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Journal of New Materials for Electrochemical Systems 8, 133-142 (2005)

c J. New. Mat. Electrochem. Systems


Evaluation of Water Corrosivity Using a Corrosion Rate Model for a Cooling Water System

Alberto Alvarez Gallegos1 , Susana Silva Martinez1 , Jos Luis Ramirez Reyes2
1 Instituto
2 CITCOR.

de Investigaciones Elctricas, Cuernavaca, Morelos. 62490, Mxico.


Unidad Acadmica Multidisciplinaria, UAT, Tampico, Tamaulipas, Mxico.

( Received September 24, 2004 ; received in revised form December 28, 2004 )
Abstract: The first part of a corrosion inhibitor model has been developed to be used in a specific Mexican Power Plant. The model takes into
account the main operational conditions found in the cooling water, such as major corrosive chemical species, a wide pH range, the performance of
a commercial corrosion inhibitor (based on tolyltriazol) and the material of the condenser (admiralty). The objective is to replace the old criteria
based on Langelier Saturation and Ryznard Stability Index for a better approach that can suggest a variable inhibitor dosage to achieve a desired
mpy value in the cooling water system (e. g. 1 mpy). Five pairs of admiralty coupons were sunk in five different beakers containing synthetic cooling
water with an increasing concentration factor (1 to 5) at fixed pH and temperature. The experiment was repeated at different corrosion inhibitor
concentrations, testing three different pH values (6, 7 and 8). Admiralty corrosion rates were obtained (from 0.04 to 2.7 mpy) in the laboratory,
in the presence and absence of a commercial corrosion inhibitor, using a jar test and synthetic cooling water. The corrosion rates in admiralty
were assessed by means of the Linear Polarization Resistance technique. It is demonstrated that, basically admiralty corrosion rate is a function of
water chemistry, pH and corrosion inhibitor concentration. Experimental data can be fitted to an empirical equation to predict the performance of
a corrosion inhibitor versus inhibitor dosage. The model runs in a personal computer allows the prediction of information related to the treatment
cost to achieve a desired mpy value in the cooling water system.
Key words : corrosion, indices, inhibitors, modeling.

1.

INTRODUCTION

dicting the water corrosive potential under the assumption that


if water is scale forming, corrosion rates will be negligible. Otherwise, waters that are not scale forming are considered corrosive. Since then, both indices have been used [3-5] to predict
scaling and corrosion in a number of industrial process waters.
Both indices measure only the directional tendency or driving
force of water. They cannot be used as a quantitative measure.
Indeed, two different waters, one of low hardness and thus corrosive, and the other of high hardness and thus scale-forming,
can have the same Saturation Index. Under this approach, calcium carbonate is the sole parameter for determining the corrosivity of water. Using indices to determine scaling or corrosion
in cooling water system is problematic for a number of reasons
that were discussed elsewhere [6]. Although the experience has
shown that, there is no definite relationship exist between corrosion rate and the indices [7], an improved version of a new index

For most recirculated cooling water systems in the electric utility industry, corrosion control is a common problem and it is
linked to condenser performance. Clean heat transfer surfaces
are essential to minimize forced outages. Optimizing the performance of cooling water system depends strongly upon the
method followed to predict corrosion in aqueous solutions.
In 1936, the Langelier Saturation Index, LSI, [1] was introduced
as the first attempt to quantify the solid-liquid equilibrium status of calcium carbonate in water. A few years latter, a new
index appeared [2], the Ryznard Saturation Index (RSI), claiming a better alternative to assess the same chemical equilibrium.
Shortly thereafter, both indices became universal tools for pre To
whom correspondence
algga56@hotmail.com

should

be

addressed:

email:

