a

-u

! Abstract

anodic and-cathodic processes have

f: . curves. The effect of temperature o
e m f o r the overall corrosion process.,

The prediction of the corrosivity of C02 dissolved in watcr is very ...e aii.. -.the present !.-...&o inv
important in connection with the transport of COzcontaining wet.
, .
natural gas. Except for the combined action of CO with osygeii or
'." H2S. this problem has received little attention.' '
Alihough ii is
recognized that g r b o n i c acid can be..c?m$~e corrosive than a
'
anodic afid catliodic reaction mec.

- - -5.cbmpletely dissociated acid at the 'e*-. -

') ;-

*
qiwha-glanation
a-satishetory
of this fact Iias noi yet been g i v e n 7
Wiih t h e usual formulation of the cathodl reaction y u r r i n i ;
In a first series or experiments, corrosion y t e s mere determiiiw
for polislied cylindrical speciniens (&?= 45 mm. d = 6n.m) macliined _ _ --
f r o m i X - i ~mrbon steel bar. Por i singk run. threesuch specirnen": +.:
G.
i

'L.
... .
: on.st 1 carroding i s P ( . R D = rate determining step):
'

1
were polished with grade 600 emery paper, brushed with
abrasive dcteigent, rinsed with distilled water, and depxased wilh
u mildly . .- -
. .; 4 @

RD acetone after mounting on a tliree-electrode probe, by ineans.of

.h. ..- ~ + + e+ - ti
- ,
! (la) threaded connections, thus providing measuritig; reference and "... *. ''
II - 211 +H2 or H++H++e - + H 2 , i (lb)
auxiliary electrodes. The test medium consisted of u 0.1% NaCl
I soliition through wliich an adjustable mixture oí Coz ancl specially
purilíed oxygen-free N2 was hubbled. Tests were. carried, óut 'jn 1
the relation =en-th~corrosion current (is) ind pH &n always
I be shown to be of the f o r r n ? T k - ~ k ,
about 1 liter of thk solutioti. which was thermost:iited at thc
desired temperature and stirred vigoroiisly in such eway Bat-c-fjw-
' '
.=
.. .
..
I

speed of liquid arouiid lhe electrodes of about, l .in/s .gas uchieved.

log ic = -A. p~ + B
. . -. _~_ ' i (2) ,& - l ~ h corro:ion
e n t e was monitored by means of the linear polarira- . ,;
I , ~ o ~ & * ~ tion teclinique. Tlie instruments used ,werei (1). tlie Petral* 9
When it is assumed that the aiiodic dissolution reaction does not. bc' c~~~~~~~~ ,Rate M ~ ~ ~ model ~ M-lOOO
, (2),a Wenking
depend on pH, A = 1. Bowever, Bockris, Drazic, and ~ e s ~ i c ~ta-p drive? by a Philips (PMS 168) square wave oscillator (10 ,c.
obtained evidence of a-- --
pHdependent mechanism:. I,,~o mV arnplitÜde) with an adjustable dc-bias. ?liis bias was used to . .
b<%'-.!t correct fo the open voltage between reference and iiieasuring
Fe + OH-+FeOH + e-
(3J electrodes. f
:
1 All the readings obtained were correctcd f o r i R d r o ~in tlie
electrolyte; the associated resistance (R)was determincd at regular
N
RD I intervals by impressing a 2 kHz aíiernatingcurrent of known
FeOH + F ~ O H + e- . (3b) amplitiide Lbetween measurkg and ruxiliary electro&s and *ng
t v i n g voltage drop between measuriiig 3nd referen-.&c-v
F ~ O H ++FeZ+ + OH- trodes. This was done wifh the aid of a: Hewlett:Packard.4328A
-.
w h m - i ) e t e r , which gives-a direct'read6"tbf the resi2s.k).
With :;u~ mechanism, the anodic dissolution rafe al anb Constant. me mrrected rerdings vere convert& lo &%$oni&es by m a n s
potential U n v e y G y propo~tionalto the$+ concentralion, wliich . of a mlibration factor which was ,obtained ..by cpmparing time-
, leads to a les$ marked dependence of corrosion rate on PH, A!.%,
about 0.5. Aoother mechanism, proposed by w6leads to A =
integrated readings with the. weight losie+.of the electrodes.
Measurements of the effect of C02 pressuré at. a given !emperalure.
. .
. .?
-0 were made by beginning at a low partial CO; pressure, and after
.
\ '
. reaching ihe steady-state corrosion rate after about 24 hours, raising .
'7
'h.
*~ubmittedfor publication Jaiiuary, 1974.
* ~ ~ ~ i ~ k l i , k ~ / ~~ h ~ ~ ~- (Sheu' ~ ~ b ~~~~~~h
the panial pressure and allowing thiá system to 'rench.its new stcady -
~ ~ ~ ~ ~~ ~ @, ~ i which
~~ ~ ,then only ~ requiredd about 3 hounil'hls
~ ~procedure was
, ,
. ' . ' j

