pH Measurements in Aqueous

CO, Solutions Under

High Pressure and Temperature*

J. L. CROLET* and M. R. BONIS*

Abstract
In order to determine the acidity of corrosive media prevailing in oil and gas wells where 00 2
corrosion is encountered, a pH meter has been built which enables pH measurements under
pressures from 0.1 up to 100 MPa. The usual physical chemistry of calcocarbonic equilibria is
also presented in a new form which better emphasizes the influence of the partial pressure of
CO 2 as the controlling variable in the system. According to both theoretical and experimental
results, the pH of a production water depends as much upon its alkalinity as upon the level of
the 002 partial pressure. The effect of calcareous saturation or supersaturation is also em-
phasized. It is then shown through a survey of production waters that their acidity under well
conditions is much weaker than is commonly assumed. This stands for both 00 2 corrosion
and sulfide stress cracking.

Introduction Experimental
The 002 corrosion of steels is an old problem in industry,' in-
cluding oil and gas fields which have a noticeable amount of Apparatus
CO2 , but no H 2 S. However, the recent development of offshore The experimental device was a pH meter which had been
production has reinforced the need for corrosion forecasting adapted to enable measurements under pressures of 0.1 to 100
and has renewed interest in the problem. MPa. A general sketch of the apparatus is shown in Figure 1.
In the oil industry, work carried out by NACE in the The sensitive elements, glass electrode [Figure 1, (1)] and
1950's 2-5 produced the best documents on this subject. In par- Ag/AgCI reference electrode [Figure 1, (2)], were commercially
ticular, they showed that besides the 00 2 partial pressure, the available (Tacussel(') TB/HS and AgCI 4). The Ag/AgCI elec-
very nature of each well, and probably of their production on trode was preferred to the calomel electrode due to its better
water, also play a determining role in the severity of corrosion. stability with temperature and its low sensitivity to pressure
More recent studies have been devoted to the electrochemical variations 2° The external electronic device (Tacussel ISIS
properties of carbonic acid 6 7 or to laboratory measurements
' 20000) gave a numerical display of the measurement to the
of corrosion rates 8-10 under high pressures of 00 2 , but in each nearest 0.001 pH unit.
case using solutions of NaCI alone. None of these studies, Electrodes were settled in an autoclave [Figure 1, (3)]
however, were able to reproduce for long periods of exposure made from an austenitic precipitation-hardened stainless
mean corrosion rates which would be high enough to account steel ASTM A 286 (Uginox('> FLX 130) which can withstand an
for the forms and rates of actual tubing failure. internal pressure of up to 100 MPa. Both ends of the
Again, the exact nature of production waters is probably autoclaves were closed by a piston [Figure 1, (5)] compressing
at the origin of such differences. Indeed, these waters are well- a self-sealing gasket in PTFE [Figure 1, (6)].
known 11 12 as complex solutions of cations, Na, M g + +
' Electrical connections were set up in a compartment
Ca++, and possibly Fe++, and of anions Cl , SO 4 °, and
- which was completely filled with silicone oil [Figure 1, (4)] of a
HCO 3 . In the systems of water distribution (either domestic
- high resistivity (Rhone Poulenc RHODORSIL( 1 > 47 V 20). The in-
or industrial), the role of this chemistry of calcocarbonic ternal pressure of this compartment remained in equilibrium
equilibria, as well as its influence on the corrosion of steel, is with the pressure of the whole autoclave through a mercury
well-known. 13 In this case, however, the 00 2 partial pressure siphon (not shown in Figure 1) according to a system derived
was never really considered, neither as an experimental from those proposed by Disteche and Le Peintre. 15- 7 The oil
'

parameter, or as the controlling variable of the system.
The aim of the present study was thus to reconcile both
approaches, and with the help of accurate pH measurements,
try to determine the exact acidizing effect of the partial
pressure of 00 2 and its interaction with the calcocarbonic
species of water.
*presented during Corrosion/82 (Paper No. 123), March, 1982,
Houston, Texas.
*Société Nationale Elf Aquitaine (Production), Pau Cedex,
France.
and electrolytes inside the electrodes were thus isolated from
the general atmosphere of the autoclave in order to prevent
any pollution by acid gases.
The electrical junctions [Figure 1, (8)] to the measuring
electrodes required the development of a special fittings
technology. In a pH meter, the internal resistance of the
measuring circuit may be as high as 20 to 50 Mg, which re-
quires a rigorous isolation of electrical leads. Quartz sleeves
[Figure 1, (9)], piles of flat grounded quartz plates [Figure 1,
'>Trade marks.
(

