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Calculation of Seawater pH at Polarized Metal Surfaces in the Presence of

Surface Films

Article  in  Corrosion -Houston Tx- · January 1992

DOI: 10.5006/1.3315918

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SCIENCE
Calculation of Seawater pH
at Polarized Metal Surfaces
in the Presence of Surface Films✫
S.C. Dexter and S.H. Lin*
ABSTRACT
A model was developed for calculating the pH at a cathodi-
cally polarized metal surface. The model accounts for the
buffering capacity and ionic strength of seawater, and it is
valid in the presence of uniformly distributed calcareous,
biological, or corrosion-product-type surface films. The
model does not yet account for hydrogen evolution, and it
cannot directly handle chemical reactions or the metabolic
activities of microorganisms within the film. Calculated pH
values are dependent on applied current density, film thick-
ness, and the various diffusion coefficients. A diffusion
correction factor is used to modify diffusion coefficients
within the film. The model predicts increasing pH with in-
creasing applied current density and film thickness,
reaching a maximum of 9.9 at the limiting diffusion current
for oxygen under quiescent flow conditions with no hydro-
gen evolution. Direct measurements of pH by micro-
electrode techniques were in agreement with model predic-
tions at an applied current of 20 µA/cm2. Measured pH
values were higher than calculated at 100 µA/cm2, the dif-
ference due to hydrogen evolution.
KEY WORDS: pH, cathodic protection, seawater, biofilm,
calcareous deposit, mathematical model
INTRODUCTION
Cathodic protection has long been recognized as an
effective corrosion control method, especially in sea-
✫
Submitted for publication November 1990; in revised form, August 1991.
*University of Delaware, College of Marine Studies, Lewes, DE 19958.
0010-9312/92/000015/$3.00/0
50 National Association of Corrosion Engineers
water where conductivity is sufficient for a reasonably
uniform current distribution. In addition, the inorganic
chemistry of seawater permits the formation of ben-
eficial calcareous deposits on the metal surface
during cathodic protection. Many researchers have
worked to understand the formation of calcareous de-
posits.1-5 The major factors that influence calcareous
deposition, such as temperature,6-8 velocity of flow,9-12
surface preparation,13 applied potential and cur-
rent,5,14 and pH4,15 are also well known.
The ability of an applied current to change the pH
at the metal surface is one of the most important fac-
tors in calcareous deposition. Thus, it is not surprising
that several models have been developed for calculat-
ing the surface pH under cathodic protection con-
ditions. Engell and Forchhammer16 and Wolfson and
Hartt7 formulated models to calculate the pH at a bare
metal surface based on the rate of cathodic oxygen re-
duction. In these models, the total amount of OH– ions
generated (proportional to applied current) was used
to calculate the high pH. However, in seawater, some
of the OH– must be used to convert HCO3– to CO3–2
before a dramatic change in pH can occur. The pH
values predicted by these models are a full pH unit
higher than that of direct measurements.18 Thus, the
buffering capacity must be considered when develop-
ing an interface pH model to be used in seawater.
Sadasivan19 developed a model that predicts the
current density during calcareous deposition. In his
model, mass balances were set up, and a concentra-
tion profile in the diffusion boundary layer was
calculated using a finite element technique. However,
CORROSION–JANUARY 1992

