Stability and solubility relationships between some solids

in the system Pb0-C02-HzO1

PETERTAYLOR AND VINCENT J. LOPATA
Research Chemistry Branch, Atomic Energy of Canada Limited, Whiteshell Nuclear Research Establishn~ent,
Pinawa, Man., Canada ROE ILO
Received May 9, 1983

PETERTAYLORand VINCENT J. LOPATA.Can. J . Chem. 62, 395 (1984).

We have determined equilibrium conditions for each reaction in the solid interconversion sequence PbO =
PbloO(OH)6(C03)6(plumbonacrite) E Pb3(OH)Z(C03)Z =
(hydrocerussite) PbC03 (cerussite), in aqueous carbonate solutions
near 25°C. Our data yield the following Gibbs energies of formation from the elements, bfG0(298.15 K): plumbonacrite,
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* *
-53 10 3 1 kJ mol-I; hydrocerussite, - 1705 1 1 kJ mol-I; cerussite, -628.0 ? 3.9 kJ mol-' . Corresponding estimated
*
values of ArG0(373 K) are -5120 2 50, - 1643 18, and -612 * 9 kJ mol-', respectively. We have demonstrated the
existence of a narrow stability field for plumbonacrite, and convenient small-scale preparations of hydrocerussite and plum-
bonacrite are described. Gibbs energy data for the solids have been combined with selected data for aqueous lead species in
a detailed computation of solubility behaviour for this system at 25°C.

PETERTAYLORet VINCENT J. LOPATA.Can. J. Chem. 62, 395 (1984).

Nous avons determine les conditions d'tquilibre de chaque reaction dans les interconversions suivantes a l'ttat solide: PbO
= PbloO(OH)6(C03)6(plumbonacrite) S Pb3(0H)Z(C03)2 =
(hydrocerussite) PbCO3 (cerussite), dans des solutions aqueuses
de carbonate i environ 25°C. Nos donntes fournissent les energies de Gibbs suivantes pour la formation i partir des Cltments
*
AfG0(298,15 K): plumbonacrite, -53 10 31 kJ mol-'; hydroctrussite - 1705 ? 1 1 kJ mol-I; cCrussite -628,O 2 3,9 kJ
mol-'. Les AfG0(373 K) sont respectivement tvaluts comme ttant suivantes; -5120 * 50, - 1643 & 18 et -612 ? 9 kJ
mol-'. Nous avons dtmontre l'existence d'un champ ttroit de stabilitt pour le plumbonacrite et nous dtcrivons une preparation
convenable a faible tchelle de l'hydrocerussite et du plumbonacrite. On a combine les donnees d'tnergie de Gibbs des solides
Can. J. Chem. 1984.62:395-402.

avec des donntes choisies pour des composts du plomb en solution aqueuse dans un calcul detail16 du comportement de ce
systeme en ce qui a trait a la solubilitC 5 25°C.
[Traduit par le journal]

Introduction ronmental and mineralogical behaviour of lead (14- 18). We

Many solids exist in the system PbO-C02-H20. Of these,
two polymorphs of PbO (litharge and massicot) and three car-
bonates (cerussite, PbC03; hydrocerussite, Pb3(OH)2(C03)2;
plumbonacrite, PbloO(OH)6(C03)6)occur in aqueous systems
near ambient temperature and pressure (1, 2). Garrels and
Christ (3) have discussed the stability fields of PbO, cerussite,
and hydrocerussite in the system Pb-0,-C0,-H,O at 25°C.
Recently, plumbonacrite was reported (4) to be metastable with
respect to decomposition according to reaction [I]:
[I] PbloO(OH)6(CO3)6 + PbO + 3Pb3(OH)z(CO3)2
-
Several phases of the type a P b C 0 3 bPbO occur during thermal
decomposition of the named carbonates, but d o not normally
occur in aqueous systems (5-7). Grisafe and White (7) deter-
mined the stability fields of these phases in the system
PbO-CO, at elevated temperatures and pressures. A hydrated
lead(I1) oxide, 3PbO-H,O or Pb60,(0H),, is also known
(8- 1 l ) , and early solubility measurements indicate that it may
b e marginally stable with respect to reaction [2] at ambient
temperature (1 I):
have studied interconversions among the five named solids to
determine equilibrium constants and hence t o compute solu-
bility and stability relationships.
Experimental
Starting materials were reagent-grade PbO. KOH, KzCO3 (Fisher),
and CO, (Matheson). Carbonate-free KOH solutions (J. T. Baker)
were used in key determinations. Potassium salts were used in prefer-
ence to sodium salts to avoid precipitation of NaOH -2PbC03, which
is less soluble than KOH.2PbC03 (19). The PbO reagent was a
mixture of litharge and massicot; this was adequate for most purposes,
since their Gibbs energies of formation differ by only about 1 kJ mol-'
(20, 21). Samples of litharge and massicot were collected whenever
they were obtained as pure reaction products. Recrystallized litharge,
prepared in an earlier study (22), was also used in a few experiments.
( a ) Preparation of cerussite
Pure cerussite was readily made by bubbling COZ through a sus-
pension of PbO (20 g) in dilute acetic acid mol dm-3, 200 cm3)
at room temperature for 6 h. Unlike Olby (2), we did not obtain
plumbonacrite or hydrocerussite as pure intermediates, although they
did occur sequentially as major phases. Our preparation was on a
smaller scale than Olby's, with a more dilute suspension of PbO.

