CORROSION SCIENCE SECTION

Potential-pH (Pourbaix) Diagrams as Aids for Screening Corrosion Inhibitors and Sequestering Agents
D.C. Silverman,* and A.L. Silverman*

ABSTRACT
Potential-pH (Pourbaix) diagrams are used as road maps for aiding in predicting the most stable states of a metal, its corrosion products, and its associated ions in an aqueous solution. It is presented in a plot of equilibrium potential vs. hydrogen ion activity. Organic ions, including those of biological importance such as amino acids, can affect the most thermodynamically stable states associated with the metal. This paper explores how potential-pH diagrams might be used as aids for screening such organic corrosion inhibitors and sequestering agents. The diagrams were generated using a newly developed, internet-accessible, Web-based application. The Web application and its advantages over comparable single user personal computer platform-based applications are also summarized. Key WOrds: 1-hydroxyethylidene-1,1-diphosphonic acid, amino acid, copper, corrosion inhibitor, glutamic acid, hippuric acid, internet, iron, nickel, potential-pH diagram, Pourbaix diagram, sequestering agent, tartaric acid, Web-based applications

INTRODUCTION
A theoretical tool that is sometimes overlooked, which can aid in practical corrosion prediction, is the thermodynamic potential-pH (Pourbaix) diagram.1 The equilibrium potential and hydrogen ion activity coordinates in which this diagram is plotted are variables useful to the corrosion practitioner. Hydrogen
Submitted for publication January 8, 2010. Presented as paper no. 07616 at CORROSION/2007, March 2007, Nashville, TN. Corresponding author. E-mail: dcsilverman@argentumsolutions. com. * Argentum Solutions, Inc., Chesterfield, MO 63017.

ion activity as a measure of acidity and equilibrium potential as a measure of oxidizing or reducing power are two very important determinants of corrosion in electrolyte solutions. The potential-pH diagrams are theoretical in that they are derived from thermodynamic data. The species shown at each coordinate of hydrogen ion activity and equilibrium potential is that bulk species that would have the minimum free energy for the system at those conditions used for the calculation. As with all thermodynamic calculations, the species determined to have the lowest free energy (the most stable from an energy standpoint) depends entirely on which species are considered for the calculation. If all components important to the corrosion problem are included in the calculation and the thermodynamic data are valid and accurate, the diagrams can show the conditions under which corrosion does not occur, e.g., immunity or pure metal. Coordinates lying in regions predicting solid oxides, hydroxides, or dissolved ions are regions of possible corrosion, a process that might occur in the time frame of the observation. These diagrams might be considered analogous to road maps in which the towns and cities might be represented by the states of the system and the longitude and latitude might be represented by the pH and potential. They show which system states have the lowest free energy and are the most energetically stable as a function of pH and potential (analogous to towns at lowest elevation or with the least number people as a function of longitude and latitude). The reactions used to generate the diagrams would be the possible paths to move between the system

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states. But, the diagrams are silent with respect to the actual reaction kinetics between system states (rate of moving between towns), or that reaction pathway (map direction) that provides the highest reaction rate (shortest distance). System states having corrosion mass-loss rates of kilograms per second or micrograms per century would appear as regions of corrosion on the diagrams. Using the potential-pH diagram as a practical aid in designing appropriate experiments for predicting corrosion is an application that has received somewhat spotty attention. Authors2-5 have discussed in detail how these diagrams can be interfaced with the real world. An important conclusion was that as long as all components important to the corrosion process are included in the calculation, a reasonable indication of corrosion may be obtained by placing the measured corrosion potential or controlled potential and measured or calculated pH onto the theoretical diagram. The assumption is that the steady-state corrosion or controlled potential can be used as a substitute for the equilibrium potential and the measured or calculated pH can be used as a substitute for the hydrogen ion activity. By placing the coordinates (pH, corrosion or controlled potential) directly on the diagram, the practitioner can get a handle on the state of the corroding system. Good agreement has been found between the prediction of the diagram and the actual corrosion observed.2-7 Most applications of potential-pH diagrams involved interaction with either water alone or water containing inorganic ions. But, any ion, organic or inorganic, could be incorporated into the potentialpH diagram as long as reasonable thermodynamic data can be estimated. Such applications have been reported.4,6-9 If the organic ion can form a thermodynamically favored adduct with the metal in question, the resulting product could be either a corrosion inhibitor or corrosion accelerator. It may also serve as an intermediary to facilitate passivation or corrosion. Sometimes, the nature of the interaction may be a function of acidity or potential. This functionality has been demonstrated with respect to the interaction between iron and aspartic acid.5 The potential-pH diagram was able to guide the experiments to determine in what potential and pH range the interaction resulted in corrosion inhibition. One goal of this work was to provide examples of how the potential-pH diagram might be used to aid in practical screening of organic corrosion inhibitors and sequestrates. The effort was based on the concept that if an adduct of a metal and a dissolved species is thermodynamically stable in the potential and pH range of interest, then that molecule might be a corrosion inhibitor or sequestering agent. The diagrams could then be used to guide simple experiments for