the buffering capacity and high ionic strength of sea-
water and the activities of the chemical species
involved still were omitted. In the present work, a
model was developed to calculate the pH at the sur-
face of a cathodically protected metal electrode in the
presence of surface films (both calcareous and bio-
logical), taking into account the buffering capacity and
ionic strength of seawater. The model accounts for the
physical effects of surface films, but it does not yet ac-
count for chemical reactions or metabolic activity of
organisms within the film.
INTERFACE pH MODEL
Under cathodic protection conditions in seawater,
three cathodic reactions occur that cause an increase
in pH at the metal surface. These are:
Oxygen reduction: O 2 + 2H 2 O + 4e – → 4OH –
Hydrogen evolution: 2H 2 O + 2e – → H 2 (g) + 2OH – (2)
Peroxide production: O2 + 2H2O + 2e– → H2O2 + 2OH–
In seawater, a change in pH also means a
change in the concentrations of all the species in the
CO2 system, according to Equations (4) and (5) be-
low.20
CO 2 + H 2O = H+ + HCO –3
a H [HCO–3 ]
K'1 =
[CO2 ]
HCO 3– = H + + CO 3–2
a H [CO–2 ]
K'2 = 3 surface; however, only those species involved in the
[HCO–3 ]
where K’1 and K’2 are the apparent first and second
equilibrium constants of carbonic acid, and aH is the
activity of hydrogen ions (aH = 10–(pH)). The apparent
equilibrium constants for carbonic acid, as calculated
from the concentrations of CO2, CO3–2, and HCO3–
rather than the activities, were used because of the
difficulties in obtaining the activities of the various car-
bon species required for the true equilibrium
constants.
The model was developed to be valid under the
following set of conditions: (1) oxygen reduction is the
major cathodic reaction, and hydrogen evolution is ne-
glected; (2) any surface films are distributed uniformly,
and their physical presence provides a diffusion bar-
rier resulting in sharp concentration gradients through
the film; (3) transport of oxygen and other chemical
CORROSION–Vol. 48, No. 1
SCIENCE
species to the metal surface is a diffusion-controlled
process; and (4) total titration alkalinity is constant.
Thus, the model as presently formulated was not
meant to account for either the hydrogen evolution ex-
pected at very negative potentials or the metabolic
activity of the organisms in a biofilm. Suggestions
have been made later in the paper as to how such ca-
pabilities could be added to the model.
Upon cathodically protecting an electrode having
a surface film, two distinct diffusion zones can be de-
fined (Figure 1). These are the film itself and the liquid
diffusion zone (or boundary layer) between the film
surface and the bulk solution. Within the film and diffu-
sion zones, the concentration profiles of the various
chemical species follow Fick’s diffusion law, while in
the bulk solution, the concentrations are assumed to
be constant. An increase in pH at the metal surface
(according to Equations [4] and [5]) should result in a
high CO3–2 concentration but low HCO3– and CO2 con-
(1)
centrations. Thus, one would expect species CO3–2
and OH–, which are being produced at the interface, to
diffuse away from the metal surface, while species
(3) CO2 and HCO3– should diffuse toward the metal sur-
face. These expectations are reflected in the direc-
tions of the arrows in Figure 1. The concentrations of
species X at the metal surface and at the film surface
are shown as [X]m and [X] f, while the diffusion fluxes
of these species within the film and diffusion zones are
shown as J (X)f and J (X)d, respectively. At steady
(4) state, the amount of any species diffusing into a zone
must equal the amount diffusing out, and the concen-
tration of that species must be continuous across the
zone boundaries. The positive direction in this work
has been defined as being toward the bulk solution.
The model was based on charge and mass bal-
(5)
ances at the interface between film and diffusion
zones. All species are able to diffuse across the film
cathodic reaction (Equation [1]) or the CO2 buffering
system were considered important for the purposes of
this model in calculating the interface pH. Thus, the
charge balance can be expressed as:
J (OH)f – J (HCO3)d + 2J (CO3)f =
4J (O 2 ) f – J (HCO 3 ) f + J (OH) d + 2J (CO 3 ) d (6)
The carbon balance can be expressed as:
J (CO3)f – J (HCO3)d – J (CO2)d =
– J (HCO 3 ) f – J (CO 2 ) f + J (CO 3 ) d (7)
where J (X) is the diffusion flux of species X and the
subscripts d and f indicate action in the diffusion and
film zones, respectively.
51
SCIENCE

The flux, J (X)d, in the diffusion layer follows Fick’s
first law:
J (X)d = D (X) { [X]f – [X]
d } (8)
where D (X) is the diffusion coefficient of species X,
[X] f, and [X] are the concentrations at the film surface
and in the bulk solution, respectively, and d is the
thickness of the diffusion layer. One might consider
including the hydrogen diffusion flux in Equations (6)
and (7), but it has been neglected in this edition of
the model.
To calculate the diffusive fluxes of OH–, HCO3–,
CO3–2, CO2, and O2 in the expressions for the charge
and carbon balances, the concentrations of these spe-
cies in the bulk solution and at the metal and film
surfaces are needed. These concentrations can be
calculated from Equations (9) through (12) using mea-
sured values of the pH, temperature, alkalinity, and
salinity of the bulk solution.21
- (K 'w ) f H
[OH ] = (9)
aH
a 2H (TA)
[CO2 ] = (10)
a H (K 1' ) + (2K '1 ) (K '2
where F is Faraday’s constant, DO2 is the diffusion
coefficient of oxygen in the bulk solution, O2 and O2f
are the oxygen concentrations in the bulk solution
and at the film surface, respectively, and d is as
defined previously. The value of d reasonably can be
assumed to be 200 µm for a quiescent solution. The
oxygen concentration at the metal surface (O2m) can
also be calculated from Equation (13), if the appropri-
ate diffusion coefficient for oxygen in the film is
known, and the thickness of the film, f, is estimated
or measured.
The objective of this work was to calculate the pH
at the metal surface, and perhaps at the film surface
as well, as functions of bulk water chemistry, applied
current density, and the properties of the film. This has
been done using Equations (4) through (13). First, the
diffusion fluxes in Equations (6) and (7) were replaced
with their equivalent expressions involving the diffu-
sion coefficients, concentrations, and film thicknesses
from Equation (8). For simplicity, the chemical species
OH–, O2, CO2, HCO3–, and CO3–2 will be represented
by OH, O 2, CO2, HCO3, and CO3, respectively. Do-
ing this yields:
DOHf{[OH]m – [OH]f} DHCO3d {[HCO3]f – [HCO3]}
–
f d
2DCO3f {[CO3]m – [CO3]f} 4DO2f{[O2]m – [O2]f}
+ +
f f