Our interest arose from the possible use of lead compounds
to precipitate I4CO3 species, which are radioactive con-
taminants produced in the heavy-water moderator systems of
Canadian nuclear reactors (12). The formation of lead carbon-
ates may also be important in high-level radioactive waste
disposal, since lead has been proposed as an investment mate-
rial for used nuclear fuel in a deep underground disposal vault
(13). Lead carbonates are also of some importance in the envi-
' Issued as AECL-7974.
( b ) Preparation of hydrocerussite
Pure hydrocerussite was prepared by shaking a suspension of ce-
russite (5 g) in a solution of KzCO3 (8 g in 200 cm3) for 48 h at room
temperature. Alternatively, cerussite (5 g) was added to aqueous KOH
mol dm-3, 200 cm3), and the pH of the stirred suspension was
maintained at 11 for 24 h, using an automatic titrator charged with
KOH solution (0.1 mol dm-3).
( c ) Preparation of plumbonacrite
Hydrocerussite (5 g) was suspended in a solution (200 cm3) of
KZC03(13 g) and KOH (2 g), which was then stirred for 48 h at
100°C. The filtered product comprised plumbonacrite (>80%) and
 CAN. J . CHEM. VOL. 62, 1984

TABLE1. Solution data for final series of hydrocerussite/cerussite equilibration runs (a) 5 days,
(b) 13 days

Final [C,] x 10' Final HCO,

Initial (mol dm-') pH(meter) pH(calcd)$ (%)t§
HCO, p(cOz)ll
Run* ( 7 (a) (b) (0) (b) (a) (b) (0) (b) (Pa)
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*Initial [C,] = 3 x lo-' mol dmd3.

iPercentage of total carbonate concentration.
$Calculated from titration data.
I Calculated from average of meter and calculated pH values.
IICalculated from average of all pH measurements and calculations.

hydrocerussite. This was crushed using a pestle and mortar, and re- (3, 23). T h e anionic activity quotient, {OH-)'/{co:-), ob-
turned to the soIution for a further 24 h at 100°C. Care was needed to tained from equilibria such as [6], is sometimes more
maintain the pH near 13, to remain within the narrow stability field of convenient.
plumbonacrite (see below). This procedure was repeated until hydro-
cerussite was reduced to %3 - (usually two or three cycles); it was [6] Pb,(OH)z(C0,)2(s) + cO:-(aq) *
3PbC03(s) + 20H-(aq)
difficult to eliminate completely. The p ( C 0 2 ) value associated with a solution is conveniently
( d ) Interconversion reactions manipulated between and l o 2 Pa by adjusting pH and [C,].
Can. J. Chem. 1984.62:395-402.

