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Redox Reactions and Electrochemistry 1 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Electrochemical processes are oxidation-reduction reactions in which: • the energy released by a spontaneous reaction is converted to electricity or • electrical energy is used to cause a nonspontaneous reaction to occur 0 0 2Mg (s) + O2 (g) 2Mg O2 + 4e- 2+ 2- 2MgO (s) 2Mg2+ + 4e- Oxidation half-reaction (lose e-) 2O2- Reduction half-reaction (gain e-) 2 Oxidation number The charge the atom would have in a molecule (or an ionic compound) if electrons were completely transferred. 1. Free elements (uncombined state) have an oxidation number of zero. Na, Be, K, Pb, H2, O2, P4 = 0 2. In monatomic ions, the oxidation number is equal to the charge on the ion. Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2 3. The oxidation number of oxygen is usually –2. In H2O2 and O22- it is –1. 3 4. The oxidation number of hydrogen is +1 except when it is bonded to metals in binary compounds. In these cases, its oxidation number is –1. 5. Group IA metals are +1, IIA metals are +2 and fluorine is always –1. 6. The sum of the oxidation numbers of all the atoms in a molecule or ion is equal to the charge on the molecule or ion. HCO3− Identify the oxidation numbers of all the atoms in HCO3− ? O = −2 H = +1 3x(−2) + 1 + ? = −1 C = +4 4 Balancing Redox Equations The oxidation of Fe2+ to Fe3+ by Cr2O72- in acid solution? 1. Write the unbalanced equation for the reaction ion ionic form. Fe2+ + Cr2O72- Fe3+ + Cr3+ 2. Separate the equation into two half-reactions. +2 Oxidation: Reduction: +3 Fe2+ Fe3+ +6 Cr2O72- +3 Cr3+ 3. Balance the atoms other than O and H in each half-reaction. Cr2O72- 2Cr3+ 5 Balancing Redox Equations 4. Add electrons to one side of each half-reaction to balance the charges on the half-reaction. Fe2+ Fe3+ + 1e6e- + Cr2O722Cr3+ 5. For reactions in acid, add H+ to balance electronic charge and H2O to balance O atoms and H atoms 6e- +14H+ + Cr2O722Cr3+ 6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O 6. If necessary, equalize the number of electrons in the two halfreactions by multiplying the half-reactions by appropriate coefficients. 6Fe2+ 6Fe3+ + 6e6 6e- + 14H+ + Cr2O722Cr3+ + 7H2O Balancing Redox Equations 7. Add the two half-reactions together and balance the final equation by inspection. The number of electrons on both sides must cancel. Oxidation: 6Fe2+ Reduction: 6e- + 14H+ + Cr2O72- 6Fe3+ + 6e2Cr3+ + 7H2O 14H+ + Cr2O72- + 6Fe2+ 6Fe3+ + 2Cr3+ + 7H2O 8. Verify that the number of atoms and the charges are balanced. 14x1 – 2 + 6 x 2 = 24 = 6 x 3 + 2 x 3 9. For reactions in basic solutions, add OH- to instead of H+ to balance electronic charges. 10. Balance the reaction in the molecular form. 7 Galvanic Cells anode oxidation cathode reduction spontaneous redox reaction 8 Galvanic Cells The difference in electrical potential between the anode and cathode is called: • cell voltage • electromotive force (emf) • cell potential Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq) [Cu2+] = 1 M and [Zn2+] = 1 M Cell Diagram phase boundary Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s) anode salt bridge cathode 9 Standard Reduction Potentials Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s) Anode (oxidation): Zn (s) Cathode (reduction): 2e- + 2H+ (1 M) Zn (s) + 2H+ (1 M) Zn2+ (1 M) + 2eH2 (1 atm) Zn2+ + H2 (1 atm) 10 Standard Reduction Potentials Standard reduction potential (E°) is the voltage associated with a reduction reaction at an electrode when all solutes are 1 M and all gases are at 1 atm. Reduction Reaction 2e- + 2H+ (1 M) H2 (1 atm) E° = 0 V Standard