133

134

A. A. Gallegos et al./ J. New Mat. Electrochem. Systems 8, 133-142 (2005)

[8], based on the earlier indices, was presented for forecasting


calcium carbonate scaling: the Practical Scaling Index.
Taking into account the main problems related to these indices
and the necessity of the growing Mexican industry for predicting the corrosivity, the Instituto de Investigaciones Elctricas
was charged to develop an alternate methodology to face the
problem. This work offers a different approach for improving
the performance of a cooling water system and discusses the
first part of a corrosion inhibitor model, developed to be used in
a specific Mexican Power Plant. The corrosion inhibitor model
is based on a computer program that performs a water treatment, including diagnoses about the impact of cooling water
chemistry and recommends procedures to minimize corrosion
on Admiralty surfaces. Critical parameters to develop corrosion
inhibitor dosage models are also discussed. Corrosion inhibitor
dosage model is based on laboratory test data, in the presence
and absence of inhibitor and a mathematical correlation. The
mathematical model is then used to predict the minimum inhibitor level requirement to achieve a specific degree of corrosion rate target.
2.

COPPER CORROSION

Copper alloys are the most common material for heat exchangers in cooling water systems using cooling towers. It is well
known that copper alloys form natural oxide film (Cu2 O) as
soon as they are in contact with water. The stability of this
film is a critical parameter because it protects the base metal
from further oxidation. In fact, this natural oxide film can be
degraded by the water chemistry impact on its surface, e. g.
chlorides, sulfates, pH, total dissolved solids, oxygen, etc.
It is accepted that the protective oxide film contains less copper
[9] than is indicated by the chemical formula. That means that
there are vacancies in the cuprous oxide lattice. In theory, copper is oxidized according to the following mechanism. At the
beginning Cu0 oxidizes to Cu+ . Then, this ion moves to fill the
gaps into the lattice. As the cuprous ion migrates through these
vacancies, the oxygen, on the surface of the metal, ultimately
oxidizes it to the cupric ion (Cu++ ). Oxygen accepts electrons
from the cuprous ion found in the cuprous oxide lattice and the
ion Cu++ is released in the bulk solution. The gap in the oxide lattice left behind could be replaced with another cuprous
ion, maintaining the oxidation process. This process could be
represented by means of the figure 1.
In order to minimize the oxidation mechanism it is necessary
to minimize the outward movement of the cuprous ion from
the metal. Selecting a good metal, neutralizing the nature and
amount of dissolved chemicals that enhance the corrosion rates
or a combination of both can solve the problem. In pure copper,
the natural oxide film, formed during corrosion, is highly defective and contains many gaps into which the cuprous ion can

Figure 1: Schematic representation of the protective cuprous


oxide film formation

migrate [10]. The addition of some elements (aluminum, zinc,


tin, iron and nickel) to the copper has shown lower corrosion
rates than in pure copper. These new elements basically plug
the gaps in the corrosion product film, making it more resistant
to the corrosion. One of best alloys is Admiralty.
In order to minimize the degradation of the natural protective
film, specific inhibiting chemicals are added in cooling water
treatment program in the Power Industry. Corrosion inhibitors
can interfere in the corrosion process, either anodic or cathodic
reaction or both. Among the main corrosion inhibitors for copper alloys Mercaptobenzothiazole (MBT), Tolyltriazole (TT) and
Benzotriazole (BZT) are found to be good. All of them can inhibit the oxygen reduction reaction, the predominant cathodic
process. Oxygen is necessary for formation of the protective
Cu2 O film and for the release of metal. The corrosion process
(dissolution of copper) requires oxygen, and in a neutral solution, it is based in the following cathodic reaction:
O2 + 2H2 O + 4e 4OH

(1)

Inhibitors films reinforce the resistance offered by Cu2 O in retarding the reduction of the oxygen.
3.

MODELS FOR CORROSION RATE

3.1

Indices as Indicator of Corrosivity.