0010-9312/83/000015/$3.00/0
Vol. 39, No. 2, February, 1983 1983, National Association of Corrosion Engineers 39

FIGURE 1 — Sketch of the pH meter. (1) Glass electrode;
(2) reference electrode; (3) autoclave body; (4) oil com-
partment; (5) piston; (6) self sealing PTFE gasket; (7)
threaded plug; (8) electrical junction; (9) quartz sleeve;
(10) flat grounded quartz plate; (11) PTFE film; (12)
magnetic stirrer; (13) bubbling of the gas under pressure;
and (14) test solution.
(10)], and PTFE films [Figure 1, (11)] enabled us to ensure both
a tight seal under 100 MPa and an electrical isolation of the
order of 10 5 MSZ in a dry atmosphere. Although such a rigorous
isolation was not necessary for the electrical junctions to the
magnetic stirrer [Figure 1, (12)), the same fitting technology
was also used.
The heating and cooling of the autoclave was achieved by
external resistors and coiled water tubes. Temperature varia-
tions were kept at less than ±1 C. The exact temperature
value was measured inside the autoclave by a copper-
constantan thermocouple. The autoclave was fed with gas
mixtures which bubbled [Figure 1, (13)] through the test solu-
tion [Figure 1, (14)]. It was pressurized by means of a high
pressure pumping facility. Ancillary capacities and external
lines under high pressure were heated to -70 C, to prevent
any parasitic liquefaction of the 00 2 during pressurizing.
The curves pH = f (PCO 2) were always taken in the sense
of increasing pressures. Indeed, in the reverse sense, degas-
sing delays always induced large 00 2 supersaturations in the
test solutions. Modified reference electrodes were sometimes
used for pH measurements in the presence of H 2 S. They were
based on the classical system of porous extensions, 17 18 allow-
'
ing the delay of the H 2 S diffusion towards the sensitive
Ag/AgCI element.
Calibration
The quality of classical pH meters lies mainly in the quali-
ty of calibration. For measurements under atmospheric
pressure, calibration was carried out just before and just after
the measurement, at the test temperature, and with buffer
solutions for which the pH variations with temperature were
welt known (Tacussel T 6 PKN = phosphate buffer with pH
40 CORROSION—NACE
~6.9, Tacussel TIH = "HCI" buffer with pH -1.1). The error
in the pH might then be as low as ±0.05 pH units.
For measurements in autoclaves, the duration of the ex-
periment was much longer; therefore, the stability of the
calibration could not be as strongly assessed. Besides that,
bubbling under 0.1 MPa in an opaque high pressure cell was
rather delicate. In addition, a reaction of the glass electrode to
pressurizing was sometimes noticed. Altogether, a systematic
shift seemed to occur on the curves between the value ob-
tained at 0.1 MPa and the measures obtained under higher
pressures. However, the exact origin of this shift could never
be definitely established (supersaturation at 0.1 MPa due to
over bubbling, hysteresis of the glass electrode, or shift of the
calibration with time).
The results showed that the internat accuracy along an in-
dividual curve pH = f (P00 2 ) remains --0.05 unit, but that the
error in the comparisons between different curves may reach
0.1 to 0.2 pH unit. Therefore, whenever possible, and especially
for temperatures lower than 40 C, the results of the measure-
ments in the autoclave were corrected in order to adjust the
measure at 0.1 MPa to the corresponding measure from usual
facilities under atmospheric pressure.
Theoretical Background
Necessity of an Appropriate Presentation
The physical chemistry of calcocarbonic equilibria has
been well-known for a long time. However, contrary to usual
studies, the composition of water is considered here as a
datum and the partial pressure of 00 2 as a variable. In the
same way, the pH of water is no longer an adjustable
parameter, but only the resuit of different equilibria. The ex-
pression of these equilibria here must therefore have a form
differing from traditional presentations in the literature. 1114
Thus, before considering experimental results on the varia-
tions of pH with the partial pressure of 00 2 it appears
,
necessary to express these calcocarbonic equilibria in a new
and more appropriate form.
Chemical Species
In general, chemical species present in production water
are:
1. The dissociation products of water, H+ and OH - .
2. The dissociation products of carbonic acid, bicar-
bonate HCO 3 - , and carbonate CO 3 ions.
3. Anions from strong acids CI - , SO 4 =, etc.
4. Metallic cations, either alkaline Na+, K+, or alkaline
earth Ca++ Mg++ etc.
Concentrations are expressed here in equivalents per liter
(= valency x number of mole/I). For some important species,
concentrations are also expressed as for pH on a logarithmic
scale: pX = - log X.
Reactions
In reservoir waters, the chemical species which are likely
to precipitate first are calcite CaCO 3 , followed by M9CO 3 or
CaSO 4 11,12 This study, however, wilt be limited to the case
.
when only calcareous saturation is likely to be reached.
Therefore, the only possible reactions are the two successive
dissociations of carbonic acid, the dissociation of water, and
eventually the solubility product of calcite. The mass action
laws of these four equilibria are:
H + • HCO 3 -
P K, (1)
H+.0O 3 =
=K
HCO 3 (2) 2
H+•OH - =Kw (3)
Ca++ •CO3 = = Ks (4)
 TABLE 1 — Definition of Various Water Types