hydrogen electrode (SHE) 11 Standard Reduction Potentials 0 = 0.76 V Ecell ° ) Standard emf (Ecell ° ° = E° Ecell cathode - Eanode Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s) ° = E ° + - E ° 2+ Ecell H /H 2 Zn /Zn ° 2+ 0.76 V = 0 - EZn /Zn ° 2+ EZn /Zn = -0.76 V Zn2+ (1 M) + 2e- Zn E° = -0.76 V 12 Standard Reduction Potentials ° = 0.34 V Ecell ° ° = E° Ecell E cathode anode ° = E ° 2+ ° Ecell Cu /Cu – EH +/H2 ° 2+ 0.34 = ECu /Cu - 0 ° 2+ ECu /Cu = 0.34 V Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s) Anode (oxidation): H2 (1 atm) Cathode (reduction): 2e- + Cu2+ (1 M) H2 (1 atm) + Cu2+ (1 M) 2H+ (1 M) + 2eCu (s) Cu (s) + 2H+ (1 M) 13 • E° is for the reaction as written • The more positive E° the greater the tendency for the substance to be reduced • The half-cell reactions are reversible • The sign of E° changes when the reaction is reversed • Changing the stoichiometric coefficients of a half-cell reaction does not change the value of E° 14 What is the standard emf of an electrochemical cell made of a Cd electrode in a 1.0 M Cd(NO3)2 solution and a Cr electrode in a 1.0 M Cr(NO3)3 solution? Cd2+ (aq) + 2e- Cd (s) E° = -0.40 V Cr3+ (aq) + 3e- Cr (s) Anode (oxidation): Cd is the stronger oxidizer E° = -0.74 V Cr3+ (1 M) + 3e- x 2 Cr (s) Cathode (reduction): 2e- + Cd2+ (1 M) 2Cr (s) + 3Cd2+ (1 M) Cd will oxidize Cr Cd (s) x3 3Cd (s) + 2Cr3+ (1 M) ° ° = E° Ecell cathode - Eanode ° = -0.40 – (-0.74) Ecell ° = 0.34 V Ecell 15 The electrochemical cell The electrochemical cell Redox reactions can be used to generate electric current Electrode processes Electrode processes The metallic electrode is dipped into a solution containing a salt of the metal. Some atoms of the metal can leave the electrode and form the cation in solution, leaving electrons in the metal. This form a double layer of opposite charges to the electrode surface. The electrochemical potential of the metal and its ion should be the same at the equilibrium. M(s) Mn+(aq) + neThere is the formation of an electric potential proportional at the ion concentration in solution + + + + + + - + + - + - + - + - + - + - + + Electrode potential Nernst law M+(aq) + e- M(s) GM = G°M + RTlnaM GM+ = G°M+ + RTlnaM+ ΔG = G°M + RTlnaM - G°M+ + RTlnaM+ ΔG = ΔG° + RTln(aM/aM+) ΔG = -nFE -nFE = ΔG° + RTln(aM/aM+) E = -ΔG°/nF + RT/nF ln(aM+/aM) E = E° + RT/nF ln aM+ aM = 1 The Nernst equation The potential of an electrode is expressed by the Nernst law: 2.3RT [Ox] E=E + log nF [Re d] Where Ox and Red are oxidized and reduced forms of Red-Ox couple in equilibrium: 0 ! Oxn+ + ne- Red0 R is the universal gas constant, T is the absolute temperature in Kelvins, n is a number of electrons transferred in reaction, F is Faraday constant (~ 96500 C) The electromotive force • It is useful to separate the overall redox reaction in two separated processes: the oxidation and reduction semireaction. • In the electrochemical cell we have two electrodes and we indicate as Cathode the electrode where the reductions occur and Anode the electrode of oxidation processes. • The electromotive force (EMF) of the cell is the electric potential difference among the cathode and anode. The Standard Hydrogen Electrode We cannot know the absolute potential of a single electrode (it is not possible to measure half reaction), so the E° = 0 V was assigned to the semi-reaction 2 H3O+ + 2e- H2 Reference electrodes: Ag/AgCl and SCE Metallic electrodes 3 main groups: • First kind - wire of active metal immersed in solution, contained the ions of this metal (Cu, Zn, Co, Fe, etc) Al, Cu, Sn, inox, brass and Fe electrodes • Second kind – wire of metal covered by precipitate of hardly soluble salt