The first model to predict the water corrosive potential was the
Langelier Saturation Index (LSI). It can be represented by the
following equation:

LSI = Actual pH pHs

(2)

Evaluation of Water Corrosivity Using a Corrosion Rate Model . / J. New Mat. Electrochem. Systems 8, 133-142 (2005)

Where pHs is the saturation pH and is represented by:


0
pHs = pK20 pKCaCO
+ pCa2+ + pAlk
3

method for predicting the water corrosive potential. In order to


overcome this problem a mathematical model is proposed.
(3)

Where pK20 is the second dissociation constant of H2 CO3 ,


0
pKCaCO
is the solubility product constant of CaCO3 , pCa2+
3
and pAlk are the concentration of calcium and alkalinity respectively. A positive Langelier Saturation Index indicates that the
evaluated water has potential calcium carbonate scale forming
tendencies. In contrast, waters that are not scale forming have a
negative LSI and are considered corrosive. Although this equation is theoretically correct and has been receiving too much attention [8,11-16] its predictions (scaling and corrosion) are very
limited. Indeed, calcium carbonate is the sole parameter for determining the corrosivity of the water. Under this approach, it
is not possible to predict the complex chemical behavior of a
system [6] and the necessity for a better approach is justified.
3.2

Advanced Models for predicting Corrosion Rates.

Modeling the oxidation mechanism requires understanding of


the chemistry occurring in the formation of the natural oxide
film, formed during corrosion, in a complex chemical solution.
For example, the reduction of the oxygen is not as simple as it
appears represented by equation (1). Indeed, it was proposed
[17] that one must consider a heterogeneous equilibrium at the
metal-solution interface represented by the following set of equations:

O2 O2 (ads)
O2 (ads) + H + e HO2 (ads)
HO2 (ads) + H + + e H2 O2 (ads)

H2 O2 (ads) + 2e 2OH

135

(4)

Although it is widely accepted that the cathodic reduction of


the oxygen first proceeds by a preliminary adsorption [18] on
the cathode surface, neither thermodynamic nor kinetic information related to the chemical equilibrium in the equation (4)
is known. Moreover, this equilibrium is a function of the nature
and amount of dissolved chemicals that enhance the corrosion
rates, as well as the nature of corrosion inhibitor and the alloy.
In the same way, another complex equilibrium that represents
an atom of copper that is oxidized and leaves its neutral metallic state and enters into solution as a charged ion must be understood. Off course, the minimum necessary knowledge (physicochemical interactions occurring in a real cooling water) to develop a corrosion inhibitor model that can simulate the complex
chemistry of the copper oxidation mechanism in the presence of
an inhibitor is not yet available. But, it is clear that the indices,
based on calcium carbonate equilibrium only, is not the best

Under this approach, an experimental study, taking into account


the same operational conditions that are found in a real cooling
water system, is necessary. The effects of various changes in
operating conditions, such as water composition and chemical
treatments can be evaluated with respect to specific alloy corrosion. Corrosion rates, observed in the experimental study, can
be correlated to the major chemical species, pH, temperature
and the nature and amount of corrosion inhibitor. Although this
method enables to predict accurate corrosion rates, significant
errors can result when the data are extrapolated outside the area
of investigation. Indeed, no two cooling water systems are identical. Each cooling water source differs in quality and contains
a unique combination of contaminants.
A mathematical correlation was developed [19] to predict corrosion rates on carbon steel in the presence of organic phosphorus as inhibitor. Their predictions have shown a high degree
of confidence. Using a similar approach [7], several models
for predicting corrosion rates on mild steel were developed. In
this study, it was found that the observed corrosion rates can be
correlated to seven variables: chloride, sulfate, total alkalinity,
dissolved oxygen levels and exposure, LSI and buffer capacity
of the system. Davis [20] used similar variables to develop a
model for corrosion rates on mild steel in the presence of a specific inhibitor. Using the method outlined by Pisigan [7], a water
treatment company [21] developed a mathematical correlation
for corrosion rate prediction, and for modeling the impact of inhibitor (orthophosphate) on corrosion rate (mild steel). In this
approach, experimental corrosion rate, on mild steel, was correlated to five variables: chloride, sulfate, carbonate, calcium
and corrosion inhibitor concentrations. The model was tested
in a refinery and the authors claimed that the mathematical correlation, driven by a personal computer, was able to optimize
inhibitor feed to the cooling water system. Under a particular
set of operational condition (water chemistry, pH, temperature),
the model recommended that 8 to 10 ppm of an inhibitor based
on orthophosphate, should be maintained to achieve corrosion
rates of 5 mpy or less. The theoretical predictions agreed with
experimental results.
4.