B.V.). repeated with further increases in pressure. <[:;$.:

. ..-
.. .. . 2
,
f.
. . . , .. ...
. .,
: 4 f . ., $
.
,

* ",>3 ,3:
. - .
131
'

CARBON DiOXlDE Reprinted from Corrosion, Vol. 31, No. 5 (1975). ".. .
,
. ..
: .: ;
.. .. -.%*F' ' i\ ,
- . In a second series of experiiiieiits tlie spcciiiieiis)wcrc gril-
blasted before exposure. In tliis Case, weight losscs were cleterniined
corrc)sion r:ilcs r c i ~ i i i i i ~ i ~ ~ l ~ ~lcii
; ~ l )Iiiiics
o i ~ ! iowcr Ih;iii Ihosc I'0r
gil-l>l;istcd spcciii~ciis. 'I'licsc rcsiilts wcrc iiot Ciirllicr iiiken irilo
over longer periods, e.g., *S, while thc corrosion rate was also
- monitored. In these tesis, bottled niixtures of oxygen-frce %an<!
9 were used to ensure constan1 gas composition, and tlie tests
accouiit. I:or ~ l i gril-l>l:isled
c spechiiciis ( 15 (') tlic ;ivcr;ige corrosion
ratc ovcr llic wliolc fiiiic of cxposurc is iiitlic:i!ccl.
Iii 00th cascs. ilic c;ilibrlitioi~ I';ic!!?r l;)r tJc! poI:iri~.:itioii
?
--
were carried out in an autoclave. resiikiticc ineasurciiicnis, wliicli cqii;ils tlic r;ilio oi'corrosion ciirrciil
,
b'
Potentiodynamic polarization curves werc recorded witli labora (lioin weiglil l o s ) ;iii(l polü ri?.al ion i ~ t l i i ~l:i~ic.c
il ( Troiii ~>ol;iriz;it
ion
tory-built potentiostats with a built-in electronic potential sweep incasiircriicnts), viiricd I'rorii riin lo riiii. 'l'lic v:iliic OI'Iliis kiclor wiis
and a logarithmic readout. Scans were rnade going frorn cathodic to 9.5 + 2 niV.
anodic potentials with a speed of 1 mV/s. The tneasuringelcctrodc
was embedded in bakelite, and mechanically
--- polished in successive Influence of C02 Partial Prcssure
steps down to 0.25 p just before use. In these tests, a 1% Na<!I I'hc slope A iii liqualion (2) u n :ilso be dcicrinined rrorii 1i plot.
solution was used as supporling electrolyte. A capillary conncction of log corrosiori r;ilc ag~iiistlog (:O21)ressiirc. ;is prc.wntcd iii Figiirc.
between reference electrode (saturated caloinel) and a point close to l . Froni tlie deíinition o( tlic dissoci;itioii const:int (K) oi'c;irboiiic
the measuring electrode was filled with the same solution, The acid (ncglcctiiig tlie sccond dissociation slcp), it I'ollows tliat
auxiliarv electrode consisted of a l a t i ~ e pH . rncasurernenkj
-
were carried out with a glass electr- (ti 3' = K (H2CO3) '
k i.
C U - ~ > ~ ( ~ 1 ~ 3 1( < -.y .
Results Since tlie concentralion ol' carbonic acid is proportional lo tlie C02 [~~3'4
partial pressurc (PCo2), according to Henry's law:
Influence oj'surfircePrepararion
For the polished specimens of thc first cxperirnint;il series the