or oxide: M/Mn+ (Ag/AgCl for instance) • Third kind - inert metallic electrodes (Pt, Au, etc) Pt electrode Electrochemical cell Minimum 2 electrodes are required for electrochemical measurements. Dipped in electrolyte solution these electrodes constitute an electrochemical cell. INDICATOR (or WORKING) electrode is an electrode responding to a target analyte REFERENCE electrode has a stable well defined potential value, independent on analyzed solution composition Reference electrodes: Ag/AgCl and SCE Spontaneity of Redox Reactions ΔG = -nFEcell ΔG° = ° -nFEcell n = number of moles of electrons in reaction J F = 96,500 = 96,500 C/mol V • mol ° ΔG° = -RT ln K = -nFEcell ° Ecell (8.314 J/K•mol)(298 K) RT ln K = ln K = nF n (96,500 J/V•mol) ° Ecell = ° Ecell 0.0257 V ln K n 0.0592 V log K = n 29 Spontaneity of Redox Reactions ° ΔG° = -RT ln K = -nFEcell 30 What is the equilibrium constant for the following reaction at 25°C? Fe2+ (aq) + 2Ag (s) Fe (s) + 2Ag+ (aq) ° Ecell 0.0257 V ln K = n Oxidation: 2Ag 2Ag+ + 2e- Reduction: 2e- + Fe2+ Fe n=2 ° 2+ ° E° = EFe – E /Fe Ag +/Ag E° = -0.44 – (0.80) E° = -1.24 V K=e ° Ecell xn 0.0257 V =e -1.24 V x 2 0.0257 V K = 1.23 x 10-42 31 The Effect of Concentration on Cell Emf ΔG = ΔG° + RT ln Q ΔG = -nFE ΔG° = -nFE ° -nFE = -nFE° + RT ln Q Nernst equation E = E° - RT ln Q nF At 298 K E =E° - 0.0257 V ln Q n E =E° - 0.0592 V log Q n 32 Will the following reaction occur spontaneously at 250C if [Fe2+] = 0.60 M and [Cd2+] = 0.010 M? Fe2+ (aq) + Cd (s) Fe (s) + Cd2+ (aq) Oxidation: Cd Cd2+ + 2e- Reduction: 2e- + Fe2+ 2Fe n=2 ° 2+ ° E° = EFe /Fe – ECd 2+/Cd E° = -0.44 – (-0.40) E° = -0.04 V 0.0257 V ln Q n 0.010 0.0257 V ln E = -0.04 V 2 0.60 E = 0.013 E =E° - E>0 Spontaneous 33 Concentration Cells Galvanic cell from two half-cells composed of the same material but differing in ion concentrations. 34 Electrolysis • Electrolysis is the process in which electrical energy is used to cause a nonspontaneous chemical reaction to occur. Houghton Mifflin Company and G. Hall. All rights reserved. 35 Electrolysis • Previously our lectures on electrochemistry were involved with voltaic cells i.e. cells with Ecell > 0 and ΔG < 0 that were spontaneous reactions. • Today we discuss electrochemical cells where Ecell < 0 and ΔG > 0 that are non-spontaneous reactions and require electricity for the reactions to take place. We can take a voltaic cell and reverse the electrodes to make an electrochemical cell. Houghton Mifflin Company and G. Hall. All rights reserved. 36 Voltaic Electrolytic Houghton Mifflin Company and G. Hall. All rights reserved. 37 Houghton Mifflin Company and G. Hall. All rights reserved. 38 Houghton Mifflin Company and G. Hall. All rights reserved. 39 Electrolytic conductors Houghton Mifflin Company and G. Hall. All rights reserved. 42 Fig. 21.18: Car battery, both voltaic and electrochemical cell. Houghton Mifflin Company and G. Hall. All rights reserved. 43 Increase oxidizing power Increase reducing power Houghton Mifflin Company and G. Hall. All rights reserved. 44 A standard electrolytic cell. A power source forces the opposite reaction Houghton Mifflin Company and G. Hall. All rights reserved. 45 Electrolysis Houghton Mifflin Company and G. Hall. All rights reserved. 46 (a) A silver-plated teapot. (b) Schematic of the electroplating of a spoon. Houghton Mifflin Company and G. Hall. All rights reserved. 47 Schematic of the electroplating of a spoon. AgNO3(aq) Houghton Mifflin Company and G. Hall. All rights reserved. 48 The electrolysis of water produces hydrogen gas at the cathode (on the right) and oxygen gas at the anode (on the left). Houghton Mifflin Company and G. Hall. All rights reserved. 