a H (K ' 1 ) (TA) DHCO3f {[HCO3]m – [HCO3]f} DOHd{[OH]f – [OH]}

[HCO –3 ] = (11) + –
a H (K 1' ) + (2K '1 ) (K 2' ) f d

(K ' 1 ) (K '2 ) (TA) 2DCO3d {[CO3]f – [CO3]}

– =0 (14)
[CO–2
3
]= (12) d
a H (K '1 ) + (2K '1 ) + (K 2' )

where K’w is the apparent ionization constant of and

seawater, as defined22 by the product of the concen-
trations of OH– and H+. TA is the total titration DCO3 f {[CO3]m – [CO3] f }
alkalinity, while fH and fOH are the activity coefficients22 f
of hydrogen and hydroxile ions, respectively, in
seawater. The K’ values are as defined by Equations
(4) and (5) and are available from the literature20 for DHCO3d {[HCO3]f – [HCO3]}
–
given values of temperature and salinity and cor- d
rected for the activity coefficients of CO2, HCO3–, and
CO3–2. The total titration alkalinities at the metal and
film surfaces have been assumed to be equal to DHCO3f {[HCO3]m – [HCO3]f }
+
those in the bulk solution. f
The oxygen concentration at the film surface is re-
lated to the applied current density, i, by the following
equation: DCO3d {[CO3]f – [CO3]}
– =0 (15)
d
i = 4F (DO 2 ) (O 2 – O 2f ) /  d (13)

