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Chapter 7 Electrochemistry
§7.9 Electrode potential and electromotive forces H2O O2 H2 pH / V 2 4 6 8 10 12 14 0.401 -0.828 0.000 1.229
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7.9.1. Influential factors for electrode potential
1) emf’s and rGm of a reaction in different forms Exercise: Compare G1, G2, G3 and E1, E2, E3. reaction: H2 + Cu2+ Cu + 2H G1, E1 1/2 H2 + 1/2 Cu2+ 1/2 Cu + H+ G2, E2 Cu + 2H+ H2 + Cu G3, E3
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Initial state and final state
2) between different oxidation states Give the relationship between Fe3+ Fe2+ Fe Initial state and final state Exercise
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3) of relevant electrodes
AgCl = Ag+ + Cl- Ag(s)|AgNO3(c1) ||KCl(c2) |AgCl(s)|Ag(s) Exercise: deduce the relationship between and
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Nernst equation 7.9.2. Concentration-dependence of
for Ag+/Ag electrode (Ag+/Ag) depends on [Ag+] , or (Ag+/Ag) responds to [Ag+]. The relationship between (Ag+/Ag) and [Ag+] can be used for quantitative electroanalysis of Ag+.
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Can we use hydrogen electrode for measuring the pH of the solution?
Give the principle of the measurement. Normal and italic Exercise: why electrode Hg(l)Hg2SO4(s)CaSO4(s)Ca2+(m) can be used to measure the concentration of Ca2+ in a solution?
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7.9.3. pH-dependence of : Pourbaix diagram
For electrode reaction with H+ or OH- participating in, the electrode potential will depend on pH. 2H+ + 2e- H2 H2O O2 H2 pH / V 2 4 6 8 10 12 14 0.401 -0.828 0.000 1.229 = ⊖ lgaH+ = pH O2 + 4H+ + 4e- 2H2O = ⊖ lgaH+ = pH pH-potential diagram/Pourbaix diagram
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Application of Pourbaix diagram
Cu2+ Cu(OH)2 Cu pH / V 2 4 6 8 10 12 14 CuO22 Cu2O
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Pourbaix diagram of iron-water system
Equilibrium line Fe2+ Fe2O3 Fe pH / V 2 4 6 8 10 12 14 Fe3O4 Fe3+ FeO22 Stable zone Stable state Product Reaction Protection, passivation, active dissolution, electroplating, electrosynthesis
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Group discussion -2 How can you measure the liquid-liquid junction potential of a HCl/KCl interface? Write out the notation of the cell you use to conduct your measurement. A potential is usually established across the cell membrane due to the concentration difference of K+ inside and outside a cell, which is named as membrane potential. This potential is crucial for sensation of any living thing. Can you design an experimental apparatus for measuring the membrane potential of a cell? State the principle you use.
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