Over 200 experiments were run, in which the various solids were
exposed to solutions of different pH and total carbonate concentration,
[C,].2Most experiments were run in screw-topped plastic bottles; long
equilibration runs were performed in flame-sealed Pyrex glass vials.
Solid products were identified and their purity estimated by X-ray
powder diffractometry (XRD), using CuK, radiation and a Philips
PW-1150 diffractometer equipped with a diffracted-beam mono-
chromator. When necessary, solutions were analyzed for lead by
atomic absorption spectrophotometry, and for carbonate by titration or
using a C02-sensingelectrode (Orion model 95-02). Measurements of
pH were made with a glass electrode. When precise pH measurements
were needed (see Table l), the electrode was calibrated with a fresh
sodium borate buffer solution having pH = 9.00 or 9.18.
Results and discussion
( a ) Theoretical considerations
The solid interconversion reactions are conveniently ex-
pressed by reactions [3] to [5] below. In reaction [3], dis-
tinction should be drawn between reactions involving lGharge
and massicot.
Total carbonate activity {C,}, proton activity {H'), and p ( C 0 2 )
are interrelated at 25°C by expression [7], which is derived
from equations given by Stumm and Morgan (ref. 23, chapt. 4 )
and accepted Gibbs energy data for water and carbonate species
(e.g. 21, 24):
x 3.4 x mol kg-' Pa-' (= mol dm-3 Pa-')
W e have not distinguished between molal a n d molar concen-
tration units, since the resulting errors are much less than the
experimental uncertainties. W e have used expression [8] as
proposed by Davies (ref. 2 3 , pp. 134- 136; ref. 25) to estimate
the mean ionic activity coefficient, f,, and hence bicarbonate
and carbonate activities, from the ionic charge, z, and the ionic
strength, I .
[8] -log f, = 0.5z2 0.311