COÍIROSCN RATE. mrn/yr

'Or- ko
TABLE 1 - Comparison of Experimental a n d
S
-
6- 0 W0C, POLISHED
Calculated Corrosion R a t e s of Grit-Blasted Samples
25 *C , POLISHED
4 - A 15 'C. GRIT-BLASTED Under Various Conditíons

Calculated Experimental
Partial Coz Corrosion Corrosion
e-
Ternperature Prsssure Rate Rate
("c) (bar) (mrnlvr) írnmlyr)

I - 5.5 1 0.40 0.4

8 - 12 1 0.56 0.6
6 - 15 1
0.52
0.66
0.43
0.7
0.4
4 - 0.37 0.35 0.3
0.2 1 0.24 0.2
22 2 1.51 1.6
1 0.95 O .9
2 - 30 1 1.32 1.3
40 0.92 1.99 1.7
50 0.88 2.89 2.3
0.1 - 60. 0.80 3.94 3.9
8 - 70 0.69 5.02 4.3
80 0.53 5.79 5.7
6 - '

4 -
- the temperature con~erned.With the aid of tliis expression, w1iii:h
was'experiinentally obeyed within 0.1 pH uiiit. Equation (2) can be
2 - written as:

log ic = % A Iog P c o z + B'

0.01' 1 L 1 1 1 1 1 1 1 1 1 i i i l l l ]
O O1 2 4 6 80l 2 4 6 8 1 n i e straight lines drawn in Figure 1 correspond to A = 1.3, whicli
gave tlie best fit for al1 data obtained. .

-
FIGURE 1 lnfluence of C 0 2 pressure and temperature on Effect oj' Tetnperature
corrosion rate of carbon steel. Corrosion rates for grit-blasted steel at various temperatures iip
to 80 C are given iii Tnblc 1. The COZ partinl pressures iii this table
have been corrected for tlie vapor pressure of water. Especinlly a!
- corrosion rate, :is measurcd witli ilie polarization teshniqiie, teinperatuU-~$yve 60 C, some of !he electrodes beciiiiie c e c d -
increased witli tilile until ü virtiially coiistiint level w,is rcaclied;'í'his w i t h _ ~ A a c klayer, wliilc tlie corrosion rate dropped lo a low value..
level is the corrosion r ~ t given
e for two test series (25 ;irid 60 C ) in- In a stagnant environnient, this effect was observed even at l(J.In
-
Figure l . 'l'he corrosion rale ol'grit-blnsted
-.
stcel, however. decreased these caces tlie results were rejected, and the tests were repeated
until sufficient data were obtained from e!ec!rz?esin j-he active-
rBjnii.i&iuah va@, unti the 6nal Icvcl =Id uirs 30%)hirher
!h&t-&iQLp~J&&&&&Aii exceptioii lo this were tests at S (:. --
state,Above 80 C al1 specirnens became passive in a matter of hours.
where polisheid spediniens often Ciilcd to becoinc active, and In order to be able to account for changes in COZ solubility and

CARBON DlOXlDE
 POTENTIAL 1%). rnv

FIGURE 3 - Potentiodynamic polarization curve in stirred

Coz-saturated water (1%NaCI, 25 C).