Fundamental
Water Type Ions13 Example A Alk

Inert — NaCI 0 0
Purely Calcic Ca+ + CaCl2 Cao 0
Purely Bicarbonated HCO3- NaHCO3 -Alk >0
Stoichiometric Ca++ = HCO 3 -111 Ca(HCO3)2 0 Cao
General Ca++ + HCO3 - CaCl2 + NaHCO3 Ca o -Aik >0

11 Iln equivalent per liter

P is the fugacity of carbonic acid, directly expressed as the
partial pressure of CO 2 . Therefore, K l does not necessarily
have the value published in tables under the name. In the same
way, the K 2 and K s coefficients correspond to concentrations
in equivalents per liter, and one would have to apply the ap-
propriate corrections to tabulated values which could corre-
spond to molarities.
Equations (1) through (4) strictly apply to only very dilute
solutions. For concentrated solutions, the effect of ionic
strength on the ratio between concentration and chemical ac-
tivity would have to be taken into account. This leads to
replacement of the K coefficients by corrected K' ones. 11 ' 13
The K values corresponding to a given application are rarely
tabulated for the actual conditions of concentration, pressure,
and temperature, but are done in the units of this study when
they need to be directly established.
Beside the four mass action equations [Equations (1)
through (4)], the condition of the electric neutrality of the solu-
tion was also respected:
Ca +++E mi+H+=HCO 3 + CO + OH +Em1. (5)
In this equation, E represents the sum of all cations other than
Ca ++ and H+, and E the sum of all anions other than OH - ,
CO3 =, and HCO 3 =. Following Poirier's diagrams, 13 we will call
X, by analogy, 121 the excess of anions E over cations E:
X= Emj-Em. (6)
Therefore, salts other than calcium salts or carbonates have a
zero contribution in X. A positive X value represents an excess
of anions, corresponding either to strong acids or to calcium
salts. On the other hand, a negative value means an excess of
cations, corresponding to either bases or soluble carbonates
and bicarbonates.
When a water is analyzed in atmospheric conditions, the
residual partial pressure of 00 2 is very low (---10 -5 MPa). In
this practical lack of 00 2 , the residual value of the sum Alk =
HCO 3 - + CO 3 = is titrated by adding H 2 SO 4 until the methyl-
orange end point is reached (pH 4.5), and therefore labeled
"the total alkalinity of water." (It is worth noting that through a
paradox of vocabulary, an acidic water, that is with pH < 7,
may nevertheless have some alkalinity.)
Taking into account the value pK w -14, pK 2 -10, and
pH values <<10, it follows that in any case:
OH - CO3°
« <<1
HCO 3 HCO3_
so that the equation of electric neutrality [Equation (5)] takes
the simpler form:
Ca++ - X + H+ = HCO3 . ( 7)
The determination of calcocarbonic equilibria thus results
from the resolution of the system of Equations (1), (2), (3), and
(7). This system can be solved in various situations, as il-
lustrated in Table 1.
It seems to follow that the total number of cases is quite
high. However, production waters are basically of the genera)
type, while the test solutions in the laboratory are almost
always of the NaCI or CaCl 2 type. 21
In order to really understand the imbricated effects of 00 2
dissolution, alkalinity, calcium content, and calcareous
saturation, we reviewed the laws of pH variation for the first
four main types of solutions.
Acidity of the Simple Types of Solutions
Solutions of the Inert Type (NaCI). In the total lack of any
dissolution of calcite (X = Ca+ + = 0), the pH of an NaCI solu-
tion having dissolved 00 2 is given by Equations (1) and (7)
which becomes:
H + = H CO 3 ~ = JR1P (8)
or:
1 1
pH w = 2 pK, - 2 log P (9)
and results in the equation proposed by de Waard and
Milliams 8
Solutions of the Purely Calcic Type (CaCl 2 ). By com-
parison with the previous case, adding stoichiometric calcium
salts other than the bicarbonate (X = Ca+ +) does not change
the equation of electric neutrality [Equation (7)]. The solution
pH thus keeps the same value pH w . Besides, the dissolution of
CO 2 introduces bicarbonate Tons into the solution which did
not originally exist. The solubility product of calcite is then
defining in a very genera) way an upper limit Ca s for the
calcium content, given by Equations (4), (1), and (2):
Ks
Cas = K
1 K 2 P H (10)
which may be written as:
p Ca s = 2pH - 2pHw - L,K (11)