DEVELOPING A CORROSION INHIBITOR MODEL

In this work, the basic method described in previous studies


[7,20,21] was followed to develop a particular corrosion inhibitor
model. The basic equations are the following:
Corrosion rate (CR) can be correlated to the water chemistry by
means of the general equation (5).

2 4
2
2+ 3
5
CR = K (Cl )1 (SO2
4 ) (Ca ) (CO3 ) (inhib) . . . (5)

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A. A. Gallegos et al./ J. New Mat. Electrochem. Systems 8, 133-142 (2005)

Where 1 , 2 , . . . n are regression coefficients; K is temperature dependent constant; inhib is a corrosion inhibitor concentration and the rest of the variables are chemical species concentrations. Because the objective of the method is to look for
the best mathematical correlation between corrosion rate and
the water chemistry, there is not a fixed limit in the number of
variables.

number of parameters. This n-parameter linear model can be


expressed as an n x n linear system. The matrix form is:

A11
A21

A31

A41

At room temperature, equation (5) can be linearized by logarithmic transformation to:

A12
A22
A32
A42

A13
A23
A33
A43

A14
A24
A34
A44


b1
1
2 b2

3 b3


4 = b4

(9)

The matrix is symmetric and its elements are defined as:


ln(CR) = 1 ln(Cl ) + 2 ln(SO2
4 )+
3 ln(Ca2+ ) + 4 ln(CO2
3 ) + . . . (6)

A11 =

ln(Cl )k ln(Cl )k ;

A12 =

k1

Equation (6) can be solved by a multiple linear regression analysis [22]. Indeed, it is possible to find a smoothing function
g(Water Chemistry) (with parameters 1 , 2 , . . . n to be determined) whose graph is capable of assuming the shape determined by M experimental data points. In this way, the square
error E(g) is an indicator of how well g(Water Chemistry) fits
these experimental data points. This can be done by minimizing E(g), defined by:

[g((Water Chemistry)k ln(CR)k ]2

ln(Cl )k ln(Ca2+ )k ;

A14 =

k1

k1

Where M
k1 denotes the sum over all M data points.

(7)

ln(Cl )k ln(CO2
3 )k ;

E(g) =

k1

A13 =

ln(Cl )k ln(SO2
4 )k ;

A22 =

k1

2
ln(SO2
4 )k ln(SO4 )k ; A23 =

k1

2+
ln(SO2
4 )k ln(Ca )k ;

k1

E(g) can be viewed as a differentiable function of n variables


1 , 2 , . . . n and in the absence of other constrains, the minimum value of E(g) occurs when all partial derivatives are simultaneously zero, that is, when:

A24 =

k1

A33 =


E(g)
= 2 [g((Water Chemistry)k ln(CR)k ] ln(Cl )k
1
k1

k1

k1

ln(Ca2+ )k ln(Ca2+ )k ; A34 = ln(Ca2+ )k ln(CO2


3 )k ;

M


E(g)
= 2 [g((Water Chemistry)k ln(CR)k ] ln(SO2
4 )k
2
k1
M


E(g)
= 2 [g((Water Chemistry)k ln(CR)k ] ln(Ca2+ )k
3
k1
M


E(g)
= 2 [g((Water Chemistry)k ln(CR)k ] ln(CO2
3 )k
4
k1

(8)

The set of equations in (8) are called normal equations and are
guaranteed to be linear, hence easily solved, regardless of the

2
ln(SO2
4 )k ln(CO3 )k ;

A44 =

2
ln(CO2
3 )k ln(CO3 )k ;

k1

Solving the linear system (equation 9) by any direct method


yields the unique last square parameter vector [1 , 2 , . . . n ]T
whose components are the coefficients of the equation (6).
5.

