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

0010-9312/83/000015/$3.00/0
Vol. 39, No. 2, February, 1983 1983, National Association of Corrosion Engineers 39

~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
FIGURE 1 — Sketch of the pH meter. (1) Glass electrode; parameter, but only the resuit of different equilibria. The ex-
(2) reference electrode; (3) autoclave body; (4) oil com- pression of these equilibria here must therefore have a form
partment; (5) piston; (6) self sealing PTFE gasket; (7) differing from traditional presentations in the literature. 1114
threaded plug; (8) electrical junction; (9) quartz sleeve;
Thus, before considering experimental results on the varia-
(10) flat grounded quartz plate; (11) PTFE film; (12)
tions of pH with the partial pressure of 00 2 it appears
,

magnetic stirrer; (13) bubbling of the gas under pressure;


necessary to express these calcocarbonic equilibria in a new
and (14) test solution.
and more appropriate form.
Chemical Species
(10)], and PTFE films [Figure 1, (11)] enabled us to ensure both In general, chemical species present in production water
a tight seal under 100 MPa and an electrical isolation of the are:
order of 10 5 MSZ in a dry atmosphere. Although such a rigorous 1. The dissociation products of water, H+ and OH - .
isolation was not necessary for the electrical junctions to the 2. The dissociation products of carbonic acid, bicar-
magnetic stirrer [Figure 1, (12)), the same fitting technology bonate HCO 3 - , and carbonate CO 3 ions.
was also used. 3. Anions from strong acids CI - , SO 4 =, etc.
The heating and cooling of the autoclave was achieved by 4. Metallic cations, either alkaline Na+, K+, or alkaline
external resistors and coiled water tubes. Temperature varia- earth Ca++ Mg++ etc.
tions were kept at less than ±1 C. The exact temperature Concentrations are expressed here in equivalents per liter
value was measured inside the autoclave by a copper- (= valency x number of mole/I). For some important species,
constantan thermocouple. The autoclave was fed with gas concentrations are also expressed as for pH on a logarithmic
mixtures which bubbled [Figure 1, (13)] through the test solu- scale: pX = - log X.
tion [Figure 1, (14)]. It was pressurized by means of a high
pressure pumping facility. Ancillary capacities and external
Reactions
In reservoir waters, the chemical species which are likely
lines under high pressure were heated to -70 C, to prevent
to precipitate first are calcite CaCO 3 , followed by M9CO 3 or
any parasitic liquefaction of the 00 2 during pressurizing.
CaSO 4 11,12 This study, however, wilt be limited to the case
.
The curves pH = f (PCO 2) were always taken in the sense
when only calcareous saturation is likely to be reached.
of increasing pressures. Indeed, in the reverse sense, degas-
Therefore, the only possible reactions are the two successive
sing delays always induced large 00 2 supersaturations in the
dissociations of carbonic acid, the dissociation of water, and
test solutions. Modified reference electrodes were sometimes
eventually the solubility product of calcite. The mass action
used for pH measurements in the presence of H 2 S. They were
laws of these four equilibria are:
based on the classical system of porous extensions, 17 18 allow-
'

ing the delay of the H 2 S diffusion towards the sensitive


H + • HCO 3 -

Ag/AgCI element.
P K, (1)
Calibration H+.0O 3 =
The quality of classical pH meters lies mainly in the quali- =K
ty of calibration. For measurements under atmospheric HCO 3 (2) 2
pressure, calibration was carried out just before and just after
the measurement, at the test temperature, and with buffer H+•OH - =Kw (3)
solutions for which the pH variations with temperature were
welt known (Tacussel T 6 PKN = phosphate buffer with pH Ca++ •CO3 = = Ks (4)

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


pHbica = 2 PH w - pCa = cst - log P . (15)
pH, pCa
This last law is also valid for supersaturated solutions when
CaCl2 calcite is not precipitating.
At low pressure, when saturation with an effective
precipitation of calcite is achieved, the system of equations to
8 CALCIUM be solved became:

p" ' BICARBONATE Ca++ + H+ = HCO3 - (16)

pCa = pCas . (17)