- E = 2 X. Keeping
( 2 )Poirier's diagrams use the definition E where
this notation, however, would add unnecessary complica-
tions to the present equations. LK = pK 2 - pK s > 0.

Vol. 39, No. 2, February, 1983 41


pH, pCa
CaCl2
8 CALCIUM
p" ' BICARBONATE
6 \
pH
calc
4
CARBON IC
ACID
pA pH
p a Bica
CaCIZ ^3
pCa
PCCak
0 pHw
CALCITE
SATURATION
_AK Pe
.001 .1 10 MPa
logP
FIGURE 2 — Effect of the CO2 partial pressure upon the
pH and the calcite saturation of a production water,
general case (Cao <1 meq).
Since pH = pH w , it is obvious that apart from extremely
concentrated brines (pCa < - OK), it is impossible to reach
the calcareous saturation in a solution of the purely calcic
type by simply dissoiving CO2.
Solutions of the Purely Bicarbonated Type (NaHCO 3). The
conditions of electric neutrality [Equation (7)] then becomes:
H+ + Alk = HCO3 - . (12)
Under a low pressure of CO2 , the content Alk in native
bicarbonate ions remains much higher than that induced by
the dissolution of CO 2 so that Equation (12) reduces to:
HCO3 - = Alk . (13)
From Equations (13) and (1), acidity is then:
pHbi ca = 2 PH w - p Alk = cst - log P . (14)
Under a high pressure of CO2, the content in native bicar-
bonate ions may become negligible with regards to those in-
duced by the dissolution of CO2. Equation (12) is then identical
to Equation (8), and pH again has the value pH w. In both cases,
no calcareous saturation is possible.
Solutions of the Stoichiometric Type (Ca(HCOI]. As
previously discussed, the presence of calcium did not modify
the pH of CO2 solutions. As far as the saturation of calcite is
not reached, a calcareous solution then behaves as an or-
dinary bicarbonate (pAlk = pCa), and its pH value is either
pH w under high pressures, or under intermediate pressures:
42 CORROSION—NACE
pHbica = 2 PH w - pCa = cst - log P . (15)
This last law is also valid for supersaturated solutions when
calcite is not precipitating.
At low pressure, when saturation with an effective
precipitation of calcite is achieved, the system of equations to
be solved became:
Ca++ + H+ = HCO3 - (16)
pCa = pCas . (17)
Thus, the case Ca ++ <H + is again impossible since it would
correspond to unrealistic calcium contents (pCa = - AK <0).
Hence, Ca+ + >> H + and pH became:
4 AK 2
pHcalc = 3 pH w +3 = cst - 3 log P
O
18
and the solubility of calcium in equilibrium with calcite is then:
2 AK 1
pCacalc = 3 pH w - 3 = cst - —log P 19
O
This solubility law was effectively checked experimentally in
the domain of high pressures and temperature. 22
The straight lines representing the four functions pH w,
pHbica, pH ca lc , and pCacalc are shown in Figure 2. These
graphs define three domains, where apart from "inert" salt
species (noted as characteristic 13 ) of the NaCI type, the pre-
ponderant fundamental species are for decreasing PCO , the
carbonic acid not saturated in calcite, then the calcium 6icar-
bonate also not saturated in calcite, and then saturated. The
calcium content is first the unsaturated value pCa, and then
the solubility limit pCacalc. pH, however, follows three dif-
ferent successive laws: two in the domain of no saturation,
pHw and then pHbica; and one in the saturation domain
PHcalc.
General Case (CaC/2 + NaHCO 3)
Next is considered a water containing, besides inert salts,
calcium (content Cao) and bicarbonates (Alk > 0) in any pro-
portion. Strong acids are excluded (then Cao > X). In this case,
Equation (16) is replaced by the general equation coming from
Equations (7) and (1):
K1P
Ca*+ -X+H+ =HCO 3 -
H + (20)
which raises two possibilities to be considered.
1. X is Negligible. The contents in calcium and bicar-
bonate in the water analysis are negligible before the contents
induced by the dissolution of calcite or CO 2 under pressure.
Then Equation (20) reduces to Equation (16), and all the for-
mulas of the stoichiometric type solutions will apply.
2. X is No Longer Negligible. The case X <0 is excluded
since it corresponds to the dissolution of calcite in a pre-
ponderant bicarbonate other than Ca (HCO 3 )2 , Le., in NaHCO 3 .
This case does not really correspond to any analysis of pro-
duction waters, which are always of the type preponderant
CaC1 2 (Cao > Alk, then X > 0). Equation (20) then becomes:
Ca+++H+=k. (21)
In practice, H+ is always lower than Ca o , and therefore also
lower than Ca so that Ca+ + = X = Ca o - Alk. Since experi-
mentally Ca o is always much larger than Alk, the calcareous
saturation of a solution of preponderant CaCl 2 always corre-
sponds to a calcium content very close to its initial content:
PCaCaCl 2 ~ P \ • (22)