52 CORROSION–JANUARY 1992

FIGURE 1. Schematic diagram of the film and diffusion zones
adjacent to a cathodically protected metal surface. The con-
centrations and diffusion fluxes shown are as defined in the
text.
At pH values of 8 and above, typical of seawater,
the speciation of the carbonic acid system23 is such
that 93% of the total inorganic carbon is present as
HCO3–, 6% as CO3–2, and only 1% as CO2. Thus, the
two terms in Equation (7) involving diffusion fluxes of
CO2 were considered insignificant and have been ne-
glected in Equation (15).
Now substituting in Equations (14) and (15) the
expressions for the concentrations of the various spe-
cies in Equations (9) through (13) and rearranging,24
one obtains the following two equations involving the
activity of hydrogen ions at the film, aHf, and metal,
aHm, surfaces. From Equation (14) one obtains
A1 (aHm2 aHf2) + A2 (aHm2aHf ) + A3 (aHmaHf2 )
+ A4 (aHmaHf ) + A5 (aHm2 ) + A6 (aHf2 )
+ A 7 (a Hm ) + A 8 (a Hf ) = 0 (16)
From Equation (15) one obtains
B1 ( aHm ) – B2
aHf = (17)
B3 ( aHm ) + B4
where the coefficients A1 to A8 and B1 to B4 are
complicated algebraic functions of the applied current
density, total alkalinity, and the various equilibrium
constants and diffusion coefficients.
The activity of H+ at the metal surface now can be
calculated by substituting the value for a Hf from Equa-
CORROSION–Vol. 48, No. 1
SCIENCE
tion (17) into Equation (16). Writing out the equation,
rearranging and regrouping by order of terms, one ob-
tains the following fourth order polynomial equation:
C4 (aHm)4 + C3 (aHm)3 + C2 (aHm)2 + C1 (aHm) + C = 0 (18)
The H+ activity and hence the pH at the metal sur-
face can be calculated from Equation (18) by an
iterative technique provided that the values of the
physical, chemical, and electrochemical parameters in
the coefficients C to C4 are known or can be mea-
sured.
VALUES FOR THE PARAMETERS
To calculate the pH at the metal surface from
Equation (18), values are needed for:
(1) The diffusion coefficients of OH–, HCO3–,
-–2
CO3 , CO2, and O2 in the bulk solution and in the film;
(2) The first and second equilibrium con-
stants, K’1 and K’2, of carbonic acid as defined in
Equations (4) and (5);
(3) The ionization constant of seawater, K’w,
and the activity coefficients of H+ and OH–;
(4) The thicknesses of the film and the diffu-
sion layer; and
(5) The pH, total alkalinity, dissolved O2 con-
centration, temperature, and salinity of the bulk water
and the applied current density.
Consider each of the above parameters. The
tracer diffusion coefficients for OH–, HCO3–, and CO3-–2
in the bulk solution were obtained from Li and Gre-
gory,25 and those for CO2 and O2 from Lerman.26 The
diffusion coefficients of these species in the film, how-
ever, will vary from those in the bulk solution due to
differences in the viscosity, porosity, and tortuosity
within the film and interactions between the film and
the diffusing species. Several works reported in the lit-
erature were helpful in determining the result of such
effects. Li and Gregory found that the apparent diffu-
sion coefficients for the ions Cl –, Na+, SO4-–2, and Ca+2
in red clay were 20 to 50% of the free-solution diffu-
sion coefficients in seawater. LaMotta found that the
effective diffusivities of glucose within a porous bio-
logical slime were 19.5 to 50.5 percent of the
molecular diffusivities in water.27 Aller measured the
diffusion coefficients of inorganic solutes within or-
ganic materials from eight species of marine
invertebrates to be 10 to 40 percent of their values in
pure water.28
The general consistency of these data from the lit-
erature has led us to take the approach of Bungay and
coworkers29 and define a diffusion correction factor, ,
with which to modify the bulk diffusion coefficients for
the effect of the film. Thus, the diffusion coefficients
53
SCIENCE
used for the species, OH–, HCO3–, CO3–2, CO2, and O2,
in the film were those for the bulk fluid, modified by the
correction factor ranging from 0.1 to 0.5. In the results
shown in this paper, we have applied a single value of
 uniformly to all diffusing species. Individual values of
 for each diffusing species could be used without
changing the model if data were available on which to
base the choice of the individual values. Values of the
diffusion correction factor will be independent of film
thickness as long as the film is homogeneous. If, how-
ever, the film is layered (e.g., biofilm on top of
calcareous deposit) then two film zones would have to
be defined, each with its own properties.
The values of the first and second equilibrium
constants for carbonic acid, K’1 and K’2, were taken
from the work of Milero.20 He measured these values
directly from seawater of a given temperature and sa-
linity, and he corrected them for the activity
coefficients of CO2, HCO3–, and CO3–2. The ionization
constant K’w of seawater was defined as the product of
the concentrations of OH– and H+. The value of this
constant, along with the values of the activity coeffi-
cients of H+ and OH– in seawater (fH and fOH, respect-
ively) were taken from the work of Culberson and
Pytkowicz.22
The thickness of the film could be measured di-
rectly by any one of several methods. For the results
shown in this paper, we have used film thicknesses
ranging from 20 to 100 µm. The thickness of the
boundary diffusion layer has been assumed to be 200
µm for a quiescent solution. Values different from
these could be used as needed for other hydrody-
namic conditions. The bulk water properties and
FIGURE 2. Calculated pH values at the metal surface of a
filmed electrode as a function of applied current density and
diffusion correction factor, . Film thickness = 20 µm, and
diffusion layer thickness = 200 µm.
54
applied current density (mentioned in [5] above) typi-
cally would be measured directly by conventional
methods. The values used to generate the results
shown in the next section are those typical of full-
strength open-ocean seawater.23
RESULTS FROM THE MODEL
Figure 2 shows computer-calculated pH values
for a cathodically protected metal surface in seawater
of 35 ppt salinity at 25°C as a function of applied cur-
rent density and diffusion correction factor in the
presence of a 20-µm-thick film. The model predicts
that interface pH increases with increasing applied
current density and with decreasing  value. This is
reasonable because a decreasing  value indicates
an increasing resistance of the film to outward diffu-
sion of OH– (i.e., a higher interface pH). The model
predicts a maximum pH of about 9.9 even at low 
and high applied current density. Under these condi-
tions, the oxygen diffusion flux to the surface becomes
limiting, and the pH will reach a plateau unless an-
other cathodic reaction occurs. Calculations from the
model show little effect of the film until  reaches ap-
proximately 0.5 and then a substantial effect for 
values below that as shown in Figure 2.
At an average diffusion correction factor of  =
0.3, the calculated pH at the metal surface is shown
for various film thicknesses and applied current densi-
ties in Figure 3. These results reveal that with all other
factors held constant, the interface pH increases with
film thickness. This agrees with our expectation that a
FIGURE 3. Calculated pH values at the metal surface of a
filmed electrode as a function of film thickness and applied
current density for  = 0.3.
CORROSION–JANUARY 1992