APPARATUS AND MATERIALS

Solutions were prepared using distilled water. The chemicals


were used as supplied by different sources (Merck, Aldrich and
J. T. Backer). Admiralty tube and the inhibitor based on tolyltriazole were obtained directly from a Mexican Power Plant. Admiralty coupons (2 cm x 1 cm x 1mm) were made from Admiralty tube according to the norm ASTM D2688-90. Corrosion
rates on Admiralty coupons were obtained by means of ACM
Instruments, model AutoTafel/AutoLPR V1, driven by a PC.

Evaluation of Water Corrosivity Using a Corrosion Rate Model . / J. New Mat. Electrochem. Systems 8, 133-142 (2005)

6.

EXPERIMENTAL METHOD

current density plot can be considered linear in the studied region and can be represented by the following equation [23]:

Five 250 ml-beakers were filled with five different synthetic


cooling waters with an increasing concentration factor, ranging from 1 to 5, at fixed pH and temperature. Main operational
conditions (chemical composition, temperature, etc) were similar to those found in a particular Mexican Power Plant. The
chemical composition, of the five synthetic cooling waters used
in this work is shown in table 1.

icorr =

Reactor 1
CF 1

Reactor 2
CF 2

Cl
SO2
4
Ca+2
CO2
3
HCO
3
Na+
K+
Mg+2

283
480
40
0.005
73
368
39
24

567
1056
80
0.009
98
736
117
48

Reactor 3
Reactor 4
CF 3
CF 4
ppm (as ion)
851
1134
1536
2016
120
160
0.028
0.040
214
299
1104
1472
156
195
72
96

B=

Reactor 5
CF 5
1418
2592
200
0.052
354
1840
273
120

B
R

(10)

where icorr = corrosion current density (related to the corrosion


rate), R = polarization resistance and B = Stern-Geary constant
of the system. This constant is related to the Tafel constants by
the relationship:

Table 1: Chemical composition of synthetic cooling waters used


in this work.
Specie

137

ba bc
2.303(ba + bc )

(11)

where ba and bc are the anodic and cathodic Tafel constants


respectively. At the end of each experiment, the electrodes were
polarized (from +1000 mV to 1000 mV) and Tafel constants
were experimentally evaluated (by the potentiostat) and used
in equations 10 and 11. A typical set of experimental points,
obtained at pH 6, room temperature, concentration factor of 1
and inhibitor-free (first column of table 1), are shown in figure 3.

A pair of admiralty coupons were sunk in each beaker and Admiralty corrosion rates were assessed at room temperature, by
means of the Linear Polarization Resistance (LPR) technique
(ASTM, 1989), at three different pH values (6, 7 and 8). During the experiment, the pH was maintained constant ( 0.1 pH
units), by adding NaOH or H2 SO4 . Each set of experiments
lasted at least 4 hours. Experiments were repeated in the presence of three different inhibitor concentrations (6, 12 and 25
ppm). A schematic diagram of a representative jar test is shown
in figure 2.

Figure 3: Experimental corrosion rates obtained by LPR at pH


6, room temperature, concentration factor of 1 and inhibitor-free
Finally, figure 3 represents the average corrosion rate for a particular chemical system.
Figure 2: Diagram of a jar set-up and Admiralty coupon
7.
6.1

Linear Polarization Resistance Technique.

During the experiments the electrodes (admiralty coupons) were


polarized ( from +15 mV to 15 mV) at various intervals of time
and the potentiostat measured and recorded the corresponding
change in the current (icorr ). Therefore, each experiment gave
a set of five experimental points (icorr vs time). The potential-

7.1

RESULTS AND DISCUSSION


Corrosion Rates in the Absence of Inhibitor.