log 1-'
FIGURE 3 — Effect of the CO 2 partial pressure upon the
pH and the calcite saturation of a production water with
a high calcium content (Ca o >100 meq).
The pH of the saturated solution is then directly given by Equa-
tions (22) and (11):
PHCaCl 2 = PHw + p 2 K = cst - 1 log P . (23)
The straight lines representing pHCaCl2 are also shown in
Figure 2. Although the lines of Figure 2 are just asymptotic
laws, they do enable a better comprehension of the succes-
sion of different domains corresponding to the evolution of
preponderant species with an increasing pressure of CO 2 . The
system of equations may also be solved more precisely with
numerical methods. However, this is only notable for the ac-
tual compositions of production waters which can be effec-
tively encountered in the practice.
Practical Cases
Physical Reality of the Studied Cases. In the domain of
the low partial pressures of CO 2 , the calcareous content of a
water in equilibrium with the atmosphere (PCO 2 -- 10 -5 MPa)
is always very low (<1 meq). On the other hand, all production
waters exhibit more than 1 meq Ca+ +. So, they must all be
considered as of the type preponderant CaCl 2 in the condi-
tions of their analysis, whatever their content in NaCI or other
metallic salts.
Results also show that a water of the NaCI type may be
encountered only in laboratory tests, or in a gathering or
transport line, when the condensation of water vapor occurs
below a separator. Above the separator, even in a gas welt
where the water at the welt head comprises 99% of condensa-
tion water, the production water is always considered as of the
type preponderant CaC12. On the other hand, for very high par-
tial pressures of CO 2 , all the domain with pH <2 in Figure 2 is
totally inaccessible in any actual situation. Point A, in par-
ticular, is essentially for the graphical construction of Figure
2.
Vol. 39, No. 2, February, 1983 43
pH, pCa
FIGURE 4— Enlargement of Figure 3 in the range of the
CO2 partial pressures encountered in the field.
In the intermediate pressure range, the transitions be-
tween the domains preponderant calcium chloride, calcium
bicarbonate, or even carbonic acid may really occur under the
PCo 2 encountered in wells only when X is particularly low.
Thus, in 0.5 M NaCI at room temperature (Figure 2), the type
preponderant carbonic acid cannot be obtained when the
calcium content exceeds 1 meq. In the same way, a water with
a content Ca o > 100 meq wilt always remain of the type
preponderant CaCl 2 whatever the partial pressure of CO 2 in the
welt. This case is by far the most frequent in practice, as
shown by the analysis sheets of production waters, and
therefore requires a more detailed study.
The Frequent Case of Concentrated CaC1 2 Solutions (Cao
> 100 meq). Besides a high Ca o content, the analyses of pro-
duction waters also most of ten exhibit a non-negligible
alkalinity (Alk ~ 1 to 30 meq) denoting some supersaturation
of the solution in calcite. Therefore, pH is no longer controlled
by the calcareous saturation [Equation (18)], but by the
alkalinity [Equation (14)]:
PHAIk = 2 pHw - pAlk. (24)
The equilibrium pressure of CO 2 is then defined by pHAlk =
PHCaCl 2 , which corresponds to a pressure P e such as:
pHAlk = PHCaC1 2 = pAlk + p X + A K. (25)
Three possible graphical constructions are shown in
Figures 3 and 4 (points B, C, D, and E). For CO 2 pressures
higher than the equilibrium pressure P e , the pH of unsaturated
solutions follows the curve pHAlk (here pH w is inaccessible to
experiment).
 pH
pH pH
5 5
4 . 0
CO2 CH4 +23%CO2 oC

