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Corrosion: The Galvanic Series

1.0 Learning Objectives
After successfully completing this laboratory workshop, including the assigned reading, the lab blue sheets, the lab quizzes, and any required reports, the student will be able to:

Define oxidation and reduction reactions. Define electromotive potential. Calculate the EMF generated by a Galvanic cell. Make a standard electrode to measure electrochemical potentials. Use the standard electrode to develop the galvanic series for a variety of alloys in salt water at room temperature.

2.0 Resources
Callister, Materials Science and Engineering: An Introduction, Chapter 18.1-18.10 Links to Electrochemistry & Corrosion sites: http://www.steelynx.net/corrosion.html More Corrosion Links: http://www.geocities.com/materialsworldweb/Corrosion.html

3.0 Materials Applications

Corrosion is a phenomenon familiar to all students. All have seen instances of metals and alloys reacting when moistened to form various color corrosion products. The most commonly observed corrosion product is rust of iron and steel items. Check that potato peeler in the drawer at home this evening and see if you don't spot at least a little rust! It has been estimated that from 80 to 210 billion dollars are lost annually in the U.S. due to corrosion. In your engineering career, no matter which technological sector you enter, you will undoubtedly encounter corrosion related issues. While corrosion is thought of as a negative attribute, the principle behind corrosion is the same as that used in electroplating of a metal. In electroplating, metal is removed from a target (corroded) and deposited in the desired location. The reaction is controlled using applied voltages, targets, and transporting solutions that are carefully chosen using the Galvanic series.

4.0 Theory of Corrosion

The purpose of this experiment is to develop an understanding of electrochemical potential and galvanic corrosion. In the lab, you will determine the relative `electron-giving' potential of different commercial alloys when placed in salt water. The information will be used to rank the alloys in a galvanic series. From the ranking, you will be able to predict the tendency for corrosion to occur

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when, for example, two alloys in the series are coupled galvanically; and, you will be able to predict which alloy in the couple will corrode. Galvanic corrosion occurs when one metal (or alloy) is electrically coupled to another in some electrolyte. Two or more metals placed in sea water, for example, and electrically isolated will not experience galvanic corrosion, regardless of the proximity of the metals or their difference in electrochemical potential. Electrical contact between the two electrodes is required. During galvanic coupling, corrosion of the less corrosion- resistant metal (the one with the more negative potential) increases over what it would be if the two electrodes were not coupled. This `active' metal becomes the anode in the couple. Corrosion of the more corrosion-resistant metal (the more positive potential) decreases over what it would be if uncoupled. This metal becomes the cathode in the couple. The difference in potential between dissimilar metals, in contact and placed in an electrolyte, causes electrons to flow. The direction of electron flow is from the more active metal, the anode, to the more noble metal, the cathode. At the anode, metal ions go into solution and electrons are `freed'. At the cathode, hydrogen (typically) is produced by the consumption of electrons. Reduction reactions occur at the cathode.

4.1 The Galvanic Series

It is possible to construct a list of metals and alloys based on their relative corrosion potential in a given electrolyte. Such a list is useful for predicting potential galvanic corrosion situations. The separation between two metals in the galvanic series gives an indication of the magnitude of the driving force for corrosion. In general, the greater the distance between metals and alloys in the series, the greater the tendency for galvanic corrosion to occur. The electrochemical potential of a metal or alloy is affected by environmental factors. Corrosion product films and other changes in surface composition can occur in some environments. This requires a galvanic series to be measured in each environment of interest. Most commonly, however, the galvanic series has been constructed from measurements in seawater, and at ambient temperature. In our experiment, we will determine the galvanic series in salt water. Because most engineering materials are alloys, the measurement of galvanic corrosion employing the actual material is much more useful than predicting current flow from a similar ranking of pure elements (pure Fe instead of steel, for example). A ranking of pure elements under carefully controlled laboratory conditions is also available. It is called the electromotive force (emf) series. The emf series is a list of half-cell potentials and these potentials are proportional to the thermodynamic free-energy changes of the respective elements for standard state conditions. The Galvanic Series should not be confused with the emf series.
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The Electromotive potential series for various alloys is shown in Figure 1. This is not to be confused with the Galvanic Series (Figure 1A). Note that the measured potentials of this series are referenced to something termed the SCE (see top of Figure 1). SCE stands for the Standard Calomel Electrode. The standard electrode is explained next.
Element / Other Gold Platinum Silver Copper Copper Hydrogen (acid) Iron Lead Tin Iron Chromium Titanium Aluminum Magnesium Sodium Calcium Potassium Lithium Calcium Reaction Au+ + e- = Au Pt2+ + 2 e- = Pt Ag+ + e- = Ag Cu+ + e- = Cu Cu2+ + 2 e- = Cu 2 H+ + 2 e- = H2 Fe3+ + 3 e- = Fe Pb2+ + 2 e- = Pb Sn2+ + 2 e- = Sn Fe2+ + 2 e- = Fe Cr2+ + 2 e- = Cr Ti2+ + 2 e- = Ti Al3+ + 3 e- = Al Mg+ + e- = Mg Na+ + e- = Na Ca2+ + 2 e- = Ca K+ + e- = K Li3+ + e- = Li Ca+ + e- = Ca Electrode (V) Potential (assumptions) 1.692 1.18 0.7996 0.521 0.3419 0 -0.037 -0.1262 -0.1375 -0.447 -0.913 -1.63 -1.662 -2.7 -2.71 -2.868 -2.931 -3.0401 -3.8

Figure 1. The Electromotive Potential Series. From Efund.com: http://www.efunda.com/materials/corrosion/electrochem_list.cfm?sort=com

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Figure 1A. Galvanic Series for Metals in Flowing Seawater. (source: http://www.corrosionsource.com/handbook/galv_series.htm)

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4.2 The Standard Electrode

To measure the voltage of one electrode, another `reference' electrode is needed. The voltage of the reference electrode must remain constant in making all other measurements. The standard electrode provides a reproducible half-cell potential that is constant over a broad range of conditions. There are a number of standard electrodes; the SCE mentioned earlier being one of the most common. In the SCE, a Copper/Copper Sulphate standard electrode is used (depicted in Figure 2). If placed in seawater along with some metal electrode as shown in Figures 3 and 4, the galvanic potential of the second electrode can be measured.

