION OF LEAD IN THE ABSENCE OF DISSOLVED
CARBON DIOXIDE
10 II 12 15 1415 On Fig. 3 we have drawn the lines for which the
total solubility of lead and its oxides under the form
Pb ++ + HPbO2- + PbO~ - has the value 10-6 gram
,.6 atom of lead per liter (0.207 milligram Pb/liter).
The lines are considered as separating the domain of
corrosion from the domain of passivity which cor-
08 responds to the metallic lead area and from the do-
main of passivation corresponding to the lead dioxide
area (See Fig. 1 and 2).
0.2 We use the terms passivity or passivation accord-
ing to whether the protected surface is essentially
,02 metallic and cannot corrode or consists of a protec-
tive coating of oxide or other adherent compound.
In the present case the distinction between passivity
and passivation is a particularly clear one and there is
-__,0.8 - I no doubt that the use of both terms is advantageous.
-12 This corrosion diagram of lead indicates that, in
I0 II 12 13 14 15
the absence of passivating substances (e.g., carbon-
ates), any oxidizing action can cause the corrosion of
lead except at the high potentials which correspond
to the stability of lead dioxide Pb02. As stated by
Schikorr (9) lead oxide (PbO) is too soluble to give
any protection to lead.
In the absence of complexing ions (e.g., tartrates)
lead can be cathodically protected if its potential is
lowered below about - 0 . 3 volt in acid or neutral
solutions or below - 0 . 3 to - 0 . 8 volt according to
pH in alkaline solutions.
CORROSION OF LEAD IN PRESENCE OF CARBONIC
ACID AND ITS IONS
In presence of aqueous solutions containing car-
bonates and bicarbonates lead may form lead car-
bonate PbC03 whose conditions of stability with re-
spect to metallic lead, its oxides, and its ions are
given by foiznulas (30) to (46) below. For the sake
of simplicity conditions of stability of basic carbon-
ates are not included.
 Vol. 98, No. 2 P O T E N T I A L - p H D I A G R A M OF L E A D 61

Reactions and Equilibrium Conditions Corrosion Diagram of Lead in Presence of Carbon

A. Homogeneous Reactions without Oxidation Dioxide
The influence of p H on the solubility of lead car-
(28) H C O ~ + H + = H~CO~
bonate is shown in Fig. 4 for activities or concentra-
log anco~- - tions of total CO~ (i.e., H~CO3 + HCO~- 4- C 0 3 - - )
6.37 + p H
aH2coa varying from l0 -s to 1 mole per liter, and in Fig. 5
for partial pressures of COs varying from 10-e to 1
(29) CO~- + H + = HCO~
atmosphere. The intersections of the horizontal line
log a c o a - - _ _10.34 + p H of ordinate 10-6 of Fig. 4 with the solubility curves of
aHcoa- lead carbonate give the p H values corresponding to
the boundaries between corrosion and its essential
B. Heterogeneous Reactions Involving Two Solids and absence for various amounts of total COs. The addi-
with Oxidation tional domains of passivation resulting from the pres-
(30) PbCO3 + H20 = Pb(OH)2 + COs(g)
log Pco~ = - 7 . 1 5 0
(31) PbCO3 = P b O + CO2 (g)
log Pco~ = - 7.36
(32) PbCOa+2H ++2e- = Pb+COs(g)+H20
E = 0.031 - 0.0591 p H - 0.0295 log Pco~
(33) P b C O ~ + 2H + + 2e- = P b + H2C03
E = 0.012 - 0.0591 p H - 0.0295 log aH2co~
(34) PbCO3+H ++2e-=Pb+HCO3-
E = - 0 . 2 0 0 - 0.0295 p H - 0.0295 log anco,-
(35) PbCO3 4- 2e- -- P b + C O 3 - -
E = - 0 . 5 0 6 - 0.0295 log a c o 3 - -
(36) Pb02 + COs (g) + 4H + + 2e-
= PbCO3 4- 2H..O
E = 1.324 - 0.0591 p H + 0.0295 log Pco~
(37) Pb02 + H2C03 + 2H + + 2e-
= PbCO~ + 2H20
E = 1.367 - 0.0591 p H + 0.0295 log aH2co~
(38) PbO~ + H C O , - + 3H + + 2e-
= PbCO~ + 2H:O
E = 1.555 - 0.0886 p H + 0.0295 log a.co~-
(39) PbO2 + C 0 3 - - 4- 4H + + 2e- 7 9 II 15
= PbCO3 + 2H~0 pH
E = 1.861 - 0.1182 p H + 0.0295 log a c o ~ - -
FIG. 4. Solubility of lead c a r b o n a t e as a f u n c t i o n of p H
for a pressure of carbon dioxide v a r y i n g from 1 to 10-"
C. Heterogeneous Reactions Involving One Solid and atmosphere. T h e n u m b e r i n d i c a t e d on each curve cor-
without Oxidation responds to the value of log Pc02.