FIGURE 4. Calculated pH values at the film surface as a
function of applied current density and . Film thickness = 20
µm, and diffusion layer thickness = 200 µm.
FIGURE 6. Calculated oxygen concentration profiles near the
metal surface at applied current densities of 20, 50, and 100
µA/cm2. Film thickness = 20 µm, diffusion layer thickness =
200 µm, and  = 0.3.
FIGURE 7. Calculated OH– concentration profiles near the
metal surface at applied current densities of 20, 50, and 100
µA/cm2. Film thickness = 20 µm, diffusion layer thickness =
200 µm, and  = 0.3.
CORROSION–Vol. 48, No. 1
SCIENCE
FIGURE 5. Calculated pH values at the film surface as a
function of film thickness and applied current density for  =
0.3.
thick film should retain more of the OH– ions produced
than a thin film of the same properties. The data in
Figure 3 represent an average value for the diffusion
correction factor and cover the general range of film
thicknesses and current densities used in cathodic
protection. Thus, it should be useful in predicting inter-
face pH values under conditions in which hydrogen
evolution is not significant.
The model was also used to predict the pH at the
film-water interface. These results are shown as a
function of applied current density in Figure 4 and film
thickness in Figure 5. These data show that the model
predicts an increasing film surface pH with increasing
applied current density, increasing  and decreasing
film thickness. Note that the effects of  and of film
thickness on pH at the film surface are opposite to
their effects on pH at the metal surface. The more effi-
ciently OH– ions are retained in the vicinity of the metal
surface, the more the pH is changed there, but the
less it is changed on the outside of the film.
Using the interface pH values predicted from the
model, the concentrations of each of the chemical
species involved in the charge and carbon balances at
the metal and film surfaces could also be calculated.
Thus, the concentration profiles vs distance from the
metal surface are shown for O2 (Figure 6), OH– (Figure
7), HCO3– (Figure 8), and CO3–2 (Figure 9). In each
case, the profiles are shown for applied current densi-
ties of 20, 50, and 100 µA/cm2, and the calculations
were done for film and diffusion layer thicknesses of
20 and 200 µm and a diffusion correction factor of  =
0.3. Note that most of the change in concentration for
O2 and OH– takes place within the film, while most of
the change for HCO3– and CO3–2 takes place within the
liquid diffusion layer.
55
SCIENCE
FIGURE 8. Calculated HCO3– concentration profiles near the
metal surface at applied current densities of 20, 50, and 100
µA/cm2. Film thickness = 20 µm, diffusion layer thickness =
200 µm, and  = 0.3.
COMPARISON TO MEASURED VALUES
Several pH measurements near the metal surface
were made using microelectrode techniques. A micro
pH-sensitive glass electrode of tip diameter 200 µm
was made at Montana State University for the authors,
and the pH measurements reported in this paper were
made at the Center for Interfacial Microbial Process
Engineering at Montana State using that electrode.
The pH-sensitive glass tip was recessed within an
outer sheath of lead glass, which was brought into
contact with the metal surface by a micromanipulator.
During a measurement, the distance between the
metal surface and the curved bulb of the pH-sensitive
glass tip was estimated to be between 50 and 100 µm,
and the measurement represents an average over the
surface of the tip. An electrometer was used to mea-
sure the potential difference between the pH-sensitive
glass tip and a saturated calomel reference electrode.
Measurements were made at five-minute intervals
within a period of 30 min. The electrode was calibrated
using pH 4 and 7 buffer solutions before the start of
each series of six measurements. The amount of
recalibration was always below 0.1 pH unit. Thus,
each of the pH values reported here is the average of
six measurements. The error shown for each mea-
surement was ±0.1 pH unit, corresponding to the
largest recalibration increment, rather than to the stan-
56
FIGURE 9. Calculated CO3–2 concentration profiles near the
metal surface at applied current densities of 20, 50, and 100
µA/cm2. Film thickness = 20 µm, diffusion layer thickness =
200 µm, and  = 0.3.
dard deviation of the measurements themselves,
which was smaller.
Values of pH near the surface of both bare and
filmed metal electrodes were measured under ca-
thodic protection conditions. The measurements were
made in a NaCl/NaHCO3 solution, prepared to have
the same ionic strength and buffering capacity as sea-
water, but without the microorganisms to prevent
biofilm formation during the measurement and without
calcium and magnesium ions to prevent calcareous
deposition. The solution was open to the atmosphere
during the pH measurements but was not actively
stirred or aerated. The specific metal surface used
was that of the nickel-based superalloy C-276, which
forms a stable passive film and is not susceptible to lo-
calized corrosion initiation in Cl– containing media.
Filmed electrodes were prepared by mixing a cul-
ture of the marine bacterium, Vibrio harveyi, with 2%
marine agar in 3% NaCl and brushing this mixture
onto the C-276 electrode surface. The density of the
stock bacterial culture was 109 cells per mL of solu-
tion, and this was diluted six times in making the agar
mixture. Thus, the density of bacterial cells in the agar
film was in the 108 cells per mL range. Measurement
of pH on a given electrode was always finished within
three hours of the time the bacteria were mixed with
the agar. The thickness of the film was estimated to be
about 4000 µm by measuring the distance between
the outer part of the film and the metal surface using a
micromanipulator. Measurements of pH were taken at
galvanostatically applied current densities of 20 and
100 µA/cm2.
The results of the pH measurements are shown in
Table 1. With no applied current, there was no mea-
CORROSION–JANUARY 1992

