chapter7oxidation-reductionreactionandelectrochemistry讲解.ppt

（1） 浓度的影响 一般来说，反应物浓度增加, 反应速率增大 （2） 温度的影响 温度每增高10℃, 反应速率增大2-3倍. 例: KMnO4滴定H2C2O4,需加热至70-80℃. 一次电池（Primary Cells / batteries） Cell reaction is not reversible. 二次电池（Secondary Cells） Cell reaction can be reversed by passing electricity through the cell (charging). 燃料电池（Fuel Cells） Materials pass through the battery which converts chemical energy to electric energy. Overpotential. Competing reactions. Non-standard states. Nature of electrodes. The two vertical lines indicate three phases are present. For simplicity we usually assume that a = 1 at [H+] = 1 Mand replace 1 bar by 1 atm. 1 3 (-) Zn，ZnO│KOH│Ag2O，Ag (+) Zn + Ag2O → ZnO + 2 Ag Ecell = 1.8 V The Silver-Zinc Cell: A Button Battery Zn + 2 OH- → ZnO + H2O + 2 e- Ag2O + H2O + 2e- → 2 Ag + 2 OH- Lead-Acid (Storage) Battery The most common secondary battery PbO2 + 4 H+ + SO42- + 2 e- → PbSO4 + 2 H2O Oxidation: Reduction: Pb + SO42- → PbSO4 + 2 e- PbO2 + Pb + 2H2SO4 → 2 PbSO4 + 2 H2O E°cell = ? °PbO2/PbSO4 - ? °PbSO4/Pb = 1.74 V – (-0.28 V) = 2.02 V Cell diagram: (-) Pb│H2SO4 │ PbSO4 (+) PbSO4 + 2 H2O → PbO2 + 4 H+ + SO42- + 2 e- Oxidation: Reduction: PbSO4 + 2 e- → Pb + SO42- 2 PbSO4 + 2 H2O → PbO2 + Pb + 2H2SO4 充电过程 PbO2 + Pb + 2H2SO4 2 PbSO4 + 2 H2O 放电 充电 Cd + 2 NiO(OH) + 2 H2O 2 Ni(OH)2 + Cd(OH)2 Cd + 2 OH- Cd(OH)2 + 2 e- The Nickel-Cadmium Cell (-) Cd │Cd(OH)2 │KOH│Ni(OH)2│NiO(OH) (+) 2 NiO(OH) + 2 H2O + 2e- 2 Ni(OH)2 + 2 OH- O2 + 2 H2O + 4 e- → 4 OH- H2 + 2 OH- → 2 H2O + 2 e- 2H2 + O2 → 2 H2O E°cell = E°O2/OH- - E°H2O/H2 = 0.401 V – (-0.828 V) = 1.229 V Fuel Cells (-) C│ H2│KOH│O2 │ C (+) 4 Al + 3 O2 + 6 H2O + 4 OH- → 4 [Al(OH)4]- Air Batteries Al = Al3+ + 3e- O2 + 2 H2O + 4 e- → 4 OH- O2(g) + 2 H2O(l) + 4 e- → 4 OH-(aq) 2 Fe(s) → 2 Fe2+(aq) + 4 e- 2 Fe(s) + O2(g) + 2 H2O(l) → 2 Fe2+(aq) + 4 OH-(aq) Ecell = 0.841 V ? O2/OH- = 0.401 V ? Fe/Fe2+ = -0.440 V In n