3.7 7 dilute HCI this Tafel line shifted as a function of pH. A linear
relation between log i, (ia = anodic current density) at 400 mV and

4
O 1 0 2 0 3 0 4 0 5 0 6 0 ~ ~pH was found (Figure 4) w&hh_.a slope of +1, which provides a
TEMPERATURE, 'C further indication of the validity of 3 7 m e c h a n i s m given in
Equation (3). Similar measurements were not carried out for
carbonic acid, since the pH range which could be covered,
FIGURE 2 - Effect of temperature on pH at 1 bar Coz
experimentally (3.8 to 4.4 at 25 C)ES too small.
(corrected for water vapor pressure). .
The c a t h o d i c x o f the polarization curve (Figure 3) shows
a lir&tina cunent, bew -- influe~cedb-y ,changes in-stining
' ,'d
speed. This effect. which was further confirrned by preliminarytests
m a rotating disc electrode, indicates that ~ ~ - ~ is~ e n t
dissociation constant, the pH was measured as a function of controued b y diffusion of one of the cathodically reacting $ p e z -
temperature for PCoz = 1 bar (corrected for water vapor pressure) In HCl at the same pH, ~ ~ T U I Y ~ S ' O ~ S ~ W ~
Figure 2 shows that in the range of temperatures studied, a linear current, having the same magnitude. This similarity sugga%tsthat the
relation between pH and temperature [t (C)] is obtained: same factors determine the limiting current in the two solutions.
For HCI the existence of a limiting current is well known:
pH (yCO,= 1) = 4.17 x 10y3 t + 3.7 1 (7) Vielstich and ~ a h n ' have shown tliat (on Pt) the limitation here can
b-dfiusoin of H* ions. This, however, does not imply
thatdiffusiong 2 the corrosion po%al of
Polarization Curves steel in farbonic acid, as wiil be discussed below.
In Figure 3, a typical polarization curve is represented, which The variation found for the ratio of conosion current and
clearly shows anodic Tafel behavior, The Tafel slopes (ba) from a polarization admittance does not enable conclusions to be drawn
number of curves varied between 30 and 60 mV,.but a slope of 40 about its compatibility with tentative values of Tafel slopes by
mV was found for most of the runs. Al1 curves sliowed a cathodic application of the SternGeary f o r m ~ l a .These ~ variations can at
cunent plateau..
Discussion
d
least p tly be explained by changes in the effective potential sliift
after c rrection for iRdrop, which in turn affects the apparent
value of this ratio via the non-linearity of the polarization curve.1°
Polarization Ctir~es Corrosion Mechanism
With the mechanism given in Equations (3) for the snodic Thl relation between the potential (E) and the anodic dissolu-
dissolution, the Tafel constant can be derived to be4? tion cunent density (ia) ix4

6 -
E = ba ~ o ia
g ba p ~ ' ca
+

where ca = constant. When it is assumed that the reduction of

which is in agreement with tiie value of ba observ&xperimentally. , Protons, according to Equations (la) and (lb), is the catliodic
m e occasional divergence from this value which r - o mction, a similar relation can be derived for the cathodic current
density (ik):
experiments has been discussed by ~ockris: and is probably caused
by the existence of other reaction paths which are in competition
E=-bklogik-bkpH+ck (9)
with the one given in Equations (3). %en HCI was used instead of
C02 t o p b t a k th-e same pH. no-significant change-in the slope or
position-~f the.Tafe1 line co-uld-be observed, whichJaa'i?nn&,a$on assuming also that no diffusion limitation occurs in the range of
J that the anodic dissolution mechanism is the 'Samejn both media. In
potentials covered by this equation. Elimi?:!i<i?, qf E from
.- - Equations (8) and (9) yields Equati?il((2) w$hil, ! ,
x -
CARBON OIOXIDE
 However, the value of A caiculated in this way does not fit with the where k = reaction rate constant and 01 = transfer ,coefficient, the
'xperimental value of 1.3. With ba = 40 mV and bk = 120 mV, a other symbols having their usual meaning. After elimination of
L v a I u e of 0.5 is calculated. w h i with bk =.Oo (dif usion-iimited (H2C03) [Equation (4)], and taking logarithms, this becomes:
a t a ? , A = l . The larga for A"iynd
-mentaiiy suggests that the corrosion rate could ossi E=-bkLogik-2bkpH+ck (13)
wrrelated with the concentration of undissociated carbonic acid
rather t w t h that of the dissociated aci (pH). A mechanisin for The ,Tafel constant (bk) for this one-electron transfer can still be
&=ct this suggestion is:
-___--_----.reactlon wmch .fits
- . -.
expected to be about'l20 mV.