confirmation. Molecules considered for this paper were tartaric acid, hippuric acid, 1-hydroxyethylidene1,1-diphosphonic acid (HEDP or etidronic acid), and the amino acid glutamic acid. Metals considered were iron, nickel, and copper. A second goal of this effort was to demonstrate that potential-pH diagram generation via a Webbased application is practical. Computer programs used to generate the potential-pH diagram to date have usually been written either for a single user on either a mainframe computer or a personal computer. This approach, while being adequate for single user applications, has drawbacks if the desire is for wider accessibility across multiple platforms. Compatibility across computer systems is one of the largest problems facing software development today.10 Compatibility issues not only exist among the Windows operating system, the open source Linux operating system, and Mac OS but also across the various Windows operating systems themselves. Compatibility issues can arise because of other software packages installed on a particular computer even if the application has been demonstrated with the same operating system but on another computer. Such conflict can be a serious impediment to usage. An internetaccessible, Web-based application on a central server usually can circumvent the above issues because it needs to be compatible only with the Web browser on the users computers. The type of operating system and other installed software do not impact such compatibility. Web browsers guarantee compatibility with the standards set forth by the World Wide Web Consortium (W3C)11 as long as the code is written according to those standards. The program used to generate the potential-pH diagrams in this paper was a newly developed, internet-accessible Web application called THERMEXPERT.

WEB APPLICATION FOR GENERATING DIAGRAMS

The Web application was developed using a combination of languages such as FORTRAN, HTML (Hypertext Markup Language), JavaScript, and Perl (a popular Common Gateway Interface programming language). The thermodynamic data were stored in a MySQL database. Plots were generated in the portable network graphic (.png) format. The system was verified to be compatible with the common browsers, Internet Explorer, Netscape Navigator, and Firefox. A number of algorithms have been reported for generation of potential-pH diagrams.12 The choice of which to use in this application was made by considering speed, reliability, ease of implementation, and structure of the output. The algorithm chosen was the convex polygon algorithm mentioned by several authors.12 Although not potentially as accurate as the finely meshed point-by-point algorithm, the convex

Trade name.

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FIguRe 1. Flow of the potential-pH diagram Web application.

polygon algorithm was expected to complete the calculations in a much shorter time while providing very reasonable potential-pH diagrams.2 The overall flow of the application is shown in Figure 1. After entering the application on the Web site, the user enters name, affiliation, and e-mail address. Although not required of the user, having this information helps to track the results if questions arise. The user then chooses the metal and, if desired, the interacting ion from pull-down menus. A title can be entered and the temperature is chosen. A second page appears if the user has chosen an ion with multiple pK values that fall between the hydrogen ion activities of 100 and 1016 (pH = 2 and pH = 16). The reason is that when one or more pK values exist, the form of the interacting ion depends on the pH. That form is assumed to change abruptly between acid-base pairs at a system pH equal to the pK of the acid-base reaction. In reality the boundaries are not sharp but the error decreases exponentially the farther the actual hydrogen ion activity is from the boundary. Two diagrams are created. The first shows the form of the metal itself that has the lowest free energy as a function of hydrogen ion activity and potential. The second shows the form of the metal ion in solution that has the lowest free energy as a function of hydrogen ion activity and potential. These two diagrams are calculated individually and noted as the Metal State Diagram for the lowest free energy form of the metal and the Solution State Diagram for the lowest free energy state of the ion in solution that would be associated at the same pH and potential with the lowest free energy state species related to the metal. If a dissolved species appears in the metal state diagram, that same species also appears at the same position in the solution state diagram. If the species

in the metal state diagram is a solid, then the species in the solution state diagram is the dissolved species with the lowest free energy associated with that solid. The two diagrams are not in equilibrium with each other even though these diagrams have traditionally been drawn as a single diagram with one overlaying the other. In fact, the only place where true equilibrium exists on each diagram is along the lines bordering the regions. The positions of those lines change with concentration, temperature, etc. Within the boundaries the form shown is the species with the lowest free energy state at that hydrogen ion activity, potential, and temperature. The user is given the option of changing the species considered, the temperature, and the title, and recalculating the diagrams. The diagrams can be printed and saved.