(40) P b ++ + COs (g) 4- H20 = PbCO3 + 2H +

log apb++ = 5.31 - 2.00 p H - log Pco~
(41) H P b 0 2 - 4- C02 (g) + H + = PbC03 + H20
log aHPbO~-- = --22.85 + p H -- log Pco2
(42) P b ++ + H2CO3 = PbCO3 + 2H +
log aeb++ = 3.87 -- 2.00 p H - log aH~CO~
(43) P b ++ + HCOa- = PbC03 + H +
log apb++ = - 2 . 5 0 - p H - log a~co~-
(44) P b ++ + C O 3 - - = PbCO3
log avb++ = - 1 2 . 8 5 - log a c o ~ - -
(45) HPbO~- + HCO3- + 2H + = PbCO3 + 2H20
log aHPbO~-- = --30.67 + 2.00 p H "-- log aHCO3
(46) H P b O : + C O 3 - - + 3 H + = PbCO3 + 2H20
log aHFbO~-- ---- --41.01 + 3.00 p H -- log a c o ~ - -
ence of CO2 are represented in Fig. 6 which is easily
drawn on the basis of Fig. 1 and of the information
obtained from Fig. 4. A similar diagram could be
established from Fig. 1 and 5, the additional domains
of passivation corresponding then to various pres-
sures of CO2.
The data shown in Fig. 6 indicate t h a t minute
traces of COs in air suffice to cause the formation of
lead carbonate in slightly alkaline solutions. This
lead carbonate forms a protective layer on the metal
which, in the absence of activating ions such as
chloride, passivates the lead and protects it against
corrosion.
I t is well known (10) that, while distilled water

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 62 J O U R N A L OY T H E E L E C T R O C H E M I C A L S O C I E T Y February 1951

1 explanation of the fact that addition of COs to rain

water is not usually sufficient to render this water
nonaggressive toward lead because the resulting p H
is often too low (5.5 or less). On the contrary, good
protection of lead can be accomplished if CO2 is
added to water at a pH close to 8 or 9, i.e., when C02
is added as bicarbonate.
Fig. 6 also shows that, on the basis of the views
o -4 presented here, a certain passivating action could be
expected to occur even at very low carbonate and
bicarbonate contents of the water, e.g., l0 -~ gram
ion or 1 part per million of CaCO~, at p H values of
-6 \ 9 to 10. At higher carbonate contents these pH limits
are widened in both directions and chiefly toward
neutrality.
-8 xj i Solutions having a pH of 7 are probably passivat-
ing when the amount of dissolved COs is higher than
l0 -~.~ mole per liter, i.e., 40 parts per million of
CaCO3. The equilibrium pressure of CO2 is then
10-s.7 atmosphere corresponding to 0.2 per cent of
COs in air. I t is unlikely that carbonates could cause
7 9 II 15
pH passivation of lead when the pH is higher than 12
because of the impossibility of obtaining sufficiently
Fza. 5. Solubility of lead carbonate as a function of pH concentrated solutions.
for a total activity a~2co3 + a~coa- + a c o 3 - - v a r y i n g
from 1 to 10-t The number indicated on each curve corre- A P P L I C A T I O N OF T H E D I A G R A M TO T H E
sponds to the value of log (aHzco3 + a~co~- 4- aco~--), S T U D Y OF T H E L E A D S T O R A G E
BATTERY
-I 0 I 2 3 4 5 6 "r 8 9 I0 II 12 13 14 15
When the sulfate ion is present additional equi-
librium conditions have to be take~ into account.
These are equations (47) to (57) as follows.
II~ ~ ~ PASSIVATION I/// ,.4
A. Homogeneous Reaction without Oxidation
(47) S O ~ - 4- H + = HSO~