surable pH difference between the filmed and bare
electrodes under these conditions, and the free corro-
sion potentials of the two electrodes were similar
(within normal scatter). Note that these were short-
term laboratory measurements. Thus, the authors do
not believe that the result should be used to imply any-
thing about the ability of natural population organisms
to change the pH at a metal surface exposed in the
field for longer times. The data show that the mea-
sured interfacial pH increased with applied current
density on both the bare and filmed electrodes. The in-
crease in pH was higher on the filmed than on the
bare electrodes at each of the applied current density
levels. The rate of pH increase was higher for all elec-
trodes at the low current density level.
The potential of each electrode was monitored
during these experiments, and these data also are
shown in Table 1. At each current density level, the
shift in potential was greater on the filmed than on the
bare electrodes. At the two most negative potentials,
corresponding to a current density of 100 µA/cm2, gas
bubbles were observed to form at the metal surface
and were trapped within the agar on the filmed elec-
trode. It is presumed that the gas formed was
hydrogen, although this was not directly confirmed.
Figure 10 shows the data from Table 1 plotted
along with predictions from the model for: (1) a bare
metal surface, (2) a surface covered with a 100-µm -
thick biofilm with  = 0.5, and (3) a surface covered
with a 50-µm-thick calcareous deposit with  = 0.1.
For an applied current density of 20 µA/cm2, the mea-
sured values of pH for both the bare (solid circle) and
biofilmed (solid triangle) surfaces are in general agree-
ment with the model predictions. At the high applied
current density, however, the measured values are
considerably more basic than those predicted by the
model.
DISCUSSION
The significance of this model in comparison to its
predecessors is that it accounts for the buffering ca-
pacity and ionic strength of seawater, and it is valid in
the presence of surface films rather than just at the
bare metal surface. Consider the limitations of the
model based on the conditions stated earlier under
which it was formulated. The first condition was that
oxygen reduction was the major cathodic reaction.
This is probably valid under aerated seawater condi-
tions at low applied cathodic current density, where
the oxygen diffusion flux can keep up with demand,
and the electrode potential is more positive than ap-
proximately –0.7 V SCE (the value below which
hydrogen evolution is thermodynamically possible at
pH 8). At more negative (active) potentials and higher
CORROSION–Vol. 48, No. 1
SCIENCE
current densities, oxygen transport to the cathodic sur-
face gradually becomes diffusion limited. If the applied
current is able to polarize the electrode to a potential
more active than about –1.0 V SCE, a significant
amount of hydrogen evolution is likely to occur. This
was observed in the present work on the filmed elec-
trode at a current density of 100 µA/cm2. Thus, as
shown in Figure 10, the model, which does not ac-
count for hydrogen evolution, underestimated the
metal surface pH at the high current density. This defi-
ciency in the model could be corrected by adding an
additional diffusion flux corresponding to the amount
of OH– generated by hydrogen evolution to the charge
balance in Equation (6).
The formation of hydrogen gas bubbles within the
film may give rise to two other effects that are not ac-
counted for in the model. First, the bubbles may
physically block the diffusion pathway for chemical
species migrating both to and from the metal surface.
Second, the formation of hydrogen gas at the cathodic
surface can disrupt the formation of the calcareous de-
posit layer.30-32 Both of these effects would invalidate
the results of the model if bubble formation was exten-
sive.
The second condition was that any films present
would be uniformly distributed over the metal surface
and that they would act as a diffusion barrier. The con-
dition of uniform coverage is approached on surfaces
with mature biofilms or well-developed calcareous de-
posits. On surfaces where the film provides spotty
coverage, the model will give only an average value
for the interface pH. That average pH value may or
may not be meaningful. Any film will act as a diffusion
barrier for that portion of the surface it covers. A com-
plication, which the model cannot yet directly handle,
arises when the film becomes an active source or sink
for any of the chemical species in Equations (6) and
(7). Thus, the model does not yet have the capability
to account for the metabolic production or use of spe-
cies such as oxygen or CO2 by microorganisms within
the biofilm. For most bacteria, growth is seriously
TABLE 1