• \ 74
a 7a • 4 \\ OC
316 .5
:N ^.^:^ 1 \ S
72

16
3 N3
a
3.0
0.1 1PCO2b
MPa10.01 0.1 1 MPa

0.1 1 X PCO2 10 MPa

FIGURE 5 - Variation of the pH of a 0.5 M NaCI solution FIGURE 6 - Variations of the pH of a 0.5 M NaCI solution
with CO2 partial pressure: (a) pure CO2 ; and (b) mixture with the fugacity XPCO 2 of pure CO2.
77% CH 4 + 23% CO 2 .

Synthesis TABLE 2 - pH Values of NaCI Solutions From

These theoretical, but rather simple statements lead to the 0 to 3.5 M, Under 0.1 MPa of Pure CO 2 at 25 C
conclusion that the acidity of a production water depends as
much upon its content in native bicarbonate ions as upon the
dissolution and pressure of CO 2 . These ions indeed are able to M NaCI 0 0.05 0.1 0.5 1 1.75 3.5
pH 3.94 3.89 3.91 3.78 3.76 3.64 3.57
considerably shift the dissociation equilibrium of carbonic
acid.
The calcium content as such has no direct effect. Never-
theless, through the solubility product of calcite in saturated quantitative point of view, however, the observed pH dif-
solutions, it may also shift the equilibrium of bicarbonates and ferences are not much higher than experimental errors.
then indirectly modify the pH. Effect of Temperature. Figures 5 and 6 show that an in-
crease in temperature shifts the lines pH = f (log Pco). These
differences are far from negligible beside the proper e effects of
PCO 2 , but the temperature effect remains rather low when
Resuits
compared to the effects of the chemical composition of pro-
The above effects, which may appear somewhat intricate,
duction waters.
were all perfectly verified by experiments.
Influence of NaCI Content. Table 2 shows the pH values
of NaCI solutions. The variations appear quite negligible;
Solutions of NaCI Alone
therefore, the acidizing of water by dissolving CO 2 is not in-
Without other indications, all the tests were carried out
fluenced in practice by its total salinity.
with a 0.5 M NaCI solution (analytical grade), under a pressure
of pure CO 2 (Air liquide,(') grade N 45).
Effect of CO 2 Partial Pressure. Figure 5 shows that for
Bicarbonated Solutions
Figure 7a shows the effect of the bicarbonate content
pure 00 2 , as well as for a mixture CH 4 + CO2, the solution pH
(NaHCO 3) upon the pH of a 0.5 M NaCI solution under 0.1 MPa
follows a law in 0.5 log PCO2 , as expected from Equation (10).
of pure 00 2 . For comparison, Figure 7b shows the effect of the
These resuits were also checked and verified as closely cor-
CO 2 pressure for a 0.5 M NaCI solution with 10 meq HCO 3 . -
responding to the extension of low pressure values in the
Equation (14) (pHbica) applies particularly well here.
1 iteratu re.7,8,21'23
It must also be emphasized that the pH variations of
As mentioned previously, the pH measures under 0.1 MPa
Figure 7 are much more important than those of Figure 5. More
appear to have shifted from the extrapolation of the measures
precisely, the effect of the relative variations of alkalinity is
under pressure. On the other hand, the curvature of the
proved to be exactly the same as that of the relative variations
"straight lines" at high pressure is simply due to the Past varia-
of PCO 2 (Slope 1). As expected, it was also confirmed that the
tion of the fugacity f of 00 2 (f = XP) when the critical pressure
effect of the relative variations of PCO 2 are twice as strong in
is approached. By using the X values of literature, 24 it was con-
this bicarbonated NaCI solution as in the same solution free of
firmed that the curves pH = f (log XP) remained fairly straight
bicarbonate.
up to the critical pressure (Figure 6).
Figure 8 shows how the pH is affected by the dissolution
Effect of the CO2 Content of the Gas. By comparing the of calcite in 0.5 M NaCI or 0.25 M CaCl 2 solutions. At room
pH measures carried out with pure 00 2 or with a mixture 77% temperature, the dissolution of 1 to 2 gll of calcite enhances
CH 4 + 23% CO 2 (Figure 5), a shift of nearly 0.2 pH unit be- the pH by 1 to 2 units. The slopes of these lines also corre-
tween pure and diluted 00 2 was observed for the same partial spond effectively to the theoretical forecasting: slope 1 for 0.5
pressure of CO 2 . Thus, one finds again with methane an effect M NaCI not saturated with calcite [Equation (15)]; slope 213 for
already known for mixtures 00 2 + N 2 or H 2 ; 25 namely, that the 0.5 M NaCI saturated with calcite [Equation (19)]; and slope 112
proper solubility of 00 2 decreases with the increasing for CaCl 2 0.25 M saturated with calcite [Equation (23)].
simultaneous dissolution of other gases. For example, con-
cerning the acidifying induced by the 00 2 dissolution in water, Discussion
a partial pressure P for a crude gas with - 25% CO 2 would be The purpose of this study is not to assess definitive pH
equivalent only to a -112 P pressure for pure 00 2 . From a values, as that would only be of limited application. The alm is