THERMODYNAMIC DATA
The overall logic flow for generating consistent thermodynamic data (free energies, entropies, and heat capacities) for the metal and metal-inorganic adducts is shown in Figure 2. Free energies and entropies of solid oxides, solid hydroxides, and one cation per valence were obtained from tabulations.13-14 Tabulated hydrolysis constants were used to obtain the free energies and, where possible, entropies of any dissolved hydroxides that could form.15 Measured equilibrium constants were used as a secondary check. Adducts of metal-inorganic ions were obtained from tabulations and again, where possible, checked against measured stability constants.16 The overall logic flow for generating consistent thermodynamic data (free energies, entropies, and heat capacities) for the metal-organic adducts is shown in Figure 3. Although some aqueous thermo-

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of the ionic forms of the organic molecules.20 Finally, measured stability constants were used to estimate the properties of the metal-organic ion adducts. As mentioned previously, the assumption was made in the Web application that the acidity constant value equals the pH at which one form of the ion transforms to another. In reality, the two forms coexist beyond the line pH = pK, but the activity of the more acidic form would decrease quickly as the pH would increase. Unless otherwise mentioned, the activities of all metal-containing ions in the diagrams were 106.
FIguRe 2. Estimating thermodynamic properties of inorganic species.

SYSTEMS CONSIDERED SteelTartaric Acid

Tartaric acid exists in both the L form and the D form as shown below. These are mirror images of each other.

FIguRe 3. Estimating thermodynamic properties of organic adducts.

dynamic information has been reported for organic ions,17 the data are fairly limited and do not tend to include molecules of interest to corrosion practitioners. The fact that thermodynamics is path-independent was used to start from an initial state in which properties were known or could be estimated. A path was created that had intermediate states for which free energies could be estimated. Group contributions were combined with measured stability constants to establish the thermodynamic properties in each state with the final state being that of the ion in solution. In theory, this method could be applied across a broad range of organic molecules. The major shortcoming is the possible error caused by a lack of information on all groups contributing to form a molecule. Some groups are well established, some are not, so the error must be judged on a case-by-case basis. The organic molecule was formed first in a virtual state in the vapor phase at 1 atm and 298 K using tabulated group contributions.18 The molecule then was dissolved in solution at unit activity, 298 K. Group contributions were used to calculate the free energy and entropy change following this path.19 Measured pK values and entropy changes where possible were used to estimate the thermodynamic properties

Both are di-carboxylates with two additional hydroxides that have an ability to liberate their hydrogens. An adduct of a cation with tartaric acid could form a six-member ring structure through the hydroxyl and carboxylate moieties. In the case of iron, both Fe(II) and Fe(III) have been reported20 to form adducts with tartaric acid in the form of Fe(II)-tartrate, Fe(III)-tartrate+, Fe(III)2-(tartrate[H])2, and Fe(III)2(tartrate[H]2)2. Note that the terminology of (H) 2 means that one of the hydroxyl moieties has given up a hydrogen. A subscript of 2 means that both have given up their hydrogen. These characteristics suggest the possibility that conditions might be found in which tartaric acid (or its salt) could interact with iron. Several years ago, tartaric acid was shown to decrease the corrosion rate of steel in simulated cooling waters under slightly alkaline conditions (pH ~8.5) and slightly elevated temperatures (35C to 50C).21 The concentration was between 10 ppm and 100 ppm. The discussion above suggests that incorporation of tartaric acid in the potential-pH diagram for iron might provide additional insight into experimental conditions that maximize the chance of such interaction and an explanation of the resulting corrosion behavior. The implicit assumption has been made that the thermodynamics of the iron-tartaric acid interaction can be examined independently of the other ions present. Tartrate ion has three pK values across the pH range of 2 (hydrogen ion activity of 100) to 16 (hydrogen ion activity of 1016). At the pH of the experiments, the predominant form of the tartrate ion has a charge