Interface pH and Potential as Measured on Bare and
Agar-Filmed Electrodes Galvanostatically Protected
at Current Densities of 20 and 100 µA/cm2
Current Agar and
Bare
Density V. harveyi filmed
0 8.2 ± 0.1 8.2 ± 0.1
–250 –290
20 9.0 ± 0.1 9.4 ± 0.1
–650 –820
100 10.2 ± 0.1 10.4 ± 0.1
–970 –1030
57
SCIENCE
FIGURE 10. Values of pH calculated from the model as
compared to measured pH values (solid points).
Bare Bio- Calcareous
Surface Filmed Filmed
Diff. layer thickness (µm) 200 200 200
Film thickness (µm) 1 100 50
Diff. correction factor 1.0 0.5 0.1
limited33 at pH values above 9. Data from the model
for an average diffusion correction factor of  = 0.3
(Figure 3) indicate that pH 9.5 at the metal interface is
achieved at a film thickness of 60 µm for an applied
current of 20 µA/cm–2 and less than 10 µm at 100 µA/
cm–2. Thus, for applied current densities above 20 µA/
cm–2, including most practical cathodic protection cur-
rents, bacterial metabolism should not be a serious
problem.
For current densities below 20 µA/cm–2, corre-
sponding to those sometimes used for protecting
stainless alloys from pitting, bacterial metabolism may
influence the interface pH in ways not accounted for
by the model. Evidence that bacterial activity can influ-
ence cathodic protection at low applied current
densities is found in the works of Johnsen and
Bardal34 and Dexter and Lin.35 Johnsen and Bardal
2 (1+)] (19)
found that the current density for maintaining stainless
alloys in the 300 to 500 mV SCE range increased dra-
matically in natural seawater, and they attributed this
to the action of a biofilm on the metal surface. Dexter
and Lin found that an applied current density of 20 µA/
is the tortuosity,
cm2 was unable to maintain the potential of a stainless
alloy in the protected range once a biofilm had formed.
Low applied current conditions may also be experi-
enced in regions of restricted geometries such as in
crevices and under disbonded coatings. The model is
not expected to give valid results in such locations, es-
pecially in the presence of large populations of
microorganisms.
58
The third condition was that transport of oxygen is
diffusion controlled. Two sets of conditions can occur
under which this is not valid. The first involves non-
steady-state flow conditions in which the thickness of
the diffusion boundary layer is changing with flow ve-
locity or is under the influence of localized turbulence.
The other condition occurs when the film becomes an
active source or sink for one of the chemical species
in the charge or carbon balance equations. For ex-
ample, an actively metabolizing biofilm may either
consume or produce oxygen. Such effects are not cur-
rently accounted for in the model. Conceivably,
production or consumption of oxygen by the microor-
ganisms in the film could be modeled as an effect on
the oxygen diffusion coefficient. Thus, it could be in-
cluded in the value of the diffusion correction factor for
oxygen. However, this would require another level of
complexity in the model, as separate values of 
would have to be used for each diffusing species,
rather than the overall value that is currently used.
The final condition was that the total titration alka-
linity remains constant. Two effects need to be
considered here. First is the ability of microorganisms
in the film to use or produce CO2, and second is the
removal of CO3–2 in the calcareous deposition process.
Generation or consumption of CO2 gas by the organ-
isms within the biofilm is not expected to change the
total alkalinity21,31 because that process is separate
from the carbonic acid buffering system of the water.
However, the removal of CO3–2 in the calcareous
deposition process (or by bacteria) will change the al-
kalinity. Thus, the model would have to be modified in
order to be valid under conditions in which a calcare-
ous deposit is actively forming.
In some cases, it may be possible to estimate the
diffusion correction factor in more detail than has been
done so far in this work. Li and Gregory found that the
diffusion coefficients of various chemical species in-
side deep sea sediments, Dsed, could be related to
their values in the bulk water, D, by a dimensionless
correction factor, ’.25 Thus, Dsed = ’D, where
’ = [ /
In Equation (19), is the ratio of the viscosity of
the bulk solution to the average viscosity of the solu-
tion in the pore waters of the sediment. It is a function
of both porosity and salt content.
which is the ratio of the length of the actual tortuous
diffusion path of ions around the particles in a sedi-
ment (or in a film) to the equivalent straight-line
distance.  is the distribution coefficient, which repre-
sents the excess percentage of ions absorbed in a unit
volume of sediment.
Theoretically, Equation (19) could be used to esti-
mate values of  to use for each diffusing species in
CORROSION–JANUARY 1992