'
By combining Equation (13) with Equation (8) for the anodic
RD reaction, and eliminating E, we now f í d for the dependence of the
H2C03 + e- H + HC03- (1181 mnosion nurent on pH:
_U.-- +

HCO; + H + + H ~ C O ~ (llb) ba-2bk logK+ci,-ca

--- - . __..C.. - - . . C _ C

'Ogk=b,+bk~H+ ba + bk (14) .
Afta an initial adsorption o* metal surface, an undissociated
carbonic acid molecule is directly reduced. The subsequent combi-
nation of H atoms to Hz is probably much faster, and, hence, will The slope of Equation (2). with ba = 40 mV and bk = 120 mV,now
has the value A = 1.25, which does not differ significantly from the
not be ratedetermining. íbis &o holds for the iecombi{ation of
the bicarbonat* ion, with H* diffusing from the b u , of the observed vllue of good woment alro idimtw that
diffusion limitations are negiigible at the conosion potential, since ,,
aectrolyte towards themetal in step However, when step lla is
made t" g" by of cathodic shift in P ~ the ~ with
the such
~ limitations
~ A ~would be~equal to~2. It Lould
? be noted that
diffusion of H+ eannot keep up with the amount of HC03 formed,
A should be independent of temeerature, sinceae
temperature dependen= of the Tafel constants in Equation (14)
and step *in become rat-ntroltiw. magnitu& of the
Out.
resulting limiting current would be the m e as in ths case of direct

'
The mechanism given in Equationa ( l l a ) and ( l l b ) explains
whyLoeroonrc acrd can tTB more corrosive than a completely
aAñmT EFcsrrr, m ~ l d dissochted acid at the sarna concentration. On me one hand. the
101) higher pH associated with earbonic acid increases the rate of tht

4
f 0
IN H U / I % N o t l
IFI co2-SANRAl'ED 1 X NaGL
¡ron dissolution reaction, whiíe on the other, undissociated carbonic
acid catalyzes the hydrogen evolution reaction.
Work carried out by Neumann and C!ariusil indicates that a
similar mechanism may be operative with H2S. Although not in,
connection with corrosion, the possibility of this nechanisrn has ..
already been recognized long ago,12 and was described as accel-
ferated hydrogen formation by proton donation, in the cases of
molecules containing SH, NH, CH, and OH groups.

Effect of Ternperaíure
When the overall corrosion process is activationcontrolled, the
corrosion rate (v) can be expected to follow an Arrhenius-type
relation:

where Q is the activation energy.