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of 2 with both carboxylates having lost their hydrogen ion. The pK of the acid-base reaction leading to this form at 25C is approximately 4.4. As indicated previously, the assumption was made that as the pH increased above the pK of the acid-base reaction, the form with the lowest free energy state changes from the form with one missing hydrogen ion to that with two. In reality, the transition is smooth with both forms existing on each side of the pH = pK line, but as shown in Figure 4, the concentration of the form missing one hydrogen ion quickly falls to zero as the pH is increased. The software package MINEQL+ (Environmental Research Software, Hallowell, Maine) was used for the calculation. Potential-pH diagrams were generated at 35C using the Web application described above. Figures 5 and 6 are the metal state diagram and solution state diagram for iron in the absence and presence of tartaric acid at 100 ppm by weight in the range of pH corresponding to the doubly ionized tartrate ion. An adduct of tartaric acid and Fe(II) (labeled as FeTAR on the diagram) replaces the region of stability of Fe+2 in some of the region coinciding with the experimental pH of 8.5. Although this diagram was not generated prior to experimentation, the results would imply that attention needs to be paid to the corrosion potential behavior to estimate where in the plot the system resides during the measurements.

FIguRe 4. Form of tartrate ion as a function of pH. Note that within a short distance from pH = pK, the concentration of the less stable species decreases to close to 0.

Figure 4 of reference 20 shows the behavior of the corrosion potential vs. time for this system. As reported, the corrosion potential increased very quickly over about 1.5 h from about 0.35 V vs. saturated calomel electrode (SCE) (~ 0.1 V vs. standard hydrogen electrode [SHE]) to about 0.15 VSCE (~0.1 VSHE) in the presence of tartaric acid but showed little change in its absence. This trajectory means that the system potential moved from in or close to the region of stability of Fe(II)-tartrate through the region of stability of magnetite (Fe3O4) and into the region of stability of goe-

(a)
FIguRe 5. (a) Metal State Diagram and (b) Solution State Diagram for iron without tartrate2 ion.

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3 2

(b)

FIguRe 6. (a) Metal State Diagram and (b) Solution State Diagram for iron with ~10 tartrate ion.

suggest that tartaric acid may initially enhance corrosion (oxidation of iron), enabling faster formation of the passivating oxide because of the increased interactivity of oxidized iron with water or oxygen.

CopperHippuric Acid
Hippuric acid has been reported to inhibit corrosion in both steel and copper.22 This result was found during a mass loss screening of corrosion inhibition properties of what were stated to be some biologically important molecules at a pH of 8, room temperature, and concentration of about 0.02 molal with 100 ppm sodium chloride (NaCl). Hippuric acid was reported to inhibit corrosion of steel with an efficiency of 95% and of copper with an efficiency of 100%. This case demonstrates the knowledge that might have been gained had potential-pH diagrams (and related thermodynamic calculations) been generated prior to running the experiments. Hippuric acid has the structure shown below.

FIguRe 7. Percent of iron as Fe+2, Fe-tartrate adduct, and magnetite as a function of pH. At a pH of 8, ~25% of the iron is present as the adduct.

thite (FeOOH) (not shown) or hematite (Fe2O3) (shown). The fact that the potential increased in the presence and not absence of tartrate would suggest that this molecule facilitated the passivation process. Although Fe(II)-tartrate is not the component with the lowest free energy state at the final pH and potential, as shown in Figure 7, some is present at equilibrium. About 25% of the iron in solution may be associated with tartrate. This ion seems to continue to play a role even at the elevated potential. The experimental results when tied with the thermodynamic predictions

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(a)

(b)

FIguRe 8. (a) Metal State Diagram and (b) Solution State Diagram for copper without sequestrant or inhibitor.

