Department of Metallurgical and Materials Engineering

Basic Corrosion: Recurring Questions & Answers
Prof. Garry W. Warren

November 2007

Department of Metallurgical and Materials Engineering

Rationale

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This presentation provides common examples of recurring questions students pose in developing their proficiency in electrochemistry & corrosion. Typically these questions recur every year, year after year. The vast majority of such questions relate to critical basic information covered in the first few weeks, i.e. the foundation upon which the rest of the course depends. Computer software is a practical way to expose students to these questions.

Department of Metallurgical and Materials Engineering

Recurring Questions

Most recurring questions asked fall into one of the following areas:
– – – – – – Terminology (knowing new terms, e.g. cathode vs. anode) Thermodynamics (e.g. using the Nernst equation) Sign conventions (e.g. G = +nFE vs. G = –nFE) Reference electrodes Understanding the significance of the cathodic reaction Understanding “corrosion potentials”

Department of Metallurgical and Materials Engineering What are the critical terms to know?  Electrochemistry (corrosion) is loaded with interrelated terms somewhat unique to the discipline. but are NOT equal. for example: Anode Anodic Active Oxidation Oxidation potential EMF series Electrolytic cell Cathode Cathodic Noble Reduction Reduction potential Galvanic series Galvanic cell    Terms on left & right are related. It is best to clearly define all of these from day one! .

Department of Metallurgical and Materials Engineering Critical Terminology (con’t)    On the first day of class students are provided a handout entitled “Important Corrosion Concepts to Remember” defining most of these terms. . galvanic cells is best covered after some exposure to the EMF series and Nernst equation (also found at the end of this presentation). That handout is available here: http://bama.edu/~gwarren/ The explanation of electrolytic cells vs.ua.

Always include V vs. SCE (only then is choice of reference half cell clear). Eº” Each potential is tied to a half cell reaction. The half cell assigned a voltage of zero is the “reference” half cell.Department of Metallurgical and Materials Engineering What are the most important things to know about the EMF Series?      Emphasize the title “Standard Reduction Potentials. Eº” or “Standard Oxidation Potentials. . SHE or V vs. Electrochemical reactions (corrosion) must involve two half cells: one oxidation and one reduction.

Department of Metallurgical and Materials Engineering Is there a connection between G & V?     The connection between Gibbs energy (G) and potential or voltage (V) is given by either: G = –nFE OR G = +nFE The choice is a convention. . until students have some experience with the EMF series & the Nernst equation. either is correct. Persistent repetition of the text’s choice of –nFE or +nFE is worthwhile for two reasons: – To emphasize that this is the text’s convention – To emphasize the importance of identifying the chosen convention when consulting other texts or references I prefer using G = –nFE.

0 Ni2+ +2e– = Ni – 0.250 Standard Potentials (G = +nFE) Eº (V) Cu2+/Cu + 0.250 Standard Oxidation Potentials (G = –nFE) Eº (V) Cu = Cu2+ +2e– – 0. Sign of Eº does NOT change if reactions are reversed.0. hence the title omits “oxidation” or “reduction” .342 2H+ + 2e– = H2 0. The words “oxidation” or “reduction” with respect to ½ cell potentials also indicates selection of –nFE convention.0 Ni2+/Ni .0 Ni = Ni2+ +2e– + 0.250 Values of Eº in these 2 lists are identical.342 H+/ H2 0. Standard Reduction Potentials (G = –nFE) Eº (V) Cu2+ +2e– = Cu + 0. When you reverse the reactions. change sign of Eº.Department of Metallurgical and Materials Engineering Can I connect a sign convention to EMF Series?   Imagine three EMF series (no others are possible!).342 H2 = 2H+ + 2e– 0.

so only one value is ever observed. For –nFE.342 H+/H2 0. . For +nFE. Standard Reduction Potentials (G = –nFE) Eº (V) Cu2+ +2e– = Cu + 0.0 Ni = Ni2+ +2e– + 0.250 Standard Potentials (G = +nFE) Eº (V) Cu2+/Cu + 0.Department of Metallurgical and Materials Engineering Why doesn’t the sign of Eº change for +nFE?  Imagine three EMF series (no others are possible).342 2H+ + 2e– = H2 0.250 Standard Oxidation Potentials (G = –nFE) Eº (V) Cu = Cu2+ +2e– – 0.0 Ni2+ +2e– = Ni – 0. sign of Eº is the experimentally observed value of selected ½ cell when connected with H+/H2 half cell.0 Ni2+/Ni – 0.342 H2 = 2H+ + 2e– 0.250 Values of Eº in these 2 lists are identical. sign of Eº “+” or “–” is chosen to agree with the thermodynamic tendency.

 Ecorr is available at MaterialsTechnology@TMS: http://materialstechnology.org/educ/educdigital. electrode potentials & electrochemical thermodynamics.asp .Department of Metallurgical and Materials Engineering Ecorr Software  Computer Aided Instruction (CAI) is a practical way to expose students to recurring questions. – Permits students to work outside class at any time – Allows more class time for other topics  Ecorr software – An introduction to corrosion. – Focuses on many recurring corrosion questions via examples and practice problems.tms.