[3]
5
iPbO(s)
1
+ C02(g) + ?H20(I) % ; P ~ ~ ~ o ( o H ) ~ ( c o ~ ) ~ ( s )Where necessary, I was calculated from measured pH and [C,]
values by an iterative procedure.
( b ) Reactions of cerussite with KOH
Reactions between cerussite (0.25 g) and K O H solutions (40
cm3; various concentrations up to 5 mol dm-3) were in-
vestigated at room temperature (22 * 2°C). Cerussite alone
was recovered from reactions with final pH below about 9.5.
Hydrocemssite was the major product in the p H range 9.5-12.
Although these reactions involve many aqueous species, the
Plumbonacrite and hydrocemssite occurred together at pH =
equilibrium constant for each reaction can be expressed simply
12-13.5. Lead(I1) oxide w a s formed at pH = 13.5-14; both
as the reciprocal of a carbon dioxide partial p r e ~ s u r ep(COz)
,~
litharge and massicot occurred, often one or the other as a pure
phase, but with no obvious pattern of occurrence. Above pH =
'In this account, [C,] and {C,) represent the sums of the concen-
trations and activities, respectively, of non-complexed carbonate spe- 14, clear undersaturated lead solutions were formed. These
cies, i.e. "H2C03", HCO,, and c ~ : - , and do not include complexes observations are consistent with McIntyre's stability calcu-
such as P ~ C O and~ P~(co~):-. lations reported by Garrels and Christ (3), except for the occur-
Strictly speaking, this term should be fugacity, rather than partial rence of plumbonacrite. Further experiments were designed t o
pressure, but the two are indistinguishable at the pressures of concern define the stability fields more exactly, with special attention t o
here. plumbonacrite.
 TAYLOR AND LOPATA
CEWSSITE --) I 1
4
4
0 0.4
-
.-,
0.2 -
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0
HYDROCERUSSITE --,
0.5 0.6 0.7 0.8 0.9
FIG. 1 . Summary of X-ray diffraction data for products of reactions
between cerussite (0) or hydrocerussite(o) w~thsolutions having [C,]
= [HCO,] + [co:-] = 0.125 mol dm-', for 48 h at 22OC. I(3.50)
and I(3.29) are the peak heights of the most intense features in the
cerussite and hydrocerussite diffraction patterns (3.50 A and 3.29 A,
respectively).The ordinate function is thus an approximate measure of
the extent of conversion.
Can. J. Chem. 1984.62:395-402.
(c) Cerussite-hydrocerussite interconversion
Experiments in which either cerussite or hydrocerussite was
exposed to carbonate/bicarbonate solutions clearly showed
that this interconversion is readily reversible at room tem-
perature. XRD data, summarized in Fig. 1, indicated that hy-
drocerussite and cerussite were in equilibrium at [coS-]/[c,]=
0.70 + 0.02 and [C,] = 0.125 mol dm-3. At lower [coS-]/[c,]
ratios, hydrocerussite was converted to cerussite, and the re-
verse reaction occurred at higher ratios. Although equilibrium
conditions are thus narrowly defined, ionic activities could not
be estimated sufficiently well to calculate p3 as precisely as we
wished. Further experiments were therefore run at lower [C,],
down to lo-' rnol dm-3. At these lower concentrations, the
quantity of hydrocerussite or cerussite consumed or formed in
the reactions was too small to determine equilibrium conditions
by XRD. We therefore deduced the direction of reaction, and
judged whether equilibrium had been achieved, by careful
measurement of pH and [C,].
Twenty-five experiments with [C,] between and lo-'
mol dm-' yielded values for p3 between 8 and 16 Pa. In the
final determination, duplicated experiments were run in sealed
Pyrex glass vials, starting with a mixture of cerussite and hy-
drocerussite (0.5 g each) in solutions with various [HCO,]/[C,]
ratios and [C,] = 3 X lo-' rnol dm-'. This concentration
provides the best compromise between the respective lim-
itations of the carbonate analyses and the estimation of activity
coefficients. One series of experiments ((a) in Table 1) was run
for 5 days, and the second ((6) in Table 1) for 13 days. The pH
was measured immediately after opening each vial. The solu-
tions were then filtered and analyzed for carbonate and bicar-
bonate by titration; a pH value was then calculated from the
titration data. Most measured and calculated pH values agreed
within 0.04 units, the largest discrepancy being 0.08 units. We
conclude that solution analyses were not substantially affected
by exchange of C 0 2 with the atmosphere. The results are sum-
marized in Table 1. The values of p, at 25OC, determined from
these runs, range from 12.8 to 14.1 Pa, with an average of 13.3
Pa. No correction was made for the actual experimental tem-
397
perature of 22 * 2"C, since the equilibrium quotient,
[co:-]/[c,], changes only slightly between 22 and 100°C (see
below).
Our determination of p, is in fair agreement with the value
of 27 Pa obtained from the Gibbs energy data recommended by
Sadiq and Lindsay (21). The discrepancy corresponds to a
disagreement of about 1.8 kJ mol-I in the Gibbs energy of
reaction for reaction [5]. Our result is also consistent with
Garrels' estimate of p3 = 10 Pa, which was based on de-
ductions from the natural occurrence of cerussite and hydro-
cerussite ( 17).
(d) Interconversions involving plurnbonncrite
Preliminary experiments indicated a narrow stability field for
plumbonacrite, so subsequent work concentrated on con-
1.0 firming this observation and defining the boundaries of the
field.
Plumbonacrite persisted unchanged for seven days in solu-
tions with [C,] = 0.125 rnol dm-3 and [KOH] between 0.02 and
0.4 mol dm-3. It was converted to massicot at [KOH] 2 0.6
rnol dm-3, with partial conversion occurring at 0.5 rnol dm-'.
In similar experiments starting with PbO, plumbonacrite was
formed at [KOH] = 0.1 , but not at 0.5 mol dm-'. Slow, partial
conversion of plumbonacrite to hydrocerussite occurred at
[KOH] 5 0.01 rnol dm-3, and the reverse reaction was ob-
served in some runs with KOH concentrations between 0.05
and 0.08 rnol dm-'. The latter reaction, accelerated by heating
to 100°C, provided the basis for our synthesis of plum-
bonacrite, described above. In triplicated experiments starting
with mixtures of plumbonacrite and hydrocerussite at [KOH] =
0.01 and 0.1 mol dm-3, the relative amount of plumbonacrite
in the product was consistently higher at the higher KOH con-
centration. Although these interconversions are less clear-cut
than the hydrocerussite-cerussite reaction, w e could never-
theless observe reversible reactions in the sequence PbO =
plumbonacrite G hydrocerussite, thus confirming that plum-
bonacrite has a narrow stability field. This narrowness can
account for the scarcity of plumbonacrite in nature (4).
Further experiments in sealed glass vials were run for 7- 14
days with mixtures of PbO and plumbonacrite (0.3 g each) in
20 cm3 aliquots of solutions with various KOH concentrations
at [K2C03]= lo-', lo-', and rnol dm-'. Most runs did not
reach equilibrium, but the direction of reaction [9] (equivalent
to reaction [3]) could be determined from solution analyses for
carbonate and/or hydroxide.
[9] $ PbO + C O ~ -+ 23 Hz0 = 61 PbIuO(OH),(CO,)i+ 20H-
'The results are presented in Fig. 2. From these we estimate the
equilibrium constant {OH-}'/{co:-} = lo0.' '0.6 mol dm-3,
which corresponds to p , = 10-4.9'0.6 Pa. We did not discern
reproducible differences between reactions involving PbO re-
agent and our synthetic litharge, except that the latter material
reacted more lethargically. Based on the free energies of for-
mation of rnassicot and litharge, p l values for the two forms of
PbO should differ by a factor of about 1.5, whereas we estimate
an error of a factor of four in p , .
Interconversion between hydrocerussite and plumbonacrite
was too slow at [C,] 5 lo-' rnol dm-' to pin-point the equi-
librium at low ionic strength. The close crystallographic simi-
larity between these phases may promote epitaxial crys-
tallization with consequent passivation of one phase by the
other. Furthermore, their solubility behaviour is very similar
(see Fig. 5), so the driving force for interconversion is slight.
 398 CAN. J. CHEM. VOL. 62, 1984

