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10.3 Half-reactions and electrodes
Two types of electrochemical cells: 1. Galvanic cell: is an electrochemical cell which produces electricity as a result of the spontaneous reactions occurring inside it. 2. Electrolytic cell: is an electrochemical cell in which a non spontaneous reaction is driven by an external source of current.
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Other important concepts include:
Oxidation: the removal of electrons from a species. Reduction: the addition of electrons to a species. Redox reaction: a reaction in which there is a transfer of electrons from one species to another. Reducing agent: an electron donor in a redox reaction. Oxidizing agent: an electron acceptor in a redox reaction. Two type of electrodes: Anode: the electrode at which oxidation occurs. Cathode: the electrode at which reduction occurs
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Typical Electrodes
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Electrochemical cells
Liquid junction potential: due to the difference in the concentrations of electrolytes. The right-hand side electrochemical cell is often expressed as follows: Zn(s)|ZnSO4(aq)||CuSO4(aq)|Cu(s) The cathode reaction (copper ions being reduced to copper metal) is shown on the right. The double bar (||) represents the salt bridge that separates the two beakers, and the anode reaction is shown on the left: zinc metal is oxidized into zinc ions
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In the above cell, we can trace the movement of charge.
Electrons are produced at the anode as the zinc is oxidized The electrons flow though a wire, which we can use for electrical energy The electrons move to the cathode, where copper ions are reduced. The right side beaker builds up negative charge. Cl- ions flow from the salt bridge into the zinc solution and K+ ions flow into the copper solution to keep charge balanced. To write the half reaction for the above cell, Right-hand electrode: Cu2+(aq) + 2e- → Cu(s) Left-hand electrode: Zn2+(aq) e- → Zn(s) The overall cell reaction can be obtained by subtracting left-hand reaction from the right-hand reaction: Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq)
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Expressing a reaction in terms of half-reactions
Example : Express the formation of H2O from H2 and O2 in acidic solution as the difference of two reduction half-reactions. Redox couple: the reduced and oxidized species in a half-reaction such as Cu2+/Cu, Zn2+/Zn…. Ox + v e- → Red The quotient is defined as: Q = aRed/aOx Example: Write the half-reaction and the reaction quotient for a chlorine gas electrode.
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Varieties of cells
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Notation of an electrochemical cell
Phase boundaries are denoted by a vertical bar. A double vertical line, ||, denotes the interface that the junction potential has been eliminated. Start from the anode.
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Cell Potential Cell potential: the potential difference between two electrodes of a galvanic cell (measured in volts V). Maximum electrical work : we,max = ΔG Electromotive force, E, Relationship between E and ΔrG: ΔrG = -νFE (10.4.1) where ν is the number of electrons that are exchanged during the balanced redox reaction and F is the Faraday constant, F = eNA. At standard concentrations at 25oC, this equation can be written as ΔrGθ = -νFEθ (10.4.2)
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