The molecule has one measured acid-base pK at about 3.5 or so. Copper(II) has been reported to form an adduct with hippuric acid of the form Cu(II)-hippurate+ (CuHIP+ in the diagrams discussed below) in which the cupric ion associates with the singly charged hippuric acid. The stability constant is about 2. The pK values for iron, unfortunately, are not available20 so this analysis could not be done for iron. The thermodynamics of this molecule and its anionic acidbase product were estimated using the group contribution technique described above. The free energy of the copper-hippurate adduct was estimated from the tabulated pK20 of the reaction forming the ion. Figures 8 and 9 are the metal state and solution state diagrams for copper with and without hippuric acid across the pH range of stability of the conjugate base HIP. The interacting ion is the singly charged hippurate ion in which the hydrogen on the hydroxyl has been lost. The main difference in the diagrams is that the copper-hippurate adduct (Cu-HIP+) replaces Cu+2 and other hydrolyzed forms of copper as the most thermodynamically stable species in the lower pH portions of the diagram at elevated potential. Figure 9 suggests that from a thermodynamic standpoint at a pH of 8 and depending on the corrosion potential, Cu, cuprous oxide (Cu2O), or cupric oxide (CuO) would be likely candidates for causing passivity. As suggested by Figures 8 and 9, that result is independent of the presence of hippuric acid. Since the original paper reports that hippuric acid has an

effect on corrosion, what additional information might be gleamed from Figures 8 and 9 to aid in designing simple experiments to aid in interpreting this finding? The free energy change for the reaction Cu +2 + HI P Cu-HIP + HIP (1)

is slightly negative (e.g., approximately 500 cal/mol) at the activities of the species. As shown in the theoretical speciation plot in Figure 10, a measurable amount of both cupric ion and the Cu-hippurate adduct are present at equilibrium above about a pH of 3.5. This behavior persists until the pH conducive to the formation of CuO (approximately 8) is reached. Combining the solution state diagram in Figures 8(b) and 9(b) with the equilibrium calculation in Figure 10 provides some insight into a possible reason for the effect and experimental conditions that might be used for confirmation. Figures 8(b) and 9(b) show that the copper-hippurate adduct is the most thermodynamically stable species in the solution phase at a pH of 8 and somewhat elevated potential when hippuric acid is at 0.02 molal. The hydrolyzed cupric ion species are not thermodynamically stable until somewhat higher hydrogen ion activities (lower pH values) are reached. Figures 8(a), 9(a), and 10 suggest that at the pH of 8, the most stable metal state is cupric oxide. If the corrosion potential lies above about 0.2 V vs. standard hydrogen electrode (SHE), the most stable states of copper would be as cupric (or possibly

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(a)

(b)

FIguRe 9. (a) Metal State Diagram and (b) Solution State Diagram for copper with ~0.02 m hippuric acid.

rosion potential was in the region where Cu-HIP+ is stable on the solution state diagram. If it had, hippuric acid might be acting as a corrosion accelerant causing a more rapid formation of a passivating oxide.

Copper1-Hydroxyethylidene-1,1-Diphosphonic Acid (HEDP)

HEDP or etidronic acid has been suggested to be a sequestration agent for copper at a pH of 6. This suggestion was made because of the finding that HEDP could bind copper.23 The suggestion was made that this finding might have application in electroplating and ore extraction. Since electroplating is potential-dependent, the question is if potential-pH diagrams might be used to define possible conditions in which such sequestration results in a thermodynamically stable adduct. If so, maintaining those conditions could aid in sequestration. HEDP has the structure shown below.

FIguRe 10. Percent of copper as Cu+2, Cu-hippurate+ adduct, and cupric oxide as a function of pH. Cupric oxide has been allowed to form in this calculation.

cuprous) oxide in the solid (metal) state and the adduct of cupric ion and hippuric acid (CuHIP+) in the solution state. The fact that the thermodynamic calculations leading to Figure 10 resulted in no cuprous oxide at equilibrium suggests that the corrosion potential lies in the region in which cupric oxide forms. Figures 9(a) and (b) suggest that this situation would most likely occur at potentials in which the adduct forms. Monitoring the corrosion potential at a pH of 8 would have confirmed if the steady-state cor-

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(a)

(b)

FIguRe 11. (a) Metal State Diagram and (b) Solution State Diagram for copper in the presence of HEDP at an activity of 104.