A set of five experiments were performed in the absence of


inhibitor using the chemical composition showed in table 1 at
pH 6 and room temperature. Experimental corrosion rates (expressed as mpy) on Admiralty coupons were obtained as a function of the chemistry of the water. The corrosivity of each sam-

138

A. A. Gallegos et al./ J. New Mat. Electrochem. Systems 8, 133-142 (2005)

Table 2: Experimental corrosion rates on Admiralty coupons as a function of the chemistry of cooling water, pH = 6 0.1, room
temperature and inhibitor-free. Water corrosivity prediction using LSI model [4]

Experimental Corrosion
Rate (mpy)
Assessed by LPR
LSI (Betz,1980)

Reactor 1
CF 1

Reactor 2
CF 2

Reactor 3
CF 3

Reactor 4
CF 4

Reactor 5
CF 5

1.27

1.39

1.51

2.34

2.69

-2.1

-1.7

-1.2

-1

-1

ple of water was predicted by means of LSI [4]. The main results are showed in table 2.
As expected, corrosion rate on Admiralty increases as sulfates
and chlorides concentration increase in the cooling water. Although a negative LSI was obtained (water considered corrosive) in all the reactors, the LSI magnitude indicates a wrong
prediction. According to LSI the impact of water chemistry on
Admiralty is higher in reactor 1 than in reactor 5, but the experience [7,24] and the common sense indicate the contrary.
In the absence of inhibitor a set of five experiments were performed using the chemical composition shown in table 1, at
room temperature and at two different pH values (7 and 8).
Experimental corrosion rates (expressed as mpy) on Admiralty
coupons were obtained as a function of water chemistry and pH.
The main results are shown in a 3-D graph (fig. 4)

Figure 4: Water chemistry and pH impact on Admiralty corrosion rates in absence of inhibitor at room temperature
From the figure 4, it can be seen that keeping water chemistry
constant, experimental corrosion rates on Admiralty are higher
at low pH values and they diminish smoothly toward alkaline
pH values. On the other hand, keeping a pH constant, experi-

mental corrosion rates on Admiralty are lower at diluted cooling


water and they accelerate smoothly toward concentrated cooling
water. Experimental results further implies that it is possible to
maintain a corrosion rate < 1mpy by just keeping pH higher than
7, regardless of the water chemistry.
7.2

Corrosion Rates in the Presence of Inhibitors.

Following the same experimental procedure than before, experimental corrosion rates on Admiralty, in the presence of a
commercial inhibitor (based on tolyltriazole) were obtained as
a function of water chemistry (see table 1) at three different pH
values (6, 7 and 8). Figure 5 shows, the efficiency of 6 ppm of
inhibitor on the Admiralty corrosion rates at room temperature.

Figure 5: Water chemistry and pH impact on Admiralty corrosion rates in presence of 6 ppm of inhibitor at room temperature

The experimental corrosion rates on Admiralty are inhibited


significantly under all the experimental conditions studied: from

139

Evaluation of Water Corrosivity Using a Corrosion Rate Model . / J. New Mat. Electrochem. Systems 8, 133-142 (2005)

pH 6 to pH 8 and from CF 1 to CF 5. The efficiency of the inhibitor can be assessed by means of the following equation [25]:

E=

(CR0 CR1 )
100
CR0

(12)

Where CR0 and CR1 are experimental corrosion rates in the absence and in the presence of an inhibitor, respectively. Table 3
shows the efficiencies obtained for 6 ppm Inhibitor in five different synthetic cooling waters at room temperature and at three
different pH values.

Table 3: Efficiencies obtained at 6 ppm corrosion Inhibitor in


five different synthetic cooling waters at room temperature and
at three different pH values.
1
CR0 (mpy)
CR1 (mpy)
E (%)

1.27
0.18
86

CR0 (mpy)
CR1 (mpy)
E (%)

0.43
0.07
84

CR0 (mpy)
CR1 (mpy)
E (%)