the model. could be used to account for the increase
in viscosity within a film composed of microorganisms,
exopolymer, corrosion product, and calcareous
deposit. An increase in viscosity of the film would de-
crease , consequently causing a decrease in . This
would represent an average value of the viscosity
within a heterogeneous film that could have consider-
able variations from point to point along the metal
surface.
The value of the tortuosity,
, would be nearly one estimated  value of 0.1.
(thus, negligible) for a purely agar or gelatinous type
film. The incorporation of microorganisms, corrosion
products, inorganic debris, and calcareous deposits
into the film, however, would cause an increase in the
tortuosity of the diffusion path and a decrease in the
value of . The distribution coefficient, , could be
used to account for the injection or removal of species
such as O2 or CO3–2 within the film, as discussed
above.
Such detailed corrections to the diffusion coeffi-
cients could only be done meaningfully in a carefully
controlled model system in which the film had uniform
properties in both the lateral and thickness directions.
Any real film, of course, would be highly viable, espe-
cially in the lateral direction parallel to the metal
surface. Under such conditions, it would only be pos-
sible to define an average correction factor for the
macroscopic surface.
Figure 10 shows that the predictions from the
model were in reasonable agreement with actual
measurements of the interface pH at an applied cur-
rent density of 20 µA/cm2 but not at 100 µA/cm2.
Comparison of the measured and calculated points is
most meaningful for the bare metal surface at the low
current density. In this case, calculations from the
model were done for minimal values of the film thick-
ness (1 µm) and  (1.0). One would expect the
micro-pH electrode to underestimate the true interface
pH due to its distance from the surface, as already ex-
plained above. In contrast, the model calculates the
pH right at the surface. Thus, it is reasonable for the
measured data near the bare surface to fall below the
line calculated from the model as shown in Figure 10.
It is more difficult to make a direct comparison be-
tween the measured and calculated values of pH for
the filmed surface. The measured data were taken, as
described previously, under a 4000-µm-thick agar film
to which marine bacteria had been added. The calcu-
lated curve represents an idealized biofilm with a
uniform thickness of 100 µm, an estimated  value of
0.5, and a diffusion layer thickness of 200 µm. Using 
= 0.5 and d = 200 µm at an applied current density of
20 µA/cm2, the model can now be used to predict the
biofilm thickness at which the pH reaches a maximum
(corresponding to oxygen diffusion limited conditions).
Doing this the model predicts that the interface pH
CORROSION–Vol. 48, No. 1
SCIENCE
reaches a maximum value of 9.9 for biofilm thick-
nesses of 425 µm and above. Thus, the model
indicates that the pH under the 4000-µm-thick experi-
mental biofilm should have been at least 9.9.
Compared to this value, the micro-pH electrode again
underestimates the interface pH. Note from Figure 10
that the model also predicts a considerably higher in-
terface pH at the same current density under a film
that is predominantly calcareous in character with an
The discrepancy between the predicted and mea-
sured values at the high current density in Figure 10
points to one of the main limitations of the model as
currently configured. The electrochemical potentials of
the bare and filmed electrodes at the high current den-
sity were –0.97 and –1.03 V SCE, respectively (Table
1). Both of these potentials are negative enough that
appreciable hydrogen evolution would be expected at
the cathode surface. Indeed, gas bubbles suspected
of being hydrogen were observed to form on the
filmed electrode during the measurement. Thus, it
seems reasonable that oxygen reduction at the cath-
ode was diffusion limited under these conditions and
hydrogen evolution contributed significantly to the
overall generation of OH– at the electrode surface.
This is in agreement with the model predictions,
especially as shown in Figure 3, where the curve for
the high current density reaches a plateau at a film
thickness of 50 to 60 µm, indicating that the oxygen
reaction is diffusion limited. Thus, this version of the
model, which does not account for hydrogen evolu-
tion, underestimates the interface pH under any
conditions in which oxygen diffusion becomes the lim-
iting factor. In other words, the model underestimates
the interface pH as soon as conditions at the metal
surface become anaerobic.
SUMMARY AND CONCLUSIONS
A model has been constructed to calculate the pH
at a cathodically polarized metal surface in saline wa-
ters in the presence of both calcareous deposits and
biofilms. The model takes into account the buffering
capacity and ionic strength of the electrolyte but does
not include hydrogen evolution. Formulation of the
model was based on charge and carbon balances at
the metal and film surfaces using the chemical spe-
cies involved in the cathodic oxygen reduction reaction
and the seawater buffering system. The final equation
is a fourth order polynomial, which is solved by com-
puter using an iterative technique.
The model is valid for waters of all salinities and
temperatures and for all applied current densities be-
low the point at which oxygen diffusion to the metal
surface becomes rate limiting. Values of pH calculated
from the model will not be accurate under conditions in
59
SCIENCE
which (1) hydrogen evolution is the dominant cathodic
reaction; (2) microorganisms in the film are acting as
an active source or sink for the chemical species in
Equations (6) and (7); (3) surface films are macro-
scopically nonuniform or spotty; or (4) CO3–2 is being
consumed during calcareous deposition. Conceivably,
the relationship in Equation (19) could be used to ac-
count for the effects of either bacterial metabolism or
the depletion of carbonate during calcareous deposi-
tion. Calculated values of pH may also not be accurate
at applied current densities less than 20 µA/cm2 if a
biofilm is present due to the metabolic activity of the
organisms.
Data needed as input to the model are the bulk
seawater properties, diffusion coefficients, and equilib-
rium constants, along with the film and diffusion layer
thicknesses. These values were either measured or
estimated from the literature. Definition of a “diffusion
correction factor” allowed the bulk diffusion coeffi-
cients to be modified for use within the film region.
Published data from the literature on seawater chem-
istry and geochemistry showed that the correction
factor will usually have values from 0.1 to 0.5. In this
edition of the model, a single value of the diffusion cor-
rection factor was applied to all diffusing species.
Predictions from the model were compared to in-
terface pH measurements made by a micro-pH
electrode near the surfaces of both bare and filmed
electrodes at applied current densities of 0, 20, and
100 µA/cm2. The measured and calculated pH values
agreed well at 20 µA/cm2, the calculated values right
at the metal surface being more basic than the mea-
sured values as expected due to the distance from the
electrode tip to the surface. Agreement was not as
good at 100 µA/cm2. The calculated values were too
low because the model does not account for hydrogen
evolution. The model predicts that the maximum sur-
face pH obtainable with oxygen reduction as the sole
cathodic reaction is 9.9. A corollary to that conclusion
would be that it requires hydrogen evolution to get an
interface pH value greater than 10.
ACKNOWLEDGMENTS
The authors wish to thank Drs. Characklis and
Lewandowski of Montana State University for their
help in making the micro-pH electrode and for the use
of their laboratory facilities. We also thank Dr. W.
Ullman for helpful discussions on the model. Support
for this work was provided by NOAA Office of Sea
Grant, Department of Commerce, under Grant No.
NA86AA-D-SG-040. The U.S. government is autho-
rized to produce and distribute reprints for government
purposes not withstanding any copyright notation that
may appear hereon.
60
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