6 \
pH Thus, the case Ca ++ <H + is again impossible since it would
calc correspond to unrealistic calcium contents (pCa = - AK <0).
Hence, Ca+ + >> H + and pH became:
4
4 AK 2
CARBON IC pHcalc = 3 pH w +3 = cst - 3 log P
O
18
ACID
pA pH
p a Bica and the solubility of calcium in equilibrium with calcite is then:
CaCIZ ^3
pCa 2 AK 1
PCCak pCacalc = 3 pH w - 3 = cst - —log P 19
O
0 pHw
This solubility law was effectively checked experimentally in
the domain of high pressures and temperature. 22
CALCITE The straight lines representing the four functions pH w,
SATURATION pHbica, pH ca lc , and pCacalc are shown in Figure 2. These
graphs define three domains, where apart from "inert" salt
_AK Pe species (noted as characteristic 13 ) of the NaCI type, the pre-
ponderant fundamental species are for decreasing PCO , the
.001 .1 10 MPa carbonic acid not saturated in calcite, then the calcium 6icar-
bonate also not saturated in calcite, and then saturated. The
logP calcium content is first the unsaturated value pCa, and then
the solubility limit pCacalc. pH, however, follows three dif-
FIGURE 2 — Effect of the CO2 partial pressure upon the ferent successive laws: two in the domain of no saturation,
pH and the calcite saturation of a production water, pHw and then pHbica; and one in the saturation domain
general case (Cao <1 meq). PHcalc.

General Case (CaC/2 + NaHCO 3)


Since pH = pH w , it is obvious that apart from extremely Next is considered a water containing, besides inert salts,
concentrated brines (pCa < - OK), it is impossible to reach calcium (content Cao) and bicarbonates (Alk > 0) in any pro-
the calcareous saturation in a solution of the purely calcic portion. Strong acids are excluded (then Cao > X). In this case,
type by simply dissoiving CO2. Equation (16) is replaced by the general equation coming from
Solutions of the Purely Bicarbonated Type (NaHCO 3). The Equations (7) and (1):
conditions of electric neutrality [Equation (7)] then becomes: K1P
Ca*+ -X+H+ =HCO 3 -

H+ + Alk = HCO3 - . (12) H + (20)


which raises two possibilities to be considered.
Under a low pressure of CO2 , the content Alk in native 1. X is Negligible. The contents in calcium and bicar-
bicarbonate ions remains much higher than that induced by bonate in the water analysis are negligible before the contents
the dissolution of CO 2 so that Equation (12) reduces to: induced by the dissolution of calcite or CO 2 under pressure.
Then Equation (20) reduces to Equation (16), and all the for-
HCO3 - = Alk . (13) mulas of the stoichiometric type solutions will apply.
2. X is No Longer Negligible. The case X <0 is excluded
From Equations (13) and (1), acidity is then: since it corresponds to the dissolution of calcite in a pre-
ponderant bicarbonate other than Ca (HCO 3 )2 , Le., in NaHCO 3 .
pHbi ca = 2 PH w - p Alk = cst - log P . (14) This case does not really correspond to any analysis of pro-
duction waters, which are always of the type preponderant
Under a high pressure of CO2, the content in native bicar- CaC1 2 (Cao > Alk, then X > 0). Equation (20) then becomes:
bonate ions may become negligible with regards to those in-
Ca+++H+=k. (21)
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. In practice, H+ is always lower than Ca o , and therefore also
Solutions of the Stoichiometric Type (Ca(HCOI]. As lower than Ca so that Ca+ + = X = Ca o - Alk. Since experi-
previously discussed, the presence of calcium did not modify mentally Ca o is always much larger than Alk, the calcareous
the pH of CO2 solutions. As far as the saturation of calcite is saturation of a solution of preponderant CaCl 2 always corre-
sponds to a calcium content very close to its initial content:
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: PCaCaCl 2 ~ P \ • (22)

42 CORROSION—NACE
pH, pCa

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).