0.15
0.05
67

2
pH 6
1.39
0.21
85
pH 7
0.61
0.08
87
pH 8
0.25
0.06
76

Reactor
3

1.51
0.36
76

2.34
0.47
80

2.69
0.56
80

0.82
0.08
90

1.04
0.12
88

1.47
0.26
82

0.30
0.07
77

0.44
0.09
80

0.66
0.17
74

Experimental corrosion rates on Admiralty, in the presence of


two more concentrations (12 and 25 ppm) of a commercial inhibitor (based on tolyltriazole) were obtained as a function of
water chemistry (see table 1) at three different pH values (6,
7 and 8). Figure 6 shows the efficiency of 12 ppm of inhibitor
while figure 7 shows the efficiency of 24 ppm of inhibitor on the
Admiralty corrosion rates, both experiments were performed at
room temperature.
Table 4 shows the efficiencies obtained for 12 ppm corrosion
Inhibitor and table 5 shows the efficiencies obtained for 24 ppm
corrosion Inhibitor. Both sets of experiments were performed in
five different synthetic cooling waters at room temperature and
at three different pH values.
Experimental results can be used to establish the economics for
water treatment to a given corrosion rate. Indeed, these results
can provide useful information on the relative treatment cost for
achieving 1 mpy in a system, 0.5 mpy or other targets.

Table 4: Efficiencies obtained at 12 ppm corrosion Inhibitor in


five different synthetic cooling waters at room temperature and
at three different pH values.
1
CR0 (mpy)
CR1 (mpy)
E (%)

1.27
0.07
94

CR0 (mpy)
CR1 (mpy)
E (%)

0.43
0.04
91

CR0 (mpy)
CR1 (mpy)
E (%)

0.15
0.02
87

2
pH 6
1.39
0.09
94
pH 7
0.61
0.04
93
pH 8
0.25
0.03
88

Reactor
3

1.51
0.10
93

2.34
0.13
94

2.69
0.16
94

0.82
0.04
95

1.04
0.05
95

1.47
0.07
95

0.30
0.04
87

0.44
0.04
91

0.66
0.04
94

Table 5: Efficiencies obtained at 24 ppm corrosion Inhibitor in


five different synthetic cooling waters at room temperature and
at three different pH values.
1
CR0 (mpy)
CR1 (mpy)
E (%)

1.27
0.07
94

CR0 (mpy)
CR1 (mpy)
E (%)

0.43
0.04
91

CR0 (mpy)
CR1 (mpy)
E (%)

0.15
0.02
87

2
pH 6
1.39
0.09
94
pH 7
0.61
0.04
93
pH 8
0.25
0.03
88

Reactor
3

1.51
0.10
93

2.34
0.13
94

2.69
0.16
94

0.82
0.04
95

1.04
0.05
95

1.47
0.07
95

0.30
0.04
87

0.44
0.04
91

0.66
0.04
94

140

A. A. Gallegos et al./ J. New Mat. Electrochem. Systems 8, 133-142 (2005)

7.3

Correlation of Corrosion Rates.

Experimental corrosion rates obtained in the absence of inhibitors,


were correlated to the water chemistry by means of the equation 5. It was found that the best correlation was obtained when
the fitting equation used just three variables. At room temperature, equation 5 became:

2+
ln(CR) = 1 ln(Cl ) + 2 ln(SO2
4 ) + 3 ln(Ca )

(13)

The pH range was divided in 5 pH intervals and for each pH


value a set of s were estimated, following the mathematical
procedure described above. The main results are shown in table 6.

Figure 6: Water chemistry and pH impact on Admiralty corrosion rates in presence of 12 ppm of inhibitor at room temperature

Table 6: Regression coefficients (1 , 2 , 3 ) for five different


pH regions in the absence of inhibitors and at room temperature.

pH Region

6 pH 6.5;
6.5 < pH 7;
7 < pH 7.5;
7.5 < pH 8;
pH > 8

Figure 7: Water chemistry and pH impact on Admiralty corrosion rates in presence of 24 ppm of inhibitor at room temperature

Equation (13)
ln(CR) = 1 ln(Cl ) + 2 ln(SO2
4 )
+3 ln(Ca2+ )
1
2
3
-0.288 -0.439
1.216
-0.311 -0.415
1.088
-0.689 -0.633
1.891
-0.707 -1.270
2.820
-0.998 -1.289
3.172