Figure 2. Diagram of a Copper/ Copper Sulphate Electrode.

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Figure 3. Schematic of experiment to compare copper/ copper sulphate electrode.

Figure 4. Schematic to conduct experiment.

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5.0 Determining the Galvanic Series

Now, precisely how are the potentials of the galvanic series measured? If the common' or ground lead of a high impedance (~1012 Ohm) multimeter is connected to the standard (or reference) electrode and the plus lead of the meter to the second electrode, a potential difference will be read (see Figure 4). This potential difference, or voltage, is the measure of electrochemical potential of the second electrode and it is this value that is used to create the galvanic series. The galvanic series is a list of corrosion potentials, each referenced to a common, standard electrode.

5.1 Equipment and Materials

Standard Calomel Electrode (SCE) Copper Sulphate Electrical Connectors Multimeters Glass Tubes 3.5% Salt Solution Copper Wire Electrical Clips Beakers Corks

The following metals and alloys will be included in the galvanic series: Magnesium Gold Platinum Copper And others as well Aluminum Silver Cr/Mo Steel Eutectic Solder 1018 Steel Graphite Brass Stainless Steel

5.2 Procedure
5. 2. a. Making a Standard Electrode
Do the following to make a copper/copper sulphate electrode, as shown in Fig. 2:

1. Take one of the Cu/CuSO4 electrodes provided by your instructor. Pour some CuSO4
crystals into the solution. Copper sulfate crystals at the bottom of the tube, on the surface of the cork, are desirable, as this indicates saturation of the solution. If the solution is not saturated, the reference potential will drift. 2. Close the electrode. The copper wire must immerse well into the solution in the tube 3. It is essential that the lower cork be moist to complete electrical contact when the reference electrode is immersed in the salt water to make galvanic measurements. Keep the cork moist by storing the reference electrode in dilute salt water solution.

5.2.b Reference Electrode Calibration

4. Pour a 3.5% salt solution into the 600 ml beaker to half-full. 5. Place the copper/copper sulphate electrode in the salt solution. 6. Place a standard Calomel electrode (SCE) in the beaker as well.

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7. Connect the copper/copper sulphate electrode to the positive terminal of the multimeter; and the SCE to the negative terminal. 8. Read the voltage difference and record the value. A value of about +0.058 volts indicates that all is well.

5.2.c Measuring Galvanic Potentials

9. Using the Cu/CuSO4 electrode, make galvanic potential measurements as illustrated in Figure 4. Connect the standard electrode to the negative (or ground) terminal of the multimeter; and the alloy of interest to the positive terminal. Do not fully immerse the metal electrode: you do not want the galvanic couple of the metal and its copper lead to be exposed to the electrolyte. 10. Immerse and then connect each of the metal specimens to the positive terminal, one at a time. You may soak the prepared specimens in a second container of salt water to achieve stabilization prior to test. Take the first reading that you obtain from the multimeter. 11. Make a table of metals and voltage readings and compare to the galvanic series of Fig. 2.

6.0 Report
Your written report should include the following sections: 1. Title Page 2. Abstract 3. Introduction - Explain what the Galvanic series is and how it relates to corrosion. 4. Procedure - Explain what you did in your own words. Include sketches. Be very careful not to plagiarize these lab notes! 5. Data Analysis and Results Show the measured value for the reference electrode and your table for the measured Galvanic potentials. 6. Discussion of results Determine whether the results of your data are appropriate, i.e. whether the values make sense. Compare the results with measured Galvanic series. 7. Summary/ conclusions- Summarize what you did and your results. Comment on the importance/ relevance of the experiment. 8. References

See the grading criteria on the next page.

7.0 Acknowledgements
The contribution of graduate students, O. McWane and R. Taheri, in particular, and of the Mat.E. 220 Fall '92 Corrosion Class is gratefully acknowledged.

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This experiment is based on a suggestion in Corrosion for Students of Science and Engineering by J. Chamberlain and K.R. Trethewey, Longman Scientific & Technical, New York (1988).

Grading Guidelines for Laboratory Report Corrosion: The Galvanic Series

(May be modified during the semester)

Student Name Score Writing Style & Structure

Sentence structure Spelling &Neatness Paragraph structure, logical flow Clarity of writing (Gives ideas directly, does not complicate ideas) Voice (Creativity, Originality) (uses original voice, text not copied from outside source)

(6) Weak Total: /50

(7)

(8)

(9)

(10) Effective

Technical Content & Structure

Abstract [Overall] Introductory (Background) Section [Overall] Explain importance of corrosion Explain Galvanic Series Results [Overall]: Presents results of reference electrode Presents table with Galvanic potentials Tables are properly labeled and referenced in text Discussion [Overall] Makes some attempt to determine whether results are correct or sensible, links results to theory and published values Conclusion References

Total:

/120

Total Report Score = Sum of above/170

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