49 Electrolysis of water Houghton Mifflin Company and G. Hall. All rights reserved. 50 Electrolysis of water • At the anode (oxidation): • 2H2O(l) + 2e- H2(g) + 2OH-(aq) • • • • • E= -0.42V At the cathode (reduction): O2(g) + 4H+(aq) + 4e- 2H2O(l) E= 0.82V Overall reaction after multiplying anode reaction by 2, 2H2O(l) 2H2(g) + O2(g) Eocell = -0.42 -0.82 = -1.24 V Houghton Mifflin Company and G. Hall. All rights reserved. 51 Electrolysis: Consider the electrolysis of a solution that is 1.00 M in each of CuSO4(aq) and NaCl(aq) • Oxidation possibilities follow: • Cl2(g) + 2e– 2Cl–(aq) E° = +1.358 V • S2O82–(aq) + 2e– 2SO42–(aq) E° = +2.010 V • O2(g) + 4H+(aq) + 4e– 2H2O E° = +1.229 V • Reduction possibilities follow: • Na+(aq) + e– Na(s) • Cu2+(aq) + 2e– Cu(s) • 2H2O + 2e– H2(g) + 2OH–(aq) Houghton Mifflin Company and G. Hall. All rights reserved. E° = –2.713 V E° = +0.337 V E° = -0.428 V 52 Electrolysis • We would choose the production of O2(g) and Cu(s). • But the voltage for producing O2(g) from solution is considerably higher than the standard potential, because of the high activation energy needed to form O2(g). • The voltage for this half cell seems to be closer to –1.5 V in reality. • The result then is the production of Cl2(g) and Cu(s). anode, oxidation: Cl2(g) + 2e– 2Cl–(aq) E° = +1.358 V • cathode, reduction: Cu2+(aq) + 2e– Cu(s) E° = +0.337 V • overall: CuCl2(aq) Cu(s) + Cl2(g) E = –1.021 V • We must apply a voltage of more than +1.021 V to cause this reaction to occur. Houghton Mifflin Company and G. Hall. All rights reserved. 53 Houghton Mifflin Company and G. Hall. All rights reserved. 54 Stoichiometry of electrolysis: Relation between amounts of charge and product • Faraday s law of electrolysis relates to the amount of substance produced at each electrode is directly proportional to the quantity of charge flowing through the cell (half reaction). • Each balanced half-cell shows the relationship between moles of electrons and the product. Houghton Mifflin Company and G. Hall. All rights reserved. 55 Application of Faraday s law • 1. First balance the half-reactions to find number of moles of electrons needed per mole of product. • 2. Use Faraday constant (F = 9.65E4 C/mol e-) to find corresponding charge. • 3. Use the molar mass of substance to find the charge needed for a given mass of product. – 1 ampere = 1 coulomb/second or 1 A = 1 C/s – A x s = C Houghton Mifflin Company and G. Hall. All rights reserved. 56 Stoichiometry of Electrolysis How much chemical change occurs with the flow of a given current for a specified time? • current and time → quantity of charge → • moles of electrons → moles of analyte → • grams of analyte Houghton Mifflin Company and G. Hall. All rights reserved. 57 Fig. 21.20 Houghton Mifflin Company and G. Hall. All rights reserved. 58 Doing work with electricity. Houghton Mifflin Company and G. Hall. All rights reserved. 59 Electrolysis and Mass Changes charge (C) = current (A) x time (s) 1 mol e- = 96,500 C 60 How much Ca will be produced in an electrolytic cell of molten CaCl2 if a current of 0.452 A is passed through the cell for 1.5 hours? Anode: Cathode: 2Cl- (l) Ca2+ (l) + 2eCa2+ (l) + 2Cl- (l) Cl2 (g) + 2eCa (s) Ca (s) + Cl2 (g) 2 mole e- = 1 mole Ca C s 1 mol e- 1 mol Ca mol Ca = 0.452 x 1.5 hr x 3600 x x s hr 96,500 C 2 mol e= 0.0126 mol Ca = 0.50 g Ca 61 Houghton Mifflin Company and G. Hall. All rights reserved. 