Applying this mathematical methodology, regression coefficients


could, of course, be either positive or negative but the algebraic
sign has not a chemical meaning as was suggested by Pisigan [7]
and Ferguson [21], but it depends rather on a number of mathematical factors that are not related to corrosion rates. In fact, s
sign strongly depends on the number of variables used in fitting
equation (13) and the method employed to invert and scale matrix in equation (9). In this work, if equation (13) is transformed
back to a nonlinear form, taking into account the sets of calculated regression coefficients, the new equation would not imply
that increasing chloride and sulfate would result in lower corrosion rate. In fact, equation (13) can not imply or suggest any
physical or chemical behavior of the system, because it is not
a chemical model. Nevertheless, corrosion rates on Admiralty
could be predicted by means of equation (13) as long as operational condition remains inside the limits investigated. Indeed,
equation (13) is just a mathematical model.
Using equation (13), corrosion rates on Admiralty were predicted under the experimental condition studied. Good predictive results were obtained for all cases. Figure 8 shows the
graphical comparison between the experimental and predicted

Evaluation of Water Corrosivity Using a Corrosion Rate Model . / J. New Mat. Electrochem. Systems 8, 133-142 (2005)

corrosion rates at room temperature, pH 6 and different chemical composition (expressed as concentration factor, CF).

141

Modeling over the operating range encountered for pH and water chemistry, allows for optimization of inhibitor feed. A typical dosage profile, for a concentration factor of 3, room temperature and different pH values, is shown in Figure 9.

.9

Figure 8: Graphical comparaison between experimental () and


predicted () corrosion rates be equation 13 (1 = -0.288, 2 =
-0.439, 3 = 1.216). Correlation coefficient, R = 0.89. Room
temperature, pH = 6 and different chemical composition expressed as concentration factor.

The equation 13 is used in a computer program to model the


inhibitor dosage in a Cooling Water System using the following
algorithm: 1) the water chemical composition at equilibrium
is obtained; 2) a pH region is selected; 3) a diagnoses is formulated; 4) an inhibitor concentration is recommended (based
on experimental data) to keep admiralty corrosion rate below
1 mpy; 5) Additional comments are displayed on the computer
screen. For each pH region a set of operating rules and comments were developed based on experimental data obtained, for
example:
(No inhibitor present in cooling water)
R1: If pH < 6, Then Diagnoses: a corrosion rate on Admiralty
is estimated in 3 mpy.
Comments: 1) There is an EMERGENCY SITUATION;
2) Add, immediately, 12 ppm inhibitor; 3) Do not add
more ACID; 4) Open the blowdown to maximum.
R2: If 6 pH 6.5, Then Diagnoses: a corrosion rate on
Admiralty is estimated in 2.69 mpy.
Comments: 1) Add, immediately, 12 ppm inhibitor; 3) Do
not add more ACID; 4) Open the blowdown to maximum.
5) Do not operate, under this condition for more than 8
hours.

Figure 9: Inhibitor (Tolytriazole) dosage profile suggested by a


computer program based on equation (13). Concentration factor
3 (chemical composition), different pH values and room temperature.
Although corrosion rates predicted by this model are good, some
important restrictions limit its applicability. In deed, corrosion
rates predicted by this model are just valid for clean Admiralty
surfaces; otherwise experimental corrosion rates could be one
or two orders of magnitude higher than those predicted by the
model.
Corrosive behaviors of water predicted by means of traditional
indices are not reliable because of the simplicity chemistry in
which they are based. In contrast, good predictive corrosion
rates can be obtained correlating experimental corrosion rates
to water chemistry. This approach provide a better tool for evaluating a cooling water system under varying condition to determine the impact of water chemistry on Admiralty corrosion or
other metals, as long as enough experimental data are available.
In the future, the second part of this model will be developed
and it will include the effect of temperature and the flow velocity
on Admiralty corrosion rates.
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