FIGURE 4— Enlargement of Figure 3 in the range of the


CO2 partial pressures encountered in the field.
The pH of the saturated solution is then directly given by Equa-
tions (22) and (11):

In the intermediate pressure range, the transitions be-


PHCaCl 2 = PHw + p 2 K = cst - 1 log P . (23) tween the domains preponderant calcium chloride, calcium
bicarbonate, or even carbonic acid may really occur under the
The straight lines representing pHCaCl2 are also shown in PCo 2 encountered in wells only when X is particularly low.
Figure 2. Although the lines of Figure 2 are just asymptotic Thus, in 0.5 M NaCI at room temperature (Figure 2), the type
laws, they do enable a better comprehension of the succes- preponderant carbonic acid cannot be obtained when the
sion of different domains corresponding to the evolution of calcium content exceeds 1 meq. In the same way, a water with
preponderant species with an increasing pressure of CO 2 . The a content Ca o > 100 meq wilt always remain of the type
system of equations may also be solved more precisely with preponderant CaCl 2 whatever the partial pressure of CO 2 in the
numerical methods. However, this is only notable for the ac- welt. This case is by far the most frequent in practice, as
tual compositions of production waters which can be effec- shown by the analysis sheets of production waters, and
tively encountered in the practice. therefore requires a more detailed study.

Practical Cases The Frequent Case of Concentrated CaC1 2 Solutions (Cao


Physical Reality of the Studied Cases. In the domain of > 100 meq). Besides a high Ca o content, the analyses of pro-
the low partial pressures of CO 2 , the calcareous content of a duction waters also most of ten exhibit a non-negligible
water in equilibrium with the atmosphere (PCO 2 -- 10 -5 MPa) alkalinity (Alk ~ 1 to 30 meq) denoting some supersaturation
is always very low (<1 meq). On the other hand, all production of the solution in calcite. Therefore, pH is no longer controlled
waters exhibit more than 1 meq Ca+ +. So, they must all be by the calcareous saturation [Equation (18)], but by the
considered as of the type preponderant CaCl 2 in the condi- alkalinity [Equation (14)]:
tions of their analysis, whatever their content in NaCI or other
metallic salts. PHAIk = 2 pHw - pAlk. (24)
Results also show that a water of the NaCI type may be
encountered only in laboratory tests, or in a gathering or The equilibrium pressure of CO 2 is then defined by pHAlk =
transport line, when the condensation of water vapor occurs PHCaCl 2 , which corresponds to a pressure P e such as:
below a separator. Above the separator, even in a gas welt
where the water at the welt head comprises 99% of condensa- pHAlk = PHCaC1 2 = pAlk + p X + A K. (25)
tion water, the production water is always considered as of the
type preponderant CaC12. On the other hand, for very high par- Three possible graphical constructions are shown in
tial pressures of CO 2 , all the domain with pH <2 in Figure 2 is Figures 3 and 4 (points B, C, D, and E). For CO 2 pressures
totally inaccessible in any actual situation. Point A, in par- higher than the equilibrium pressure P e , the pH of unsaturated
ticular, is essentially for the graphical construction of Figure solutions follows the curve pHAlk (here pH w is inaccessible to
2. experiment).