The four hydroxyls associated with the phosphorus atom give HEDP the possibility of four pK values relating five different dissolved species. The HEDP species with the lowest free energy that would interact with copper at a pH of 6 is (H2)HEDP2. This species would be the most stable species in the region between a pH of about 2.53 and 7, the points at which pH = pK for the conjugate acid (lower boundary) or base (upper boundary). To address the question more fully, interaction of (H)HEDP3 was also examined. Its pH range of interaction is between about 7 and 11.1. Several adducts of HEDP and copper are possible across this pH range (CuHEDP2, CuHHEDP, and CuH2HEDP).20 Figures 11(a) and (b) show the metal state diagram and solution state diagram for HEDP across the pH range of 2.53 to 11.1. Note that the interacting form of HEDP is assumed to change abruptly at a pH of about 7, from H2HEDP2 to HHEDP3. This pH is represented in the figures by the vertical dashed line. The activity of HEDP is assumed to be 104 (about 20 ppm by weight). A dissolved adduct of copper and HEDP is predicted to be thermodynamically stable at a somewhat elevated potential across the entire pH range of interest and within the region of stability of water. Figure 12 shows the distribution of copper as a percent of total cupric ion as a function of pH. This figure was derived from the stability constants at the same concentrations as in Figure 11. Figures 11(b) and 12 are consistent. This consistency is a reasonable indicator that the potential-pH diagrams containing the adducts have been calculated with reasonable thermodynamic property estimates.

FIguRe 12. Percent of copper as Cu+2, the various adducts with HEDP and cupric oxide as a function of pH. Cupric oxide has been allowed to form in this calculation.

Figure 12 also indicates that an adduct of copper and HEDP is thermodynamically stable in the region of stability of water (between the two sloping parallel dashed lines). More importantly, the two figures serve as a road map. If formation of the adduct is required for sequestration, those potential values in which it is the most stable state, as indicated on Figures 11(a) and (b), would be the most likely conditions for initial testing.

NickelGlutamic Acid
Potential-pH diagrams can be used to investigate the thermodynamics of the interaction between metals and biologically important amino acids as functions of

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(a)

(b)

observation that aspartic acid changed from being a corrosion accelerator to a corrosion inhibitor as pH increased. The diagrams suggested that the corrosion acceleration was caused by the corrosion potential entering a region of stability of an iron-aspartate adduct in both the metal and solution state diagrams. The inhibition was caused by the corrosion potential entering a region of stability of iron oxide on the metal state diagram. An adduct of iron and aspartic acid was thermodynamically stable in this region in the solution state diagram. Nickel is known to be sequestered by a number of organic acids including amino acids.20 The question is if potential-pH diagrams might shed light on the sequestering of nickel by amino acids. If so, corrosion to a dissolved state might be the most thermodynamically stable state for nickel in the presence of amino acids. As an aside, various amino acids have been discovered to play a role in nickel detoxification and chelation in plants.25 Glutamic acid was chosen as the model amino acid. Glutamic acid has the structure shown below.

FIguRe 13. (a) Metal State Diagram and (b) Solution State Diagram for nickel without glutamic acid over pH range of (H-Glutamic).

(a)

(b)

FIguRe 14. (a) Metal State Diagram and (b) Solution State Diagram for nickel with 0.001 m glutamic acid over pH range of (H-Glutamic).

pH and potential. Periodically, results have appeared in the literature suggesting the amino acid interaction with metals has resulted in corrosion inhibition or acceleration. In one such study, potential-pH diagrams were used to examine the interaction between iron and aspartic acid.24 The goal was to explain the

Glutamic acid has 3 pK values. In the near-neutral pH range, the form with the lowest free energy, is a singly charged anionic glutamic acid with one hydrogen ion written as H-Glutamic. This form would be predominant between the pH values of about 4.3 and 9.9. Nickel is reported to form four adducts 2 with glutamic acid, Ni-glutamic, Ni-(glutamic)2 , Ni+ 4 (glutamic)3 , and Ni-HGlutamic (labeled on the poten2 4 tial-pH plot as NiGLU, Ni (GLU)2 , Ni (GLU)3 , and + NiHGLU ). Figures 13(a) and (b) show the potential-pH diagrams for nickel between pH values of 4.3 and 9.9. Figures 14(a) and (b) show the same diagrams with the nickel and nickel-glutamic acid adducts at activities of 106 and glutamic acid at an activity of 103 (e.g., ~1 millimolar). Figures 15(a) and (b) show the same diagram with glutamic acid adducts at activities of 106, glutamic acid at 103, and nickel ion at 102, similar to the levels reported in the plant study. Figure 16 shows a speciation plot as a function of pH. The adduct between nickel and glutamic acid is the most stable thermodynamic state in the neutral to slightly alkaline pH range in the region of stability of water and under the conditions of the calculation. Comparison of the results shows that formation of the nickel-glutamate adducts is more thermody-

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FIguRe 16. Percent of nickel ion as an adduct with glutamic acid or hydroxides of nickel as a function of pH.