log anso4-__ _ _ 1.92 + pH

aso4
" o.4{//////..4J. " 2 _ ! _ _ . IH .o.4
B. Heterogeneous Reactions involving Two Solids and
with Oxidation
(48) P b S O 4 + H + + 2e- = P b 4 - HSO4
-oo t E = - 0 . 3 0 0 - 0.0295 p H - 0.0295 log auso~-
~176
(49) PbSO4 + 2e- = Pb 4- SO~--
E = - 0 . 3 5 6 -- 0.0295 log aso4--
-ii:I .... PASSIIVITY. . . . ; i-i~?: (50) Pb304 + 3SO4-- 4- 8H + 4- 2e-
-i 0 I 2 3 4 5 6 7 8 9 iO II 12 1:3 14 15 = 3PbSO4 -t- 4H20
pH E = 2.912 - 0.2364 pH 4- 0.0886 log aso4--
(51) PbO2 4- H S O ( + 3H + 4- 2e-
FXG. 6. Corrosion, passivity, and passivation of lead in = PbSO4 + 2HsO
presence of carbon dioxide, bicarbonate, and carbonate ions. E = 1.655 - 0.0886 pH + 0.0295 log aHSO4--
Heavy lines correspond ~o log (a~co3 -t- aHco3- 4- aco~-- )
(52) PbO2 4- SO~-- 4- 4H + 4- 2e- = PbSO4 4- 2H~O
---- 0. The passivation domain limited by thin lines corre-
sponds to log (aH2co3 4- aHCO3- + aco~--) equal toO, --1, E = 1.712 - 0.1182 pH 4- 0.0295 log a s o , - -
--2,--3, --4, and --5. C. Heterogeneous Reactions Involving One Solid

and rain water corrode lead, this metal is not cor- Without oxidation
roded by waters containing bicarbonates but. suffi- (53) Pb + + + HS04- = P b S O 4 + H +
ciently free of aggressive CO~. Fig. 6 gives a direct log apb++ = - 5 . 8 7 - pH - log aHso~

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 Vol. 98, No. 2 P O T E N T I A L - p H D I A G R A M OF L E A D 63

(54) P b ++ + SO4-- = PbSO4 the formation of biplumbite ion HPO2-. At pH =

--7.79 -- log a s o , - -
l o g aeb ++ = 9.4 the amounts of H P 0 2 - and Pb ++ are equal to
(55) t t P b O ~ - + S 0 4 - - + 3H + = PbSO4 + 2H20 each other and at pH - 10.0 the total amount of
log aHPbo( = --35.96 + 3pH -- log a s o , - - lead in solution is l0 -~ gram atom per liter or 0.21
With oxidation milligram per liter.
At pH = 10.2 PbSO4 ceases to constitute the ther-
(56) Pb + 4 + H S O ( + 2e- = P b S O ~ + H +
modynamically stable solid phase in presence of a
E = 1.865 + 0.0295 pH + 0.0295 log apb+4.aHso~-
molar activity of SO4-- and it tends to transform
(57) PbO3 - + S O 4 - + 6H + + 2e-
itself into PbO or Pb(OH)2 or into some basic salts
= PbSO4 + 3H._,O
which we have not included in our study.
E = 2.344 - 0.1773 pH + 0.0295 log apbo~--'aso~--
The Pb-PbS04 electrode in solutions of total sul-
Fig. 7 has been constructed on the basis of formu-
fate activity equal to 1, whose equilibrium charac-
las (1) to (27) and (47) to (57). It gives a picture of
teristics are represented by lines 48-49, is thermo-
the various thermodynamic equilibria of lead and its
derivatives in presence of aqueous solutions contain-
TABLE I. Lead storage battery with I molar sulfate
ing a total sulfate activity anso~- + aso~- - equal to
1 ion gram per liter. Comparing this figure with Potentials volts Pb concentration
mg/l
pH emf volts
-I 0 I 9' 3 4 ,5 6 "7 8 9 I0 I I 12 13 14 15 _ _ + pde -- pr + pole -- pole

-1 1.74 ? / - - 0 . 2 7 ? 2.01 ? 165 ? 2.6 ?