Vol. 39, No. 2, February, 1983 43


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
pH 0.5M Na I pH 0.25M cacl 2
//// . b ó 2/3
6 a s b saturation saturation


5 °^ 1 g/I CaCO3 5 a^, 1/2 g/1 CaCO3

5 L5 ^\
° 1 \ 10
//
4 4
0.5
.
HCO3 4 co
).1 1 10 100 meq 01 1 2 MR,
\.\• 3 b Pc02
c02
.3a
0.1 1 10 MPa 0.1 MPa

FIGURE 7 — Variations of the pH of a 0.5 M NaCI solution: FIGURE 8 — Effect of the pressure of pure CO 2 upon the
(a) with its bicarhonate content under 0.1 MPa of pure CO 2 ; pH of a solution of: (a) 0.5 M NaCI; and (b) 0.25 M CaCl 2
and (b) with 10 meq bicarbonate and a variable pressure of with increasing calcite contents, up to saturation.
pure CO 2 .

much upon its alkalinity as upon the partial pressure of 00 2 .


rather to aid in the understanding of the physical chemistry of Therefore, this acidity cannot be represented by solutions of
production waters, which is why theoretical aspects are em- NaCI alone, even under the actual pressure of 00 2 . The actual
phasized. pH values of production waters are probably, on the average,
The essential results show that the acidity of a production higher by 1 or 2 units than in similar NaCI media with the same
water depends as much upon its alkalinity as upon the partial temperature and the same pressure of 00 2 . In the same way,
pressure of 00 2 . Therefore, this acidity of production waters the acidity of the corrosive medium in the NACE SSC test is
cannot be represented by solutions of NaCI alone, even under probably too strong by nearly 1 pH unit, with respect to what
high pressures of CO2 . This probably explains the failure of re- can reasonably be imagined in wells with H 2 S.
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 References
are not the only ones liable to interact in the acidifying of 1. Skaperdas, G. T. and Uhlig, H. H., Ind. Eng. Chem., Vol. 34,
water. The anions of weak organic acids, acetates, pro- No. 6, p. 748 (1942).
pionates, etc. may also induce some buffering power through 2. Hackermann, N. and Shock, D. A., lnd. Eng. Chem., Vol. 39,
their respective reassociation into acetic acid, propionic acid, No. 7, p. 863 (1947).
etc. Studies are currently being carried out to ascertain this 3. Hackermann, N. and Schmidt, H. R., Ind. Eng. Chem., Vol.
point. In the same way, the solubility of ferrous carbonate may 41, No. 8, p. 1712 (1949).
also play a locally decisive role at the surface of a corroding 4. Bilhartz, H. L., Pet. Eng., Vol. 24, No. 11, p. B78 (1952).
steel. Again, the looped interactions pH — solubility — 5. Greenwell, H. E., Corrosion, Vol. 9, No. 9, p. 307 (1953).
hydrolysis -- pH are being studied. 6. Fokin, M. N. and Borisova, T. V., Protection of Metals,
This study also has an unexpected consequence on the Vol. 12, No. 6, p. 575 (1976).
laboratory tests of the sulfide stress cracking. Hydrosulfuric 7. Schmitt, G. and Rothmann, B., Werk. u. Korr., Vol. 28, No.
acid (H 2S) has nearly the same strength as carbonic acid; 12, p. 816 (1977); Vol. 29, No. 2, p. 98 (1978); and Vol. 29, No.
therefore, in cold solutions of only NaCI, very high pressures 4, p. 237 (1978).
of H 2 S might well acidify water down to — pH 3 just as 00 2 8. de Waard, C. and Milliams, D. E., Corrosion, Vol. 31, No. 5,
does. Nevertheless, bicarbonated alkalinity plays here the p. 177 (1975).
same buffering role as with 00 2 . Depending on the degree of 9. Gratacos, J., SNEA (P), unpublished results.
the global reassociation reaction HCO 3 + H 2 S — HS - - + 10. Brelin, J. L. and Guntz, G., Rev. Metall., Vol. 76, No. 12, p.
H20 + 002, pH will be controlled either by the CO2/HCO3 or -
799 (1979).
the H2S/HS buffer. Regardless of the controlling buffer, it is
-
11. Ostroff, A. G., Introduction to Oilfield Water Technology,
not possible for the pH to become as low as in a solution of NACE, Houston, Texas (1979).
NaCI alone. 12. Schoeller, H., Geochemistry of Subterranean Waters-
The results show then, that the acidity of the test solution Application to Petroleum Formation Waters, Revue de
recommended by NACE in the TM-01-77, which is nearly pH 3, I'Institut Francais du Pétrole et Annales des Combustibles
is certainly much more severe than what can be reasonably Liquides, Vol. 10, No. 4 (1955).
imagined in a well. Taking into account Figure 7b, a value of 13. Labbe, J. P., Materiaux et Techniques, Vol. 67, No. 12,
pH 4 would certainly be more relevant. 26 p. 423 (1979).
14. Leroy, P., Materiaux et Techniques, Vol. 67, No. 12, p.
Conclusions 432 (1979).
The present theoretical and experimental study of the 15. Disteche, A., The Review of Scientific Instruments, Vol.
calcocarbonic equilibria in solutions of 00 2 under pressure 30, No. 6, p. 474 (1959).
allows a better understanding of both the diversity of the 16. Le Peintre, M., Bull. Soc. Franc. Electriciens, Vol. 8, Tome 1,
observations in the field and the failure of laboratory simula- No. 9, p. 584 (1960).
tions in oversimplistic media. In particular, the present study 17. Disteche, A., J. Electrochem. Soc., Vol. 109, No. 11, p.
suggests that the acidity of a production water depends as 1084 (1962).