Department of Metallurgical and Materials Engineering What does Ecorr do?    The following screens give a number of examples. – Standard potentials are available in a pull down menu – Menu allows user to navigate to other parts of program – Any screen can be printed. Some previous exposure to thermodynamics is useful The user interacts with the program in various ways: – Answers to questions or calculations are entered by typing in boxes or by clicking buttons – Clicking on red “hot text” opens popup windows with more information on that term. . concept or calculation.

Department of Metallurgical and Materials Engineering Can you use potentials to predict reactions? Below is one of several examples addressing this question for standard conditions. . Potentials are hot text and remind the user how each was obtained.

Activity. .Department of Metallurgical and Materials Engineering What if activities are not unity? First the relation of G to E yields the Nernst equation. activity coefficient and concentration are defined via hot text popup windows.

several examples for overall reactions are given. Standard potentials are obtained first as shown below.Department of Metallurgical and Materials Engineering What if activities are not unity? After applying the Nernst equation to half cells. .

Each box requires user input. and the final answer requires a calculation. There are several other examples similar to the one shown here.Department of Metallurgical and Materials Engineering What if activities are not unity? After obtaining Eº’s the user is led term by term through the Nernst equation to calculate the overall reaction potential. .

g. e. When selected as a reference it is assigned a value of zero volts. . but only some are experimentally convenient. hydrogen or SCE shown below.Department of Metallurgical and Materials Engineering What’s the significance of the reference electrode? In principle any half cell can be selected as a reference.

Department of Metallurgical and Materials Engineering How do I convert a potential vs. . SCE to another reference electrode? Such conversions are simply adjusting the zero point on the potential scale using the Eº value of the current reference electrode on the “new” scale. Two more examples involving different reference electrodes are given.

the oxidation of Fe and the reduction of O2? .Department of Metallurgical and Materials Engineering What’s the difference between a half cell potential and a corrosion potential? The diagram shows that a corrosion potential is a combination of two half cells.

Knowing which one occurs offers different choices for limiting corrosion. Red numbers reveal popup windows that show how the value was calculated. .Department of Metallurgical and Materials Engineering Why is the cathodic reaction important? Several possible cathodic reactions exist.

then selects an answer.Department of Metallurgical and Materials Engineering How can I determine the cathodic reaction? The decision is a thermodynamic one. . Through Nernst eqn calculations the user determines Sum A and Sum B.

the user “measures” the corrosion potential for each metal by clicking & dragging each one into the white box. This shows that Ecorr’s are not single half cells.Department of Metallurgical and Materials Engineering What’s the difference between the Galvanic Series & EMF Series? After giving a definition of each series. .

Department of Metallurgical and Materials Engineering What’s the difference between galvanic corrosion and regular corrosion? The difference is demonstrated with a “movie” that places the reduction half cell on the surface of the more noble metal for galvanic corrosion. .

how is galvanic corrosion minimized? .Department of Metallurgical and Materials Engineering Joining dissimilar metals is often necessary.

Department of Metallurgical and Materials Engineering What’s an example of a poor choice of two dissimilar metals? Shown is one example. for Fe and brass. . User must enter answers to questions in boxes.

Department of Metallurgical and Materials Engineering What’s an example of a poor choice of relative areas? Combining stainless and Al is rarely a good choice. . but if necessary one option is better than the other. The user must click on the appropriate image to answer.

–nFE = non-IUPAC +nFE = IUPAC .Department of Metallurgical and Materials Engineering Sign conventions are really confusing. what are my choices? This section of Ecorr can be omitted if desired. It is probably most useful for advanced study.

ONLY 4 permutations are possible! .Department of Metallurgical and Materials Engineering How many possibilities are there? The user can click on each button. work with the same example for each case and compare them.

practice! Using the buttons on this summary screen the user can review any of the four possible permutations.Department of Metallurgical and Materials Engineering How can I ever remember this? Practice. . practice.

Electrical energy is used to cause the desired chemical reaction. i. car battery (when it is being discharged). nearly every corrosion reaction Examples: electroplating of Cu. Electrolytic Cell Reactions do not occur without applying an external potential such that Eexternal > Ecell. Au. Chemical energy is converted to electrical energy.Department of Metallurgical and Materials Engineering What’s the difference between an electrolytic cell and a galvanic cell? This question is best answered by comparing one with the other.e. car battery (when it is being charged) . Galvanic Cell Reactions occur spontaneously when connected by a conductor or electrolyte. Examples: AA battery. Ag.

= H2 reduction . Never associate the sign of E with “anode” or “cathode.Department of Metallurgical and Materials Engineering Isn’t the anode always negative? Absolutely not! See the two examples below.” What is always true is anode = oxidation & cathode = reduction. Galvanic Cell e- Electrolytic Cell (electrolysis of water) e- + O2 PS H2 - Zn Cu + Zn+2 sol’n ANODE Cu+2 sol’n CATHODE + Pt Pt - ANODE CATHODE Zn = Zn+2+2eoxidation Cu+2+2e.= Cu reduction 2H2O = O2+2H++2eoxidation 2H++2e.

but we can reduce or minimize it. please reply via MaterialsTechnology@TMS .tms.Department of Metallurgical and Materials Engineering Remember    Corrosion is inevitable.asp Contact information: – Comments are welcome.org/educ/educdigital. Only under impractical conditions can it be 100% eliminated. Ecorr program downloads are available through MaterialsTechnology@TMS http://materialstechnology.

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