44 CORROSION-NACE
 pH • 4 pH
////
6 a s b
5 L5 ^\
//
.
HCO3 4 co
).1 1 10 100 meq 01 1 2
FIGURE 7 — Variations of the pH of a 0.5 M NaCI solution:
(a) with its bicarhonate content under 0.1 MPa of pure CO 2 ;
and (b) with 10 meq bicarbonate and a variable pressure of
pure CO 2 .
rather to aid in the understanding of the physical chemistry of
production waters, which is why theoretical aspects are em-
phasized.
The essential results show that the acidity of a production
water depends as much upon its alkalinity as upon the partial
pressure of 00 2 . Therefore, this acidity of production waters
cannot be represented by solutions of NaCI alone, even under
high pressures of CO2 . This probably explains the failure of re-
cent laboratory studies 610 in reproducing either the rates or
the forms of the 00 2 corrosion in wells.
Moreover, the chemical species considered in this study
are not the only ones liable to interact in the acidifying of
water. The anions of weak organic acids, acetates, pro-
pionates, etc. may also induce some buffering power through
their respective reassociation into acetic acid, propionic acid,
etc. Studies are currently being carried out to ascertain this
point. In the same way, the solubility of ferrous carbonate may
also play a locally decisive role at the surface of a corroding
steel. Again, the looped interactions pH — solubility —
hydrolysis -- pH are being studied.
This study also has an unexpected consequence on the
laboratory tests of the sulfide stress cracking. Hydrosulfuric
acid (H 2S) has nearly the same strength as carbonic acid;
therefore, in cold solutions of only NaCI, very high pressures
of H 2 S might well acidify water down to — pH 3 just as 00 2
does. Nevertheless, bicarbonated alkalinity plays here the
same buffering role as with 00 2 . Depending on the degree of
the global reassociation reaction HCO 3 + H 2 S — HS - -
H20 + 002, pH will be controlled either by the CO2/HCO3 or
the H2S/HS buffer. Regardless of the controlling buffer, it is
-
not possible for the pH to become as low as in a solution of
NaCI alone.
The results show then, that the acidity of the test solution
recommended by NACE in the TM-01-77, which is nearly pH 3,
is certainly much more severe than what can be reasonably
imagined in a well. Taking into account Figure 7b, a value of
pH 4 would certainly be more relevant. 26
Conclusions
The present theoretical and experimental study of the
calcocarbonic equilibria in solutions of 00 2 under pressure
allows a better understanding of both the diversity of the
observations in the field and the failure of laboratory simula-
tions in oversimplistic media. In particular, the present study
suggests that the acidity of a production water depends as
Vol. 39, No. 2, February, 1983 45
pH 0.5M Na I pH 0.25M cacl 2
. b ó 2/3
saturation saturation
5 °^ 1 g/I CaCO3 5 a^, 1/2 g/1 CaCO3
° 1 \ 10
4 4
0.5
MR,
\.\• 3 b Pc02
c02
.3a
0.1 1 10 MPa 0.1 MPa
FIGURE 8 — Effect of the pressure of pure CO 2 upon the
pH of a solution of: (a) 0.5 M NaCI; and (b) 0.25 M CaCl 2
with increasing calcite contents, up to saturation.
much upon its alkalinity as upon the partial pressure of 00 2 .
Therefore, this acidity cannot be represented by solutions of
NaCI alone, even under the actual pressure of 00 2 . The actual
pH values of production waters are probably, on the average,
higher by 1 or 2 units than in similar NaCI media with the same
temperature and the same pressure of 00 2 . In the same way,
the acidity of the corrosive medium in the NACE SSC test is
probably too strong by nearly 1 pH unit, with respect to what
can reasonably be imagined in wells with H 2 S.
References
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799 (1979).
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1084 (1962).
 18. Agrawal, A. K. and Staehle, R. W., Corrosion, Vol. 33, No.
11, p. 418 (1977).
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(Paper No. 135), Houston, Texas.