Vol. 39, No. 2, February, 1983 45


18. Agrawal, A. K. and Staehle, R. W., Corrosion, Vol. 33, No. 23. Wickert, K., Wiehr, H., and Jahr, H. G., Werks. u. Korr.,
11, p. 418 (1977). Vol. 2, No. 4, p. 125 (1951).
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22. Ellis, A. J., Am. J. Science, Vol. 261, No. 3, p. 259 (1963). (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 and stress corrosion cracking (SCC) above the tubesheet, SCC
Most nuclear steam generators in pressurized water reactor within the tubesheet, and intergranular attack (IGA) within the
nuclear power plants use U-bent tubes of milt annealed In- tubesheet. 1-3 All SCC has been intergranular and both SCC
conel 600 (Ni-Cr-Fe) in a vertical configuration with the tube- and IGA have occurred only on the hot legs (inlet sides) of the
sheet at the bottom. Reactor coolant circulates through the tube bundle. The annulus region can contain physically and
tubes, entering at about 316 C (600 F) and —15.5 M Pa (— 2250 chemically complex environments in zones of wetting, alter-
psi), and exiting at 30-35 C (50-60 F) lower. The outer surfaces nate wetting and drying, and steam blanketing with sludge
of the tubes contact conventional power plant boiler waters (largely iron oxide), scale and soluble species containing ions
which boil to produce steam. The boiler water is low in dis- or compounds of Na, K, Si, P, S, Ca, and others.
soived solids, deoxygenated, and slightly alkaline, which are The mechanism(s) of intergranular degradation processes
conditions usually maintained by AVT (all-volatile treatment) (IGA or SCC) in high-nickel alloys may not be considered well-
water chemistry. established, and considerable experimental research is cur-
Sludge and scale can accumulate on the top surface of rently in progress. This paper compares resuits from one such
the tubesheet and on outer surfaces of the tubes within the research program with features of the IGA on Inconel tubes
tubesheet. In many units, an annulus exists between tube and removed from two operating plants.
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- Experimental Procedures
nulus geometry and sludge/scale buildup. Occasional in-
stances of corrosion induced tube degradation have occurred Materials
in areas of sludge buildup; these include wastage (or thinning) All of the laboratory tested material was commercial In-
conel 600 steam generator tubing. Five heats were exposed to
*Submitted for publication April, 1982; revised July, 1982. caustic environments in both the milt annealed and thermally
*Westinghouse R&D Center, Pittsburgh, Pennsylvania. treated (1300 F/15 hours) conditions. The composition and
0010-9312/83/000017/$3.00/0
46 1983, National Association of Corrosion Engineers CORROSION—NACE