1
1.65 / --0.30 O. 26 O. 26
........ -,... Pb0 I ,
0
1 1.56 [ -0.33
1.95
1.89 0.026 0.026

~0.8
9
l
"'-.
"'..
",.,
-6
/llf-4 -2 1.2
PbOi }-.
0.8
2
3
4
5
1.47
1.35
1.24
1.12
/ -0.36
-0.36
-0.36
-0.36
1.83
1.71
1.60
1.48
0.0065
0.0033
0.0033
0.0033
0.0065
0.0033
0.0033
0.0033
6 1.00 -0.36 1.36 0. 0033 0. 0033
7 0.88 -0.36 1.24 0.0033 0.0033

T A B L E II. Lead storage batteries with vartous

concentrations of sulfuric acid
Pb
Potentials emf volts concentration
H~S04 volts mg/l
concentra- pH
-o8t Pb i ------"i -~ tion
moles/l
+ pole -- pole calc. expt. po~ole ! pole
_ _ r
-1 0 I 2 3 4 5 6 7 8 9 I0 II 12 13 14 15 --0.301 1.84 0.2 0.2
0.1 1.03 1. 535
0.5 0.48 1.603 - O. 30,~ 1.91 0.2 0.2
1 0.2{] 1.656 - 0 . 3 0 c 1.96 1.919 0.2 0.2
F r o . 7. P o t e n t i a l - p H d i a g r a m of l e a d in p r e s e n c e of s u l - 0.2
2 -0.06 1.669 - O. 307 1.98 1.971 0.2
f a t e ion. S a m e n o t a t i o n s as F i g . 1. N o t e t h a t line 52 is er- 0.2
3 -0.3C 1.696 - 0 . 3 0 ~ 2.00 2.014 0.5
r o n e o u s l y i n d i c a t e d as line 57. 2.053 1.3 0.2
4 -0.4~ 1.714 - O. 304 2.02

5 -0.6( 1. 728 - O. 30.~ 2.03 2.090 4.3 0.2

Fig. 1, one observes that the presence of sulfate
6 -0.74 1.743 - - 0 . 3 0 1 2.04 2.123 14.0 0.3
chiefly results in a considerable domain of stability
of lead sulfate PbSO4.
Fig. 7 shows that, in presence of solutions with a dynamically stable in water under atmospheric pres-
total sulfate activity of 1, Pb and PbSO4 are in equi- sure only for p H values between 6.0 and 10.2. At p H
librium for a potential which, at p i t values between values lower than 6.0 this electrode tends to decom-
approximately 3 and 10, has a very definite value of pose water with evolution of hydrogen. However,
- 0 . 3 5 6 volt. In the whole portion of the domain of this decomposition is very slow, and even negligible,
stability of PbSO4 for which the lead and sulfate in on account of the high hydrogen overvoltage on lead
solution exist essentially as Pb ++ and SO~-- ions,
[see, for instance, Creighton (8)].
i.e., at pH values between 3 and 9, the stability of
At the high potentials corresponding to lines 51-52
lead is constant and equal to 10-779 gram atom per
the sulfate PbSO4 is in equilibrium with PbO~ in
liter (or 0.0033 milligram of Pb per liter). At pH
presence of 1 molar sulfate solutions. Along the por-
values lower than 3 the solubility of lead sulfate in-
creases on account of the formation of bisulfate ion tion of 52 between a b o u t p H = 3 a n d p H - 9 the
HS04-, reaction (48). At pH values higher than 9 amount of lead in solution is constant at the same
the solubility of lead sulfate increases on account of small value (0.0033 milligram per liter) already men-

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 64 J O U R N A L OF T H E E L E C T R O C H E M I C A L S O C I E T Y
tioned above in connection with the Pb-PbSO4 elec-
trode. At pH values lower than 3 the amount of lead
in solution increases on account of the transforma-
tion of sulfate into bisulfate ions. This results in an
increase of Pb ++ ion concentration to 10-8 gram ion
per liter or 0.21 milligram per liter at p H 0.1 and, at
still lower pH values, plumbic ions Pb § are formed.
At pH values higher than 9 the amount of lead in
solution increases on account of the fox,marion of bi-
plumbite ions HPbO2-.
The PbOrPbSO4 electrode in 1 molar sulfate solu-
tions, whose equilibrium characteristics are repre-
sented by lines 51-52, is thermodynamically stable
in presence of water under atmospheric pressure only
for pH values between about 7.9 and 10.0. At pH
values below 7.9 this electrode tends to decompose
water with evolution of oxygen, but it is most likely
that this decomposition is very slow.
LEAI) STORAGE BATTERY
Fig. 7, as well as similar diagrams which could be
drawn for other sulfate concentrations, is useful in
the study of the behavior of the lead storage battery
since the equilibrium characteristics of the two elec-
trodes of the battery are represented by lines 48-49
(Pb-PbSO4 electrode, negative pole) and by lines
51-52 (PbO2-PbSO4 electrode, positive pole). Both
electrodes are dipping in solutions saturated with
PbSO4.
The amount of dissolved lead, which is extremely
low at p H values higher than 3 (10-7.79 gram ion per
liter or 0.0033 milligram per liter) increases as the
p H diminishes (10 -6.~ gram ion per liter or 0.21 milli-
gram per liter at pH = 0.1).
With the more acid solutions, which are used in
practice in storage batteries, the solubility at the
positive pole is greater than that at the negative
pole on account of the dissolution of PbO~ into plum-
bic ions Pb +4 which are not present in any appre-
ciable amounts in less acid solutions.
The electromotive force of the storage battery,
which is equal to the difference between the poten-
tials of the two electrodes, is measured b y the verti-
cal distance separating the lines 48-49 from the lines
51-52. Table I gives, at different pH values, the po-
tentials of the two electrodes, the electromotive force
and the lead concentrations around the two elec-
trodes in solutions of molarity 1 in H S O ( + S O ( - .
Differences between concentrations and activities are
neglected and the concentrations of lead are approxi-
mate, particularly at pH = - 1 . Table I shows that
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February 1951
storage batteries should be used with as high an
acidity as possible.
Table II gives the characteristics of batteries func-
tioning at various concentrations of sulfuric acid
calculated from formulas 48 and 51. 5 In addition to
the calculated electromotive forces we give the ex-
perimental values of Harned and Hamer (11) as
quoted by Latimer (4). Their approximate character
is sufficient for these calculations which neglect the
differences between concentrations and activities.
The Table shows that the calculated electromotive
forces agree rather well with the experimental values.
One also notices that an increase of acidity above 3
molar causes a rapid increase of the amount of dis-
solved lead around the positive pole on account of the
dissolution of PbO2 as Pb +4 ions.
ACKNOWLEDGMENTS
The preparation of the present paper was started
during the simultaneous presence of the three authors
at the University of Oregon during the spring of 1949.
Thanks are due to the Office of Naval Research and
to the Belgian American Educational Foundation.
Any discussion of this paper will appear in a Discussion
Section, to be published in the December 1951 issue of the
JOURNAL.
REFERENCES
I.M. POURBAIX, "Thermodynamique des Solutions
Aqueuses Dilutes--Representation Graphique du
RSle du pH et du Poteatiel," Meinema, Delft (1945).
Also Beranger, Paris (1948). An English translation
by J. N. Agar has been published by Arnold, London
(1949).
2. M. POUaBAIX, Corrosion, 5, 121 (1949).
3. P. DEL&H&Y, ~ . POURBAIX,ANDP. VANRYSSELBERGHE,
J. Chem. Education 27, 683 (1950).
4. W. M. LATIMER, "The Oxidation State of the Ele-
ments and their Potentials in Aqueous Solutions,"
Prentice-Hall, New York (1938).
5. S. GLASSTONE,J. Phys. Chem., 121, 1456 0922).
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7. H. M. SPENCER AND H. MOTE, J . Am. Chem. Soc., 54,
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8. H. J. CREmHTON, "Principles and Applications of
Electrochemistry," ~th ed., Vol. 1, p. 249, John Wiley
& Sons, Inc., New York (1943).
9. G. SCHIKORR,Korrosion u. Metallschutz, 16, 181 (1940).
10. U. R. EVANS, "Metallic Corrosion, Passivity and Pro-
tection," 2nd ed., pp. 394-398, Arnold, London (1946).
11. H. S. HARNEDANDW. J. HAMER,J. Am. Chem. Soc., 57,
33 (1935).
2 pH values measured by R. D. Williams.