TABLE2. Gibbs energy data used to determine equilibrium

relationships

A G:, 298
Species* (kJ mol-') Reference
PbC03(s) -628.0 This work
Pb3(OH)2(C03)2(s) - 1705 This work
. , P ~ I o ~ ( O H ) ~ ( C O ~ )-53
~ ( S10
) This work
I
o Plumbonocrife -PbO observed PbO(s) (litharge) -189.3 21
PbO --Plumbonocrile observed co2(g) -394.38 21
o No observable conversion
H20(1) -237.18 21
"H,C03(aq)" -623.21 21
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HCO,(aq) -586.89 21
fi (mol dm-3)"2 co:-(aq) -527.94 2I
FIG. 2. Summary of conditions under which interconversion of Pb" (aq) -24.69 21
PbO and plumbonacrite was observed. The numbering on the figure PbOH'(aq) -217.94 21
indicates carbonate concentration (mol dm-3). The bold lines corre-
spond to log K = 0.1 + 0.6 for eq. [9], using eq. [8] to estimate ~b(~~):(aq) -397.73 21
deviation from ideality. Flagged data points correspond to deter- Pb(OH),(aq) - 575.89 21
minations by visual observation ([co:-] = 0.01 mol dm-3) or X-ray Pb20H3+(aq) -250.04 21
diffraction ([co:-] = 0.125 mol dm-'). The remaining observations
are based on solution analyses. pb,(~~):+(aq) -886.42 21
Pb4(0~):+(aq) -928.22 21
Based on the results obtained at [C,] = 0.125 mol dm-, we pb6~(o~)l+(aq) - 1559.59 2 1 , 38, 29, see text
estimate that p, exceedsp, by one to three orders of magnitude, P ~ C O ~ ) -593.37 44, 45
Can. J. Chem. 1984.62:395-402.