62 Batteries Dry cell Leclanché cell Anode: Cathode: Zn (s) 2NH4+ (aq) + 2MnO2 (s) + 2e- Zn (s) + 2NH4 (aq) + 2MnO2 (s) Zn2+ (aq) + 2eMn2O3 (s) + 2NH3 (aq) + H2O (l) Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s) 63 Alkaline ba*ery • Electrolyte is a concentrated solu5on of KOH • The anode is inside the ba*ery as a powder paste • MnO2 is pasted with graphite around the Zn anode and contacted with the external steel electrode Alkaline ba*ery • Lower polariza5on • Higher dura5on • Lower self discharge Rechargeable Alkaline Ba*ery • Rechargeable Alkaline Manganese (RAM) cell • The interest is due to the higher A: Alkaline manganese 2 – 3 Ah Nickel / cadmium 0.5 – 1.0 Ah Nickel / metal hydride 1 – 1.5 Ah The number of charge-‐discharge is lower than usual Ni/Cd or Ni/MH cells Button Batteries High energy and stable discharge, ideal for long time operation with low A Mercury Battery (Silver Oxide) Anode: Cathode: Zn(Hg) + 2OH- (aq) HgO (s) + H2O (l) + 2eZn(Hg) + HgO (s) ZnO (s) + H2O (l) + 2eHg (l) + 2OH- (aq) ZnO (s) + Hg (l) 67 Batteries Lead storage battery Anode: Cathode: Pb (s) + SO2-4 (aq) PbSO4 (s) + 2e- PbO2 (s) + 4H+ (aq) + SO24 (aq) + 2e Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO42- (aq) PbSO4 (s) + 2H2O (l) 2PbSO4 (s) + 2H2O (l) 68 Acidic ba*eries • Pb ba*eries have been first reported in 1859 • Electrode reac5ons: Pb + H2SO4 PbSO4 + 2H+ + 2e-‐ ( -‐0.356 V) PbO2 + H2SO4 + 2H+ + 2e-‐ PbSO4 + 2H2O (1.685 V) Total reac5on: Pb + PbO2 + H2SO4 2PbSO4 + 2H2O (2.041 V) Pb ba*eries • Advantages: Low cost Well known Technology Good Ah • Disadvantages: Low energy density Deposi5on of low soluble PbSO4 Ni-‐Cd Cd + 2NiOOH + 4H2O Cd(OH)2 + 2Ni(OH)2.H2O e.f.m. = 1.20 V High number of cycles, reliable, low maintenance Energy density not high Cd is toxic and costly Ni-‐MH • Alterna5ve to Ni-‐Cd cells • Developed ader Ni-‐H2 cells, for military applica5ons • Electrode reac5ons: H2 + 2OH-‐ 2H2O + 2e 2NiOOH + 2H2O + 2e 2Ni(OH)2 + 2OH-‐ e.f.m. = 1.2 – 1.3 V Metallic hydride is used as hydrogen source Li Ba*ery • Lightest metal; • High nega5ve standard poten5al but: • Easy to oxidize • Unstable and not compa5ble with water Li Ba*ery • Need non aqueous solvents • Advantages: • High voltage ( >4V) • Uniform T discharge • Long shelf-‐life • Loss of capacity < 10% • Wide range of working T • Cathode MnO2 Li Ba*ery • Long self discharge (up to 10 years) • Working T around -‐40 °C and 60 °C Batteries Solid State Lithium Battery 76 Li-‐ion Ba*eries Batteries A fuel cell is an electrochemical cell that requires a continuous supply of reactants to keep functioning Anode: Cathode: 2H2 (g) + 4OH- (aq) O2 (g) + 2H2O (l) + 4e2H2 (g) + O2 (g) 4H2O (l) + 4e4OH- (aq) 2H2O (l) 78 History • The fuel cells had been conceived in 1839 by the British scientist Mr. William Grove. • Developed practical applications during years 60 and 70, for NASA. • The American astronauts consumed the water produced for the electric generators of its ships. • These generators had constituted the first operational use of fuel cells. What they are… • Electrochemical cell that converts chemical energy into electric energy; • It can have taxes of conversion in the order of 90%; • Cathode + anode + electrolyte + catalyst; • Ex.: Combustible H2 and oxidant O2 Anode – H2(g) → 2H+(aq) + 2eCathode – 1/2O2(g) + 2H+(aq) + 2e- → H2O(g) • It is important the selection of the electrolyte, and the dimensions of this and the electrodes. and its operating… Types of Fuel Cells • • • • • • Polymer Electrolyte Fuel Cell (PEMFC) Alkaline Fuel Cell (AFC) Phosphoric Acid Fuel Cell (PAFC) Molten Carbonate Fuel Cell (MCFC) Intermediate Temperature Solid Oxide Fuel Cell (ITSOFC) Solid Oxide Fuel Cell (SOFC) PEMFC • Operating Temperature: 50-100ºC • Appropriate for electric vehicles (Automobile Industry) • Anode – Platinum (0.4mg/Pt cm2) H2(g) → 2H+ + 2e- • Cathode – Platinum (0.4 mg/Pt cm2) 1/2O2(g) + 2H+ + 2e- → H2O(aq) • Common electrolyte: - Solid organic polymer poly- perfluorosulfonic acid; - Membrane of Nafion. • System Output: < 1kW - 250kW • Efficiency Electrical: - 53-58% (transportation) - 25-35% (stationary) [1] http://www.cogeneration.net/molten_carbonate_fuel_cells.htm Polymer Electrolyte Fuel Cell (PEMFC) Applications : • Backup power • Portable power • Small distributed generation • Transportation Advantages : • Solid electrolyte reduces corrosion & electrolyte management problems • Low temperature • Quick start-up Disadvantages : • Requires expensive catalysts • High sensitivity to fuel impurities • Low temperature waste heat • Waste heat temperature not suitable for combined heat and power (CHP) AFC • Operating Temperature: 90-100ºC • Anode – Zn H2(g) + 2OH-(aq) → 2H2O + 2e- • Cathode – MnO2 1/2O2(g) + H2O + 2e- → 2OH-(aq) • Common electrolyte: - Aqueous solution of potassium hydroxide soaked in a matrix • System Output: 10kW - 100kW • Efficiency Electrical: 60% [1] http://www.cogeneration.net/molten_carbonate_fuel_cells.htm Alkaline Fuel Cell (AFC) Applications : • • Military Space Advantages : • Cathode reaction faster in alkaline electrolyte, higher performance. Disadvantages : • Expensive removal of CO2 from fuel and air streams required (CO2 degrades the electrolyte). PAFC • Operating Temperature: 150-200ºC • Anode – Platinum (0.1 mg/Pt cm2) H2(g) → 2H+ + 2e- • Cathode – Platinum (0.5 mg/Pt cm2) 1/2O2(g) + 2H+ + 2e- → H2O(aq) • Common electrolyte: - Liquid phosphoric acid soaked in a matrix • System Output: 50kW – 1MW (250kW module typical) • Efficiency Electrical: 32-38% [1] http://www.cogeneration.net/molten_carbonate_fuel_cells.htm Phosphoric Acid Fuel Cell (PAFC) Applications : • Distributed generation Advantages : • Higher overall efficiency with CHP • Increased tolerance to impurities in hydrogen Disadvantages : • Requires expensive platinum catalysts • Low current and power • Large size/weight MCFC • Operating Temperature: 600-700ºC • Anode: Nickel H2(g) + CO32- → H2O(g) + CO2(g) + 2e- • Cathode: Nickel • 1/2O2(g)+CO2(g)+2e-→ CO32- • Common electrolyte: - Carbonate salt • System Output: < 1kW – 1MW (250kW module typical) • Efficiency Electrical: 45-47% [1] http://www.cogeneration.net/molten_carbonate_fuel_cells.htm Molten Carbonate Fuel Cell (MCFC) Applications : • • Electric utility Large distributed generation Advantages : • • • • High efficiency Fuel flexibility Can use a variety of catalysts Suitable for CHP Disadvantages : • High temperature speeds corrosion and breakdown of cell components • Complex electrolyte management • Slow start-up TSOFC • Operating Temperature: 800 -1000ºC • • Anode: Co-ZrO2 or Ni-ZrO2 cermet H2(g) + O2- → H2O(l) + 2e- • • Cathode: Sr-doped LaMnO3 1/2O2(g) + 2e- → O2- • Common electrolyte: - Solid zirconium oxide to which a small amount of Yttria is added • System Output: 5kW – 3MW • Efficiency Electrical: 35-43% [2] http://www.treehugger.com/files/2007/06/biogas-powered_fuel_system.php Solid Oxide Fuel Cell (SOFC) Applications : • • • Auxiliary power Electric utility Large distributed generation Advantages : • High efficiency • Fuel flexibility • Can use a variety of catalysts • Solid electrolyte reduces electrolyte • • Suitable for CHP Hybrid/GT cycle management problems Disadvantages : • High temperature enhances corrosion and breakdown of cell components • Slow start-up • Brittleness of ceramic electrolyte with thermal cycling ITSOFC • Operating Temperature: 600-800ºC • • Anode: Co-ZrO2 or Ni-ZrO2 cermet H2(g) + O2- → H2O(l) + 2e- • • Cathode: Sr-doped LaMnO3 1/2O2(g) + 2e- → O2- • Lower temperatures ⇒ increase the internal resistance of the cell • Common electrolyte: - Solid zirconium oxide to which a small amount of Yttria is added • System Output: 5kW – 3MW • Efficiency Electrical: 35-43% [1] http://www.cogeneration.net/molten_carbonate_fuel_cells.htm Applications Corrosion Corrosion is a spontaneous and irreversible electrochemical process, which results in the degrada5on of a metallic material, upon interac5on with the environment. The corrosion could occur in the presence or in the absence of water: The first one is called wet corrosion, the second dry corrosion As for all the chemical processes, the corrosion depends on both thermodynamic (spontaneous or not process) and kine5c (rate of the process) factors The interac5on with the environment could lead to: 1. The corrosion of the metal (ac5ve condi5on): the process is both thermodynamic and kine5c favored. ΔE > 0 2. The forma5on of a protec5ve film (passive condi5on): the process is favored by thermodynamic but kine5cally inhibited 3. No modifica5on of the metal: : the process is not thermodynamic favored. ΔE < 0 The corrosion is an electrochemical process, where a cathode and an anode are formed The metal is oxidized in the anodic region and leaves the electrons that migrate to the cathodic region, the corrosive region, where molecular oxygen is reduced Anodic process: Me Men+ + ne-‐ Cathodic process: O2 + 2H2O + 4e-‐ 4OH-‐ or O2 + 4H+ + 4e-‐ 2H2O The molecular oxygen is more concentrated at the surface than in the bulk of the droplet, leading to a concentra5on cell. The oxygen reduc5on produces the hydroxide ions that lead to the rust forma5on This effect produces the ring morphology for the metal corrosion The corrosion can be: Generalized: the anodic zone is big, while the cathodic zone is small Localized: is the reverse case of the generalized corrosion. It is the most dangerous Generalized corrosion This corrosion interests all the metallic surface and leads to a reduc5on of the metal thickness Uniform Not uniform Localized corrosion This corrosion interests only small parts of the metal surface and it is the most dangerous because it is impossible to evaluate the gravity of the corrosive a*ack from an external inspec5on. Temporal evolu5on of the corrosion Constant process: ex. Fe in HCl Self-‐cataly5c process: the hydrolysis of iron in the presence of Cl-‐ ion produces protons in the anodic zone that increases the corrosion rate Self-‐inhibi5ng process: the forma5on of carbonate salts in the alkaline region can produce low soluble salts that par5ally protect the metal surface from the oxygen reduc5on Passiva5ng process: the forma5on in the anodic zone of a compact oxide film that protect the metal: ex. Al Galvanic corrosion The corrosion is produced by a junc5on of two metals having different E: the metal with lower E is oxidized. Lower the ra5o of the zone anode/cathode, higher and more penetra5ng the dissolu5on of the less noble metal. Example of corrosion: the brass The brass is an alloy of copper and zinc: the zinc is oxidized and copper forms the characteris5c colored powder Protec5on methods Cathodic protec5on: cathodic current or sacrificial anode Appica5on of films resistant to corrosion: metallic, non-‐metallic, polymers Cathodic Protection of an Iron Storage Tank 107 Protec5on with metallic films Hot deposi5on: immersion or spray coa5ng Galvanic deposi5on: electrochemical deposi5on (problems: not homogeneous thickness) Chemical deposi5on: deposi5on of the film by redox reac5on Protec5on with non-‐metallic films Conver5on layers: the film is formed in situ by forma5on of chemical bond with the metal surface Ex.: chromature Protec5on with organic layers Thick films: gums or polymers Thin films: paints