A Comparison of Intergranular Attack

in Inconel Alloy 600 Observed in
the Laboratory and in
Operating Steam Generators*

G. P. AIREY and F. W PEMENT*

Abstract
Intergranular attack (IGA) has been observed in Inconel 600 tubing on the hot leg of some
operating steam generators. IGA has also been reproduced in the laboratory in both high
temperature (316-343 C) sodium hydroxide solutions and environments containing sulfur com-
pounds such as polythionic acid and sodium tetrathionate. The degradation morphology and
associated chemical species were compared in tubing from two steam generators and tubing
exposed to the above laboratory environments. The tubing was subjected to a detailed micro-
structural analysis. There was a mixture of IGA and SCC in tubing from the steam generators
and that exposed to laboratory caustic environments, whereas only IGA was present in
material exposed to sodium tetrathionate. Grain boundary carbide precipitation and an
associated chromium depleted layer were necessary for IGA in sodium tetrathionate. Such a
microstructure was not present in the tubing removed from the steam generators. It was con-
cluded that, of the two environments evaluated, caustic was more likely to have instigated
IGA in the steam generators.

Introduction
Most nuclear steam generators in pressurized water reactor
nuclear power plants use U-bent tubes of milt annealed In-
conel 600 (Ni-Cr-Fe) in a vertical configuration with the tube-
sheet at the bottom. Reactor coolant circulates through the
tubes, entering at about 316 C (600 F) and —15.5 M Pa (— 2250
psi), and exiting at 30-35 C (50-60 F) lower. The outer surfaces
of the tubes contact conventional power plant boiler waters
which boil to produce steam. The boiler water is low in dis-
soived solids, deoxygenated, and slightly alkaline, which are
conditions usually maintained by AVT (all-volatile treatment)
water chemistry.
Sludge and scale can accumulate on the top surface of
the tubesheet and on outer surfaces of the tubes within the
tubesheet. In many units, an annulus exists between tube and
tubesheet, except for the lowest several inches of tubing
which were expanded against the tube hole in fabrication.
Figure 1, adapted from Green and Paine,' illustrates the an-
nulus geometry and sludge/scale buildup. Occasional in-
stances of corrosion induced tube degradation have occurred
in areas of sludge buildup; these include wastage (or thinning)
*Submitted for publication April, 1982; revised July, 1982.
*Westinghouse R&D Center, Pittsburgh, Pennsylvania.
0010-9312/83/000017/$3.00/0
46 1983, National Association of Corrosion Engineers CORROSION—NACE
and stress corrosion cracking (SCC) above the tubesheet, SCC
within the tubesheet, and intergranular attack (IGA) within the
tubesheet. 1-3 All SCC has been intergranular and both SCC
and IGA have occurred only on the hot legs (inlet sides) of the
tube bundle. The annulus region can contain physically and
chemically complex environments in zones of wetting, alter-
nate wetting and drying, and steam blanketing with sludge
(largely iron oxide), scale and soluble species containing ions
or compounds of Na, K, Si, P, S, Ca, and others.
The mechanism(s) of intergranular degradation processes
(IGA or SCC) in high-nickel alloys may not be considered well-
established, and considerable experimental research is cur-
rently in progress. This paper compares resuits from one such
research program with features of the IGA on Inconel tubes
removed from two operating plants.
Experimental Procedures
Materials
All of the laboratory tested material was commercial In-
conel 600 steam generator tubing. Five heats were exposed to
caustic environments in both the milt annealed and thermally
treated (1300 F/15 hours) conditions. The composition and