(a)

(b)

FIguRe 15. (a) Metal State Diagram and (b) Solution State Diagram for nickel with 0.001 m glutamic acid and 0.01 m nickel ion over pH range of (H-Glutamic).

namically favorable than formation of nickel oxide or hydroxide between pH values of about 7 and 9.9 and within the region of stability of water even at very low concentrations of the partially protonated H-glutamic. When the nickel ion concentration is increased, a nickel-glutamic acid adduct is more thermodynamically favorable than other forms of nickel within most of the region of stability of water (between the parallel dashed lines) and across the entire pH range of 4.3 to 9.9. A number of other amino acids show similar results. The conclusion is that care might be exercised when exposing pure nickel or non-passivating alloys containing significant amounts of nickel to fluids containing amino acids. Iron is suggested to behave differently when exposed to comparable levels of glutamic acid over this pH range. Figures 17(a) and (b) show the metal state and solution state diagrams for iron. The concentration chosen was comparable to that used in a study26 that showed glutamic acid to be an inhibitor for steel in the pH range above about 9. Only a small region exists in which an Fe(II)glutamate adduct is thermodynamically stable. If glutamic acid acts in a manner similar to aspartic acid, the corrosion potential at a pH above 9 would likely lie in the region of the oxide, not in the region of the adduct.24 Glutamic acid might promote the oxide formation by an initial acceleration of iron corrosion in a manner similar to that proposed for tartaric acid earlier, but that hypothesis would have to be confirmed by experiment.

(a)

(b)

FIguRe 17. (a) Metal State Diagram and (b) Solution State Diagram for iron with 0.005 m glutamic acid over pH range of (H-Glutamic).

CONCLUSIONS
v Potential-pH diagrams can be useful for providing guidance for the experimental evaluation of organic corrosion inhibitors and sequestering agents. The presence of an adduct of the organic agent and the metal on a diagram may indicate an interaction that affects corrosion. v Potential-pH diagrams can be applied to examine the physical chemistry of the interaction of biologically important molecules with metals. v Thermodynamic properties of organic ions may be estimated in a reasonable manner using group contribution methods combined with measured stability constants. v Generating these diagrams using a platform-independent, internet-accessible, Web-based application

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is not only feasible but offers distinct advantages over software that is operating system-dependent.
REFERENCES
1. M. Pourbaix, Atlas of electrochemical equilibria in Aqueous solutions (Houston, TX: NACE International, 1974). 2. E.D. Verink, Corrosion 38, 6 (1982): p. 485. 3. D.C. Silverman, Derivation and Application of EMF-pH Diagrams, in electrochemical Techniques for Corrosion engineering, ed. R. Baboian (Houston, TX: NACE, 1986), p. 117. 4. D.C. Silverman, Corrosion 38, 10 (1982): p. 541. 5. T. Aben, D. Tromans, J. electrochem. soc. 142, 2 (1995): p. 398. 6. D.C. Silverman, Corrosion 50, 2 (1994): p. 138. 7. B. Beverskog, I. Pulgdomenech, Corrosion 55, 11 (1999): p. 1077. 8. B. Skrifvars, in Trends in electrochemistry and Corrosion at the Beginning of the 21st Century (Barcelona, Spain: Les Publicacions de la Universitat de Barcelona, 2004), p. 1137. 9. D.C. Silverman, Corrosion 44 (1988): p. 606. 10. A.L. Silverman, D.C. Silverman, Easily Accessible Intelligent Corrosion Tools on the Internet, CORROSION/2005, paper no. 05060 (Houston, TX: NACE, 2005). 11. World Wide Web Consortium (W3C), http://www.w3.org/. 12. P.B. Linkson, B.E. Phillips, B.E. Rowles, Miner. sci. eng. 11, 2 (1979): p. 65. 13. G.B. Naumov, B.N. Ryzhenko, I.L. Khodakovsky, Handbook of Thermodynamic Data, translated in Report no. USGS-WRD-74001, U.S. Geological Survey, 1974.

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