FIGURE 4 - Current a t -600 mV (SCEIon anodic Tafel line
vs pH.
I acids.' The constant in Equation (15) is 7.44 for grit-blasted steel.
reduction of H+ ions. It can be seen that the overall reaction of
Equations (1 la) and (1 lb) is idientical with that given i
n Equation
(la). When we assume that the electron transfer stfp l l a is
ratecontrolling at the corrosion potential. the potentd/cunrent
relationship can be written as:
The corrosion rates at different temperatures, but at constant
COZ pressure, camot be compared duectly, since carbonic acíd
concentration and pH also vary with temperature. aüow
comparison, we corrected for the influence of changes in the
environment by using the corrosion ratelpH reIation in Equation
(14). By this conection procedure, one cannot fuliy account for
changes ín COZ solubility and in dissociation constant K simulta-
neously. The second term in Equation (14) shows that any
activation energy found in this way couid represent the activation
energy of the cathodic process, the anodic process, or that for the
dissociation of the carbonic acid.
After converting al1 corrosion rates to rates which would have
been obtained at á pH of 4, an Arrhenius equation is very well
obeyed (Figure 5). wilh uil activation energy of Q = 10.7 kcal/mole.
m i s value is well within the range expected for metal dissolution in
With these data, it is possible to predict the corrosion rate of
git-blasted steel at any temperature, within the range studied. To
this end, the corrosion rate for a given temperature at pH = 4 in
Figure 5 can be converted by means of Equation (14) to the
corrosion rate at the actual pH. which can be read from Figure 2.
The result, which holds for Pcoz = 1 bar, can be corrected so as to

CARBON DIOXIDE
 Conclusions
1. The corrosion rate of steel in carbonic acid obeys the
relation:

2. The above result can be quantitatively explained with

Bockris' pHdependent mechanism for the anodic dissolution, and
the following mechanism for the cathodic reaction:

instead of a reduction of protons at the metal surface. At the

corrosion potential, the corrosion rate is not limited by diffusion of
H*.
3. The effect of temperature on the corrosion rate at constant
pH can be described with an activation energy of 10.7 kcal/mole. ,
4. Qantitative prediction of corrosion rates as a function of
the C02 partial pressure and the temperature is possible, provided
tliat passivation does not occur.

References
and H. Uhlig. Ind. Eng. Chem., Vol. 34, p. 748

2. E. C. Greco and W. B. Wright. Corrosion, Vol. 18, p. 119t

3.
p Todt.
.P B
Korrosion
m*
und Korrosionsschutz. 2nd ed., Walter de
1 I I I t I I I I I Grujter & Co.. Berlin, p. 861 (1961).
27 28 29 30 31 3.2 33 34 3536 3.7 4. H. Kaesche. Die Korrosion der Metalle, Springer Verslag, p. 135.
I/T, K-', lod (19 6). . .
.(a &' %S. 1. Cfl 'M. Bockris, D. Draric, and A. R. Despic. Uectrocbim.
-
FIGURE 5 Arrhenius plot of corrosion rates normalized to Acta, Vol. 4, p. 325 (1961),and Vol. 7, p. 293 (1962).

L..d..
pH = 4 (grit-blasted samples).
r
yubt7.
6. K. E. He~sle~~_Z..Electrochem., VoIL6~,~!1L958).
M. Stern. J. Electrochem. Soc., Vol. 102, p. 609 (1955). '
F r 8 . Wi-Vatich and RJghn. Z. Electrochem., Vol. 64, p. 43
(1960).

hold for the actual partial Coi pressure by using Equation (6).
e*. ' '

M. Stem and A. L. Ceary. J. Electrochem. Soc., Vol. 104, p. 56

(1957).
Table 1 compares corrosion rates predicted in this way with the 10. F. Mansfeld and K. B. Oldham. Corrosion Scicnce, Vol. 11, p.
experimental values obtained from weight loss experiments. Relow 787 (1971).
40 C thc agreemcnt with the predicted rates is very satisfactory, 1l . F. K. Neumann and W. Carius. Arch. Eisenhüttenw., Vol. 30, p.
while above this temperature ,small deviations occur. which are 283 (1959).
probably caused by partial coverage of the test electrodes with a 12. K. J. Vetter. Electrochemical Kinetics. Academic Press, p. 571
protective layer. Since Ihe protective properties of tliis layer can (1967).
apparently not be relied on, the calculated corrosion rates can be 13. M. Schorr and J. Yahalom. Corrosion Science, Vol.. 12, p. 867
regarded as the maximurn possible rates of attack. (1972).