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22-Mec-B8 Engineering Materials · May 2017

Question 5 of 8: Magnesium sacrificial anode in a hot water heater

Nivaar worked solution (AI-drafted; not reviewed by a licensed engineer)

Notes on this paper

Paper format. National Exams, May 2017 — 16-Mec-B8 Engineering Materials. Three hours, open book; any non-communicating calculator permitted. Eight problems, all of equal value; any FIVE constitute a complete paper, so each problem is worth 20 marks. Candidates are urged to submit a clear statement of any assumptions made. All eight problems are solved below, because the set as a whole is the study resource.

Reference texts (22-Mec-B8 Engineering Materials).

  • Askeland & Wright, The Science and Engineering of Materials, 7th ed. — the primary syllabus text.
  • Callister & Rethwisch, Materials Science and Engineering: An Introduction, 10th ed.
  • Dieter, Mechanical Metallurgy, 3rd ed. — Considère's construction and plastic instability.
  • Shackelford, Introduction to Materials Science for Engineers, 8th ed. — ceramics, glasses and glass-ceramics.
  • Fontana, Corrosion Engineering, 3rd ed. — galvanic series, sacrificial protection and Faraday's law.
  • Ashby, Materials Selection in Mechanical Design, 5th ed. — selection criteria and material indices.
  • Polmear, Light Alloys, 5th ed. — aluminium tempers, Al–Li alloys and maraging steels.

Note on this sitting. Seven of the eight problems restate archetypes seen in 2013–2016 with fresh data, and every calculation below has been re-worked from this paper's numbers. Question 8 is the genuinely new one: the familiar aluminium–lithium substitution has been expanded into a three-alloy selection problem that also asks for the beam volume and for a strength-to-density ranking, and the two halves of it do not pick the same alloy.

Question 5: Magnesium sacrificial anode in a hot water heater (20 marks)

Question text not reproduced: the examination questions are © Engineers and Geoscientists BC. Open the official past paper (linked at the top of this page) to read the question, then follow the worked solution below.

Given. A cathodic-protection anode consumed steadily over its service life:

Given data
QuantitySymbolValue
Mass of magnesium consumedm0.4 kg = 400 g
Service lifet8 years
Electrochemical valencen2
Atomic mass of magnesiumM24.3 amu
Faraday constantF96 485 C/mol

Find. (a) the half-cell reaction occurring at the anode, and (b) the average current the anode has delivered to protect the steel tank over its eight-year life.

steel hot-water tank (CATHODE)Mg rod (ANODE)Mg²⁺electrons through the metalO₂ + 2H₂O + 4e⁻ → 4OH⁻(steel is protected)Mg → Mg²⁺ + 2e⁻0.4 kg consumed in 8 yearsAverage protective current I = nFm / (M t) = 12.59 mA
Sacrificial (galvanic) protection of a steel hot-water tank. The magnesium rod is the anode: it oxidises and releases Mg2+ into the water, driving electrons through the metal to the steel wall, which is thereby forced to be the cathode and cannot itself dissolve.

Approach. Identify the oxidation half-reaction that consumes the magnesium, convert the mass lost into moles and then into charge through Faraday’s law of electrolysis, and divide by the elapsed time to obtain the average current.

  1. Part (a) — write the anode reaction. The anode of a galvanic couple is where oxidation occurs; magnesium is the most active of the common engineering metals and gives up two electrons: $$\boxed{\ \mathrm{Mg} \rightarrow \mathrm{Mg}^{2+} + 2e^{-}\ }$$ with a standard electrode potential of −2.37 V versus the standard hydrogen electrode. That answers part (a), and the valence of 2 quoted by the question is precisely the number of electrons in this equation.
  2. Note the balancing cathodic reactions, which are what the anode is protecting against. The electrons released travel through the metal to the steel tank wall and are consumed there by $$\mathrm{O}_2 + 2\,\mathrm{H}_2\mathrm{O} + 4e^{-} \rightarrow 4\,\mathrm{OH}^{-} \qquad\text{(aerated water)}$$ and, in the deaerated hot water typical of a tank in service, $$2\,\mathrm{H}_2\mathrm{O} + 2e^{-} \rightarrow \mathrm{H}_2 + 2\,\mathrm{OH}^{-}$$ Because the steel is now a cathode receiving electrons, its own dissolution reaction Fe → Fe2+ + 2e− is suppressed. This is the entire principle of sacrificial protection.
  3. Part (b) — convert the mass lost into moles of magnesium. $$n_{Mg} = \frac{m}{M} = \frac{400\ \text{g}}{24.3\ \text{g/mol}} = 16.461\ \text{mol}$$
  4. Convert moles into charge using Faraday’s law. Each mole of magnesium releases two moles of electrons, and each mole of electrons carries one Faraday of charge, so $$Q = n\,n_{Mg}\,F = 2(16.461)(96\,485) = 3.176\times 10^{6}\ \text{C}$$ Equivalently, 32.92 mol of electrons have crossed the metal–water interface over the life of the anode.
  5. Express the service life in seconds. Taking a 365-day year, $$t = 8 \times 365 \times 24 \times 3600 = 2.5229\times 10^{8}\ \text{s}$$
  6. Divide to obtain the average current. $$I = \frac{Q}{t} = \frac{3.176\times 10^{6}}{2.5229\times 10^{8}} = 0.01259\ \text{A}$$ $$\boxed{\ I = 12.6\ \text{mA}\ }$$ Combining the previous steps, the whole calculation is the single expression I = nFm/(Mt), which is Faraday’s law rearranged for current.
  7. Cross-check against the theoretical capacity of magnesium. The charge magnesium can deliver per gram is $$\frac{nF}{M} = \frac{2(96\,485)}{24.3} = 7941\ \text{C/g} = 2.21\ \text{A}\cdot\text{h/g}$$ the standard textbook figure for magnesium anodes. Four hundred grams therefore holds 882 A·h, and spreading that over the 70 080 h of eight years returns 12.6 mA, confirming the answer by an independent route.
Results for the sacrificial anode
QuantitySymbolValue
(a) Anode reaction—Mg → Mg2+ + 2e− (E° = −2.37 V)
Moles of magnesium consumednMg16.46 mol
Total charge passedQ3.176 × 106 C (882 A·h)
Service lifet2.5229 × 108 s
(b) Average corrosion currentI12.6 mA (0.01259 A)
Theoretical capacity of magnesiumnF/M2.21 A·h/g
Average mass loss ratem/t50.0 g/yr (0.137 g/day)

Check: the calculation assumes 100 % current efficiency, that is, that every magnesium atom dissolved delivered its two electrons to the steel. Real magnesium anodes run at only about 50–55 % efficiency because of self-corrosion and hydrogen evolution on the anode itself, so the current genuinely available for protection is nearer 6.5 mA and the figure calculated here is an upper bound. A 365.25-day year would give 12.58 mA instead of 12.59 mA, a difference of less than 0.1 % and immaterial. The current is also assumed steady, whereas in practice it falls as the anode is consumed and its surface area shrinks.