so we assign the value p, = Pa. Since plumbonacrite 44, 45

and hydrocerussite differ only slightly in composition, calcu-
lated Gibbs energies and solubilities are much less sensitive to
errors in p, than in p , or p,, so precise measurement of p, is
relatively unimportant in the overall description of the system,
except in determining the plumbonacrite-hydrocerussite sta-
bility boundary (see expressions [I21 and [13] below).
(e) Gibbs energies of formation of the carbonates
When expression [lo] is applied successively to reactions [3]
to [5], using Gibbs energy data from ref. 21, we obtain re-
lationships [I I] to [13]. These permit us to calculate the Gibbs
energies of formation, ArG0(298.15 K), of the three lead car-
bonates from the p(C0,) data.4
+ RT In p(C02, equilibrium, atmospheres)
[I 11 ArGO(plumbonacrite, s, 298.15 K)
= -(1593.8 - 10.28 log pi - 1.14 log pi)
= -(583.7 - 3.43 log pi - 0.38 log pi - 1.90 log pi)
(Estimated errors include our own experimental uncertainties,
plus those in Gibbs energies of formation of the parent oxides,
as indicated in ref. 24, since the latter uncertainties are not
stated in ref. 21. Data from ref. 21 were used for consistency
with the solubility computations, shown below.)
"The data of ref. 21 refer to a standard state pressure of one atmo-
sphere (1.013 X 105 Pa). In eqs. [ I l l to [13], p',, p i , pi are partial
pressures in atm.
~b(~03)i-(aq) -1141.17
*Our grounds for omission of the following species are presented in
the text: PbO(s) (massicot), Pb(OH),(s), Pb60,(OH)4(s), P~,(oH):+-
(aq), Pb,(OH):(aq), pb6(OH)it(aq).
Our experimental Gibbs energy for cerussite, -628.0 r 3.9
kJ mol-I, lies within the range of reported values cited by Sadiq
and Lindsay (21), -625.5 to - 629.0 kJ mol-I, and is not
significantly different from their recommended, recalculated
value of -629.7 kJ mol-I, originating from the calorimetric
work of Adami and Conway (26). Our value of - 1705 -+ 11
kJ mol-I for hydrocerussite agrees with their calculation of
- 17 11.6 kJ mol-I , derived from the pioneering solubility
study by Randall and Spencer, the only source they cite (1 1,
21). Our estimate of -5310 ? 31 kJ mol-I for plumbonacrite
is much more negative than the value of -5121 kJ mol-'
reported by Haacke and Williams (4). The source of so large a
discrepancy is not readily apparent, since few details are given
in ref. 4. We emphasize that our value is consistent with exten-
sive observations of interconversion reactions involving plum-
bonacrite.
If) Calculation of solubility-stability relationships
Solubility calculations were performed using the computer
program DIST, which was developed at these laboratories by
Robert J. Lemire and Nava C. Garisto.' This program calcu-
lates species distributions, at given pH and ligand activities,
from Gibbs energies of formation of the solid and solution
species concerned. The results are expressed as activities, in
molal units. We have used molar units throughout the dis-
cussion, since the resulting errors are negligible at the level of
precision of our data. Our selected Gibbs energy data are
shown in Table 2.
Strictly speaking, this program calculates the activities of species
in saturated solutions. [t is reasonable to equate the total lead activity,
{Pb,) = Cx{Pb,L,."), to solubility at ionic strengths below about 0.01
mol dm-3.
 TAYLOR AND LOPATA
Although hydroxo- and carbonato-lead(I1) complexes have
received much experimental attention, some uncertainties
about them persist. The most recent detailed assessment of
thermochemical data for hydroxo-lead(I1) complexes appears
to be that reported by Sadiq and Lindsay (21), and most of our
data are from this source. These data originate mainly from the
work of Olin and Carell (27-30), as previously compiled by
Baes and Mesmer (31) and by Smith and Martell (32). Sadiq
and Lindsay have adjusted the Gibbs energy data tabulated by
Smith and Martell for internal consistency with their re-
calculated values for PbO(s) and Pb2+(aq).
We have omitted two species which were included in Sadiq
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and Lindsay's compilation: P ~ ( O H ) ; - ( ~and
~ ) Pb(OH),(s). The
former had been included on the basis of a single report by
Aksel'md (33), cited by Karapet'yants and Karapet'yants (34).
We found that its inclusion led to unrealistically high computed
lead concentrations at high pH, exceeding 1 mol dm-, above
about pH = 13.5. The data selected by Sadiq and Lindsay
imply that Pb(OH),(s) is stable relative to litharge and water by
26.0 kJ mol-' at 25°C. This is based on two earlier thermo-
chemical compilations, but the original source is obscure.
However, there is considerable doubt about the very existence
of solid Pb(OH),, many earlier reports being referable to basic
lead nitrates (35-37). We noted above that the hydrated
lead(I1) oxide, Pb60,(OH),, may be marginally stable with
Can. J. Chem. 1984.62:395-402.
respect to PbO(s) and H20(1) (1 1). However, we have not
observed it, except in some electrochemical experiments under
conditions of high super~aturation.~ We omitted massicot,
since the consensus is that it is metastable with respect to
litharge at 25°C (2 1, 24).
Two further species, P~,(oH): and P ~ ~ ( o H ) have~ + , recent-
ly been reported (38-40). When we included P~~(oH):in our
data set, it led to unrealistically high computed solubilities for
PbO around pH = 9 to 11, with a minimum solubility of about
5 X lo-' mol dm-3. The computed minimum solubility when
P~,(oH); was omitted was about 2.5 x lo-' mol dm-,, in
better agreement with the experimental minimum solubility of
litharge, 6.7 X lo-' mol dm-, (41). The species P~,(OH); may
thus be present, but its reported stability constant appears to be
too high. We therefore omitted it from our final computations.
We also omitted P~,(oH):+, since its formation constant has
only been determined at high ionic strength (3.0 mol dm-,
LiClO,) (39, 40). The quality of agreement between Olin's
speciation model and experimental data indicates that the inclu-
sion of further species will only have minor effects on com-
puted solubility behaviour (27-30, 38-40). Ohtaki and co-
workers (39, 40) present evidence that the species formerly
identified as P ~ ~ ( o H )is~in+ fact P~~o(oH):+,which has also
been observed in the solid state (10,42,43). We have incorpo-
rated this suggestion by subtracting the Gibbs energy of for-
mation of H20(1) from that recommended for P~~(oH):+in ref.
21, the two species being related by reaction [14]:
Several workers have measured formation constants, p, for
the two lead carbonate complexes P ~ C Oand ~ P~(co,):-.
Clever and Johnston (44) tentatively recommended the re-
spective values p = 2 x lo6 and 6 x lo9 at I = 0.1 mol dm-3,
as reported by Bilinski et al. (45). We have used these data,
corrected to zero ionic strength using eq. [8]. We note that
Unpublished work, in collaboration with D. W. Shoesmith and M.
G. Bailey.
399
Bilinski and Schindler (14) recently reported somewhat lower
formation constants (log p = 5.40 and 8.86, respectively, at
I = 0.3 mol dm-3).
It is convenient to discuss the solubility calculations in terms
of PC, and pPb,, the negative logarithms of {C,) and {Pb,),
respectively (cf. pH). We computed species distributions at pH
intervals of 0.5 and PC, intervals of 1.0. A finer grid was used
to elucidate details of complex behaviour in some portions of
the pH-PC, matrix. Results are summarized in Figs. 3 to 5.
Figure 3 is a composite solubility diagram, showing pPb, and
the stability fields of litharge and the three carbonates as func-
tions of pH and PC,. Figure 4 shows the computed fields of
preponderance of the various aqueous lead species in saturated
solutions, superimposed on solubility contours corresponding
to Figure 3. Figure 5 shows the computed solubilities of the
four solids, including conditions of their metastable occur-
rence, as a function of pH at PC, = 4. Table 3 lists computed
equilibrium pPb, and PC, values, as a function of pH, for the
three stable solid assemblages (litharge t plumbonacrite;
plumbonacrite + hydrocemssite; hydrocemssite t cemssite).
(g) Description of solubility-stability relationships
Figure 3 illustrates the development of the lead carbonate
stability fields as total carbonate activity increases. At PC, >
9.5 and pPb, > 0 , litharge is the sole stable solid, with a
minimum computed solubility of pPb, = 4.6 at pH = 10.3.
(See top of Fig. 3; note that a portion of the PbO solubility
curve at PC, = 10 is obscured in this view of the solubility
surface.) Most of the litharge solubility surface at pH < 9 is
probably not accessible in practice without precipitation of
basic lead salts. As PC, decreases (i.e. total carbonate activity
increases), solid lead carbonates progressively suppress lead
solubility, and their stability fields encroach into that of li-
tharge. Plumbonacrite initially appears at PC, = 9.5, hydro-
cemssite at PC, = 9.0, and cerussite at PC, = 5.5. The stability
field boundaries (dashed lines in Fig. 3) progress to higher pH
as PC, decreases. Encroachment by the stability fields of the
complex salts MOH-2PbC03 (not shown in Fig. 3) occurs at
pH .= 10 and PC, < 1 (M = Na) or PC, < 0 (M = K), when
Na and K are the counterions in the added carbonate salts.
The preponderance diagram (Fig. 4) shows that polymeric
hydroxo-lead complexes are important only at about PC, > 8
and pH < 10 for realistic lead concentrations. At lower PC,
values, polymerization is suppressed by precipitation of the
solid carbonates. Lead solubility reaches a minimum, pPb, -
6.6, in slightly alkaline solution near PC, = 4; at still lower PC,
values solubility is enhanced by carbonate-lead(I1) complex
formation. This behaviour is consistent with the solubility data
of Bilinski and co-workers (14, 46). The field of predominance
of Pb(~0,):- (Fig. 4) indicates that the best area for further
experimental evaluation of the formation constant of this spe-
cies would be near PC, = 1-2 and pH = 9- 1 1. The low and
relatively constant computed lead solubility within the field of
predominance of P ~ C indicates
O~ that solubility measurements
are unlikely to shed further light on this complex.
There is some interest in whether cemssite or hydrocemssite
is the stable form of lead carbonate in natural surface waters
(14, 15). Our data indicate that cerussite should be the stable
phase at the usual atmospheric p(C02)of = 30 Pa, but that only
slight depletion of C 0 2 would be necessary to enter the hydro-
cerussite stability field. However, Fig. 5 shows that the solu-
bilities are similar, especially near neutral pH. This similarity
also explains the substantial uncertainty in p , , as determined
 CAN. J . CHEM. VOL. 62, 1984
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Can. J. Chem. 1984.62:395-402.

FIG. 3. Computed solid/solution equilibrium surface in the lead spectively). Dashed lines represent stability boundaries between solid
carbonate system at 2S°C, expressed as negative logarithms of proton, phases in the sequence (left to right) cerussite, hydrocerussite, plum-
total lead and total carbonate activities (pH, pPb,, and PC,, re- bonacrite, litharge.

from solubility measurements (14), compared with direct ob-

servation of phase transformations. Interestingly, the minimum
computed lead solubility varies only within the narrow limits,
5.8 < pPb, < 6.6, as p(C0,) varies between lo-) and lo5 Pa,
although the position of the minimum progresses from pH = 10
to 6.5.
Most of our lead solubility measurements were in the range
pH > 10 and PC, < 3, and thus lay within the predominance
fields of P~(co,):- and Pb(0H);. These measurements were
not sufficiently precise to permit any further critique of the
computed solubilities, but the general trends paralleled the
behaviour described in the appropriate portions of Figs. 3
and 4.
(h) Phase equilibria above 25°C
We briefly investigated the solid phase interconversions at
50, 75, and 100°C, in solutions with [C,] near 0.1 mol dm-,.
We found only a slight temperature dependence for all three FIG. 4. Computed fields of preponderance of the various dissolved
equilibria, when expressed as concentrations of carbonate and lead species (bold outlines) in saturated solutions corresponding to the
bicarbonate or hydroxide. However, applying Helgeson's data equilibrium surface in Fig. 3. Numbered contours represent total lead
for the dissociation equilibria of water and carbonic acid at activity, expressed as pPb,.
 TAYLOR AND LOPATA 40 1

By analogy with the computed high-temperature Gibbs ener-

gy data reported (24) for aragonite, strontianite, and witherite,
which are all isostructural with cerussite, and display similar
AfGO-T relationships, we would anticipate A,GO (cerussite, s ,
373 K) = -608 kJ mol-I, in reasonable agreement with our
experimental estimate. The temperature dependence of p, ap-
pears to differ substantially from that of p , and p,. Whereas p,
increases by only about an order of magnitude between 25 and
100°C, p, and p, both increase by about four orders of mag-
nitude. This is probably because H 2 0 is a reactant in the for-
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ward reaction of equilibria [3] and [4], but a product in reaction

FIG.5. Computed equilibrium dissolved lead activities for the four
solids litharge ( A ) , plumbonacrite (B), hydrocerussite (C), and ce-
russite (D) at PC, = 4, as a function of pH.
TABLE3. Computed ionic activities of saturated solutions in equi-
librium with lead oxide/carbonate phase assemblages
[5]. These p(C0,)-T relationships indicate that the stability
field of cerussite encroaches on that of hydrocerussite with
increasing temperature. The stability fields of hydrocerussite
and plumbonacrite in the presence of H,0(1) are likely to disap-
pear at about 150 and 200°C, respectively. However, the phase
diagram will probably be further complicated in this region by
the emergence of stability fields for the anhydrous basic car-
bonates, nPbC0,. bPbO (8).

Litharge + Plumbonacrite + Hydrocerussite + Acknowledgements

plumbonacrite hydrocerussite cerussite
Part of this work was jointly funded by AECL and Ontario
Hydro under the CANDEV agreement. W e are grateful to
Can. J. Chem. 1984.62:395-402.

pH PC, pPb, PC, pPb, PC, pPb,

A. M. Duclos for performing many of the XRD measurements,
and to R. J . Lemire and J. Paquette for many helpful dis-
cussions.

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