Electrochemistry Reduction Potentials • General Conclusions: • 1. The more positive the electrode potential, the stronger an oxidizing agent the oxidized form is and the weaker a reducing agent the reduced form is • 2. The more negative the reduction potential, the weaker the oxidizing agent is the oxidized formis and the stronger the reducing agent the reduced form is. Electrochemistry Oxidation/Reduction Reactions • Typical oxidizing agents: Standard Potentials,V – O2 + 4H+ + 4e- 2H2O +1.229 – Ce4+ + e- Ce3+ +1.6 (acid) – MnO4- + 8H+ + 5e- Mn2+ + 4H2O +1.51 • Typical reducing agents: – Zn2+ + 2e- Zno -0.763 – Cr3+ + e- Cr2+ -0.408 – Na+ + e- Nao -2.714 Electrochemistry Oxidation/Reduction Reactions • Net Redox Reactions: Standard Potentials,V • MnO4- Mn2+ • MnO4- + 8H+ + 5e- Mn2+ + 4H2O +1.51 • Sn4+ + 2e- Sn2+ +0.154 • Balanced Net Ionic Reaction: • 2MnO4- + 16H+ + 5Sn2+ 2Mn2+ + 5Sn4+ + 8H2O Electrochemistry Voltaic Cell • The spontaneous (Voltaic) cell reaction is the one that gives a positive cell voltage when subtracting one half- reaction from the other. • Eocell = Eoright – Eoleft = Eocathode – Eoanode =Eo+ - Eo- • Which is the Anode? The Cathode? • Convention: • The anode is the electrode where oxidation occurs the more negative half-reaction potential • The cathode is the electrode where reduction occurs the more positive half-reaction potential • anode solution cathode Electrochemistry Oxidation/Reduction Reactions • Net Redox Reactions: Standard Potentials,V • MnO4- Mn2+ • MnO4- + 8H+ + 5e- Mn2+ + 4H2O +1.51 • Sn4+ + 2e- Sn2+ +0.154 • Balanced Net Ionic Reaction: • 2MnO4- + 16H+ + 5Sn2+ 2Mn2+ + 5Sn4+ + 8H2O • Eocell = Eocat – Eoan = (+1.51 – (+0.154)) = +1.36 V Electrochemistry Nernst Equation • Effects of Concentrations on Potentials: • aOx + ne- bRed • E = Eo – (2.3026RT/nF) log([Red]b/[Ox]a – Where E is the reduction at specific conc., – Eo is standard reduction potential, n is number of electrons involved in the half reaction, – R is the gas constant (8.3143 V coul deg-1mol-1), – T is absolute temperature, – and F is the Faraday constant (96487 coul eq-1). • At 25oC(298.16K) the value of 2.3026RT/F is 0.05916 • Note: Concentrations should be activities Electrochemistry • Calculations: • MnO4- + 8H+ + 5e- Mn2+ + 4H2O Eo = +1.51 V • For [H+] = 1.0M, [MnO4-] = 0.10M, [Mn2+] = 0.010M • E = Eo – 0.05916/5 (log ([Mn2+]/[MnO4-][H+]8) • E = +1.51 – 0.1183(-1) = +1.63 V vs NHE • Note: This is more positive than Eo • Greater tendency to be reduced compared to standard conditions. Electrochemistry • Calculations: • Silver electrode/silver chloride deposit/0.010M NaCl • AgCl + 1e- Ago + Cl- E=? • Ag+ + 1e- Ago Eo = +0.799 V • AgCl Ag+ + Cl- Ksp= 1.8 x 10-10 • AgCl + e- Ago + Cl- • E = Eo - (0.05916/1) Log (1/[Ag+]) • [Ag+] = Ksp/[Cl-] = 1.8 x 10-10/(0.010) = 1.8 x 10-8 • E = +0.799 – (